Full report
Transcription
Full report
October 2009 A review of NT developments as applicable to developing countries Supported by The International Development Research Centre, Canada [Part of project: Capability, Governance and Nanotechnology Developments: a focus on India] Project Report No. 2006ST21:D2 www.teriin.org The Energy and Resources Institute © The Energy and Resources Institute 2009 Study team Manish Anand Malini Balakrishnan (Co-ordinator) Vidya S Batra Piyali Das Secretarial assistance Rajeev Pillai M K Bineesan Suggested format for citation The Energy and Resources Institute (TERI). 2009 A review of NT developments as applicable to developing countries TERI project: Capability, Governance, and Nanotechnology Developments - a focus on India New Delhi: The Energy and Resources Institute. [Project Report No. 2006ST21: D2] [Please do not cite without permission] For more information Dr Malini Balakrishnan TERI Darbari Seth Block IHC Complex, Lodhi Road New Delhi – 110 003 India Tel. 2468 2100 or 2468 2111 E-mail malinib@teri.res.in Fax 2468 2144 or 2468 2145 Web www.teriin.org India +91 • Delhi (0) 11 Table of Contents Executive summary ..............................................................................................................................i Review of nanotechnology developments as applicable to developing countries........................... 4 Nanotechnology developments applicable to environment, energy, agriculture, food and health .............................................................................................................................................. 4 Environment issues in LDCs..................................................................................................... 4 Energy issues in LDCs ................................................................................................................7 Advances in energy and environmental applications of nanomaterials ....................................10 Environmental applications .........................................................................................................12 Adsorbents ................................................................................................................................12 Catalysts ....................................................................................................................................14 Membranes ...............................................................................................................................19 Others....................................................................................................................................... 23 Energy applications...................................................................................................................... 26 Adsorbents ............................................................................................................................... 26 Catalysts ....................................................................................................................................27 Membranes .............................................................................................................................. 29 Solar Photovoltaic applications .............................................................................................. 30 Others....................................................................................................................................... 34 Summary ...................................................................................................................................... 36 Advances in agriculture, food and health applications of nanomaterials ..................................... 39 Agriculture and food processing ................................................................................................. 39 Packaging ..................................................................................................................................41 Sensors ..................................................................................................................................... 48 Delivery systems ...................................................................................................................... 50 Processing ................................................................................................................................. 51 Agriculture ................................................................................................................................ 51 Nanomaterials from plants / food sources............................................................................. 52 Health applications .......................................................................................................................53 Drug delivery ............................................................................................................................55 Diagnostics............................................................................................................................... 59 Regenerative medicine ............................................................................................................ 62 Summary ...................................................................................................................................... 64 A N N E X U R E I List of Commercial Nanomaterials producers........................................................ 65 ANNEXURE II Nanotechnology based consumer items in the food sector .................................. 78 T E R I Report 2006ST21:D2 List of figures and tables Figure 1 Water supply and sanitation coverage in LDCs................................................................ 6 Figure 2 Per capita world energy consumption .............................................................................. 8 Figure 3 NT applications in food (adapted from Weiss et al. 2006) ............................................41 Table 1 : International NT developments and applications over the last 5 years ....................... 36 T E R I Report 2006ST21:D2 Executive summary Nanotechnology (NT) is an enabling technology that can help address key needs relating to energy, environment, health and agriculture in less developed countries (LDCs). This report reviews international NT developments on the advances in nanomaterials to those applications of relevance to environment, energy, agriculture, food, and healthwith a view to draw out key lessons and issues of relevance for countries in the developing world to acquire capabilities in NT. Nano materials have been categorized on the basis of their function (adsorbents, catalysts, membranes, others) so that a variety of nano materials with multiple applications could be covered. Among the developing countries, the key environmental issues are water & sanitation, land degradation, air pollution, climate change. The energy issues cover energy access, clean & advanced energy system and energy efficiency. International R&D efforts over the past five years applicable to the environmental sector include water purification, pollutants sequestration for improved analysis of microcontaminants, wastewater treatment especially to remove recalcitrant compounds, process improvement in liquid-liquid separation, desalination, better electrode sensors etc. In the energy sector, research will impact hydrogen production and storage, fuel cells, CO2 separation, air enrichment, processes like aromatics cracking in refineries / biorefineries. In energy and environment applications, nanotechnology has provided the following main advantages / capability: Improved capacity (adsorbents for hydrogen storage, electrodes in energy storage batteries / capacitors) and rapid reaction (adsorbents for pollutants removal Higher process efficiency (catalysts / electrodes for photocatalytic / electrochemical degradation, solar cells) Lower cost (lower noble metal catalyst requirements, replacement of costly precious metal catalysts, replacement of costly silicon solar cells) Customized properties (functionalized adsorbents, antifouling membranes, specific sensor materials, lower thermal conductivity in thermoelectric materials) T E R I Report 2006ST21:D2 ii A review of NT developments as applicable to developing countries Review of developments in nanotechnology applicable to energy and environment suggests the following key lessons for developing countries: • It is observed that the research on NT related to energy and environment applications are driven by the following aspects: o Overcoming limitations of existing technology (e.g. improved selectivity & prevention of side reaction in case of catalysts; higher flux, lower fouling and better selectivity in membrane processes; higher strength with nanopowder reinforcements for a variety of materials) o Improving efficiency of processes (e.g. higher adsorption capability, lower temperature requirements, shorter time for processing) o Reducing size and cost of products (e.g. less precious metal nano catalyst requirement in case of fuel cells, lesser membrane area requirement in filtration) o Opening up new applications and markets (e.g. sensors with higher sensitivity for measuring pollutants, hydrogen storage) • Overall, the research and development scene internationally is very vibrant. The challenges in converting these developments to feasible technologies appear to be: o producing the nanomaterials in large enough volumes, with consistent quality, at acceptable costs o supplying the nanomaterials in a form (such as proper particle size, surface chemistry, dispersion capability, compatibility with various media etc.) that would allow integration into the process o engineering and customizing the nano-based system to local requirements o addressing environmental, health and safety concerns in the use and disposal of nano products. Nanotechnology advances of relevance to agriculture and food processing sector, are targeted at improving food processing and storage (covering smart packaging, delivery systems for nutraceuticals / bioactive compounds, sensors for food quality monitoring), enhancing agricultural productivity and exploiting plants for nanomaterials production. Interestingly, there are T E R I Report No. 2006ST21:D2 iii A review of NT developments as applicable to developing countries several NT applications in the food sector that are already commercial. This trend appears to be driven by the significant market for nutraceuticals / bioactive products that, unlike pharmaceutical products, do not require exhaustive field testing and regulatory approvals. At the same time, there is growing concern on lack of information on the risks associated with nanomaterials in food (e.g. degradation, durability and toxicity of polymer–nanoparticulate systems in packaging, leaching of nanosilver in various food related consumer goods like nanocoated cookware etc.). The use of nanotechnology in health offers many advantages in aspects of drug delivery, diagnostics as well as regeneration. These include enhanced sensitivity, lower dosage requirement, targeted therapeutics, combined therapeutics and diagnostics, reduced side effects etc. Many of the applications are expected to enter the mainstream by 2015 or beyond. Given the high investment required for research and the cost and time required for getting clearances, profitability of the product is important in NT application in the health sector. In this sector as well, the risks involved are not clear with a variety of materials and applications opening up. T E R I Report No.2006ST21:D2 Review of nanotechnology developments as applicable to developing countries Nanotechnology is expected to provide opportunities to developing countries to address many of their developmental needs. Salamanca-Bentello et al., (2003) point out that nanotechnology could address a number of developing country needs. The top 10 such needs are – 1. Energy storage, production and conversion, 2. Agricultural productivity enhancement 3. Water treatment and remediation 4. Disease diagnosis and screening 5. Drug delivery systems 6. Food processing and storage 7. Air pollution and remediation 8. Construction 9. Health monitoring 10. Vector and pest control The focus of this review is to highlight nanotechnology developments as applicable to developing countries with a view to draw out key lessons and issues of relevance for countries in the developing world to acquire capabilities in nanotechnology. Nanotechnology developments applicable to environment, energy, agriculture, food and health Given the potential of nanotechnology applications to address key social needs of developing countries, this report provides a review on the advances in nanomaterials to those applications of relevance to environment, energy, agriculture, food and health. Environment issues in LDCs The environmental problems faced by LDCs cover water, land and air pollution1. Access to safe water and sanitation is the major environmental issue. As per 2004 figures, over 1 billion people globally (1 in 6 persons) are without access to improved water supply and 2.6 billion people are without access to improved 1 Michos-Ederer K (2001) Agenda for the Least Developed Countries Environmental Policy & Law 31 4-5 (http://iospress.metapress.com/content/82bfmgaxu6jk4816/fulltext.pdf) T E R I Report 2006ST21:D2 5 A review of NT developments as applicable to developing countries sanitation (50% of the developing world)2. The water supply and sanitation coverage for the LDCs is shown in Figure 1. 2 http://www.wssinfo.org/en/welcome.html T E R I Report No.2006ST21:D2 6 A review of NT developments as applicable to developing countries Figure 1 Water supply and sanitation coverage in LDCs3 Lack of safe water and adequate sanitation facilities has an adverse impact on health in terms of (a) Waterborne diseases (diarrhea, typhoid, etc) that are transmitted through drinking contaminated water and (b) Water-washed disease (skin and eye infections, for instance) which occur due to lack of water for washing and personal hygiene. There are nearly 4 billion diarrhea cases per year causing around 1.8 million deaths. Apart from microbial contamination, others like arsenic contamination in ground waters in Bangladesh, pollution of ground and surface water by agricultural runoffs including pesticides also impact human health. Contaminated surface water sources also affect inland fisheries, which is a major food 3 http://www.wssinfo.org/en/26_wat_leastDev.html#; http://www.wssinfo.org/en/36_san_leastDev.html T E R I Report No. 2006ST21:D2 7 A review of NT developments as applicable to developing countries source in some parts of the world4. From the perspective of technological intervention in LDCs and developing countries, new approaches to storing, treating and disinfecting water and developing sanitation systems that minimize pathogen release are important5. Land degradation is an ecological problem that has impacts both at the local and global levels6. Land degradation occurs due to one or a combination of factors such as deforestation, inappropriate agricultural practices, overgrazing etc.7 as well as mining. Since LDCs typically have significant rural based populations whose economies depend upon the use of natural resources, land degradation can have a serious impact on livelihood of the people. Also, it can lead to food insecurity and declining ecosystem services. The technological interventions to overcome this problem would involve remediation of degraded land through biological or chemical means, development of alternative materials that reduce or replace the use of minerals etc. Indoor air pollution is the third major environmental concern in LDCs. This arises from the burning of solid fuels, including biomass fuels (wood, dung, agricultural residues) and coal, in open fires or traditional stoves. The adverse health impacts include respiratory diseases, heart diseases and cancer8. In addition, climate change is expected to aggravate some of the existing environmental problems and also pose new threats. For example, in island LDCs, global warming has severe implications both in the short term (coral bleaching) and in the long term (sea-level rise). Energy issues in LDCs There are several common issues that are key in the challenges and concerns relating to energy in LDCs and sections of other developing countries that are characterized by low per capita energy consumption (Figure 2)9. Energy is required for lighting, cooking, transportation, irrigation, telecommunication and industrial activities (agro processing). In LDCs typically, 4 http://www.un.org/specialrep/ohrlls/ohrlls/hr%20statement%2024%20APR%2003%20%20WORLD%20INFORMATION%20TRANSFER.htm 5 http://www.eurekalert.org/pub_releases/2007-03/giot-rad031207.php 6 http://www.gsu.co.za/ 7 http://www.serd.ait.ac.th/slm/background-1.html 8 http://www.mediaglobal.org/article/2007-05-09/indoor-air-pollution-athreat-to-health-in-ldcs 9 http://www.iisd.ca/sd/LDCs/sdvol52num1.html T E R I Report No.2006ST21:D2 8 A review of NT developments as applicable to developing countries household energy use occupies a large share with traditional fuel and biomass being the predominant fuel10. This causes severe indoor air quality damage and is also one of the causes of deaths in LDCs11. The share of traditional fuel use in LDCs is between 70-80%, while in developing countries it is between 20-30%. In cases where LDCs depend on imported energy, the countries are susceptible to international price fluctuations and this can create additional burden on their economies. Figure 2 Per capita world energy consumption12 Energy access is one of the major issues in LDCs and developing countries. Currently, about 1.6 billion people do not have access to electricity13. This is important because energy is required for other aspects of sustainable living such as health, economic growth, environment management and poverty alleviation. It is estimated that of the predicted increase in energy demand, 70% would come from developing countries. The benefit of having energy access also helps in meeting the millennium development goals. The direct and indirect benefits include: Increased productivity and therefore improved income levels, education 10http://www.gfse.at/fileadmin/dam/gfse/gfse7/Plenary2/4_GFSE7_Pres entation_UNDP_Takada.pdf 11http://www.unohrlls.org/UserFiles/File/LDC%20Documents/Turkey/E nergy.pdf 12 http://timeforchange.org/prediction-of-energy-consumption http://hdr.undp.org/en/reports/global/hdr20072008/papers/gaye_amie.pdf 13 T E R I Report No. 2006ST21:D2 9 A review of NT developments as applicable to developing countries Improved irrigation and better food and nutrition availability and access Improved health (refrigeration for vaccines, diagnostic tools, cleaner water, improved indoor air quality) Improved environment (pollution control devices, clean fuel) Thus MDGs 1-7 are linked to energy access. The other important aspect is clean and advanced energy systems for providing energy access. This includes renewable energy as well as better utilization of fossil/renewable fuels (e.g. biomass gasification versus direct burning of biomass). In rural areas, the energy should also be reliable and affordable. The traditional energy sources like oil lamps, wood stoves, and diesel generators can be substituted with renewable off grid electricity (solar, wind), improved cooking (e.g. biomass gasifier), devices run on battery with off grid electricity charging. This should also be combined with local capability for manufacturing / assembling and maintaining renewable based equipment. Promotion of integrated project such as combining water and energy is also important. The third important aspect is energy efficiency. This is critical also from the point of view of environmental aspects such as climate change. Environmental damage also arises from unconstrained use of biomass resources leads to deforestation, desertification. Thus, energy efficiency combined with energy diversification is also important. In summary, developing countries need clean and advanced energy technologies combined with energy efficiency to improve access to energy. Some of the environmental issues are linked to energy issues such as indoor air pollution from traditional fuel use, desertification from unsustainable biomass use etc. The energy and environmental issues are also closely linked with MDGs. At the policy level, it will help to link these with national MDG planning, mobilize investment and build institutional and technical capacity14. In the section that follows, we focus on advances in nanomaterials that may help address some of these concerns. 14 http://www.unohrlls.org/UserFiles/File/LDC%20Documents/ Turkey/Energy.pdf T E R I Report No.2006ST21:D2 10 A review of NT developments as applicable to developing countries Advances in energy and environmental applications of nanomaterials Nanotechnology (NT) is a tool that is expected to achieve a stepchange in processes by reducing resource use, improving resource efficiency and thereby generating less waste. NT has many applications in the energy sector involving both generation side and consumption side15. The applications include more efficient energy recovery / conversion from traditional (crude petroleum, coal) and renewable sources (solar, biomass, fuel cells); improvements in energy transmission (CNT for transmission) and storage (hydrogen storage); energy efficient devices, automotives and buildings. In the environmental sector, nano materials are being used for groundwater and soil remediation, water treatment, and gas cleanup. Analysis of pollutants is facilitated by nano materials as they are suitable for on-line measurement and trace analysis. They also aid in production by lowering material consumption, chemical use and byproducts / waste generation. Nano products in the form of powders, thin films, coatings, and composites are used for these applications16. In this report, the nanomaterials have been classified based on their functions, namely, adsorbents, catalysts and membranes. This has been chosen to enable coverage of the vast variety of materials with multiple applications that are being developed. Adsorbents are materials that have the capacity to accumulate a substance on their surface. Nanoporous and microporous adsorbents are predicted to have a market growth due to stringent environmental legislation. In parallel, specialized nanoporous adsorbents with novel pore structure / surface chemistry are also opening up new applications. This includes products like activated carbon, zeolites, activated alumina, pillared clay etc17. Nano particle adsorbents have the advantage of high capacity, fast rate of adsorption and desorption. Emerging applications for such adsorbents include hydrogen storage and catalyst support18. Catalysts are used for overcoming the activation energy of certain reactions or reducing the temperature of reaction. Nano catalysts as a result of their nano scale have the advantages of greater efficiency and lower operation temperature. NT offers potential to customize catalysts to improve selectivity by controlling active sites, binding sites 15 http://www.electronics.ca/reports/nanotechnology/energy_market.html 16 http://www.cleantechscandinavia.com/Lahti/Speeches/Nanotech%20promising%20cleantech%20applications_Bernd%20Nowack.pdf 17 http://www.chemicalprocessing.com/industrynews/2005/3.html 18 http://www.physorg.com/news5208.html T E R I Report No. 2006ST21:D2 11 A review of NT developments as applicable to developing countries and including flexible openings and cavities. It also has the potential for molecular level control of reaction by using for example molecular switches. It has been reported that the global market is expected to have a growth rate of around 6.3%19. Most of the sales in 2003 were from traditional catalysts such as industrial enzymes, zeolites and transition metals. The sales of transition metal oxides, carbon nano tubes etc. are expected to increase their market share by 2009. The major users were refining/petrochemical, chemicals/pharmaceuticals, food processing, and environmental remediation. Membrane processes, employing both synthetic polymeric and ceramic membranes, are employed for a variety of solid, liquid and gas separation applications. Membranes are semipermeable barriers that allow the selective passage of molecules; the process is classified by membrane pore size and the driving force for the separation (pressure, concentration etc.). The energy and environmental applications of membranes include desalination of seawater / brackish water, water purification, wastewater treatment, hydrogen separation from product streams, air enrichment, carbon dioxide recovery from fossil fuel applications, removal of volatile organic compounds from air etc. In particular, the water sector is a major market. For instance, the global market for membrane bioreactor technology (for secondary treatment of municipal and industrial wastewater) is expected to grow at a compound annual growth rate (CAGR) of 10.5%, increasing in value from $296 million in 2008 to $488 million by 201320. The following sections present a review of recent laboratory scale research on nanomaterials with applications in energy and environment sectors. In parallel with research, commercialisation of nanomaterials is also taking place. To highlight this aspect, a list of commercial nanomaterials producers is provided in Annexure I21. 19 www.the-infoshop.com/study/bc21463_nanocatalysts.html, Accessed on 8 March 2008 20 http://www.wwdmag.com/Global-Market-for-Membrane-BioreactorsWorth-488-Million-by-2013-newsPiece16320, Accessed on 28 August 2008 21 http://www.dmoz.org/Business/Materials/Nanomaterials/, Accessed on 8 September 2008 T E R I Report No.2006ST21:D2 12 A review of NT developments as applicable to developing countries Environmental applications Adsorbents Removal of heavy metal ions and micropollutants from aqueous streams using nanomaterials continues to be extensively researched. The focus is primarily on modifications to improve the removal efficiency and in some cases, the nanoparticle stability. Comprehensive reviews on related topics include nano-adsorbents targeting removal of metal ions from water / wastewater22, advances in functionalization of CNTs for various adsorption and catalytic applications23. Further to the application of nano sized zero-valent iron (ZVI), combinations of metals have been examined. For example, nano-sized bimetallic mixtures (Pd/Fe, Cu/Fe and Pd/Cu) enhanced the reduction of Cr(VI) compared to using ZVI alone24. The improvement was attributed to the reasoning that cementation of a noble metal acts as a reaction catalyst and also protects the metallic surface from inactivation. In addition to its application as an adsorbent, nano-sized ZVI can also be used as an electron donor. This has been verified in the degradation of trichloroethylene in groundwater by the microbial species Dehalococcoides spp. in the presence of nano ZVI25. This is an interesting example integrating nanotechnology and biotechnology for environmental remediation. In another application targeted at in situ subsurface environment remediation, chitosan was used as a stabilizer to prepare ZVIchitosan nanoparticles for Cr(VI) removal by adsorption followed by reduction to Cr(III)26. Due to its high efficiency in chelating the Fe(III) ions, chitosan prevents the precipitation of Fe(III)–Cr(III).The Cr(VI) to Cr(III) reduction follows pseudo first order kinetics and is dependant upon parameters like temperature, iron loading, initial Cr(VI) concentration, pH. Chitosan nanoparticles alone have also been used as adsorbents for dye removal27. 22 Sharma Y C, Srivastava V, Singh V K, Kaul S N, Weng C H (2009) Nanoadsorbents for the removal of metallic pollutants from water and wastewater Environmental technology 30 (6) 583-609 23 Meng, L., Fu, C., Lu, Q. (2009) Advanced technology for functionalization of carbon nanotubes Progress in Natural Science 19 (7) 801-810 24 Rivero-Huguet, M., Marshall, W.D. (2009) Reduction of hexavalent chromium mediated by micro- and nano-sized mixed metallic particles Journal of Hazardous Materials 169 (1) 1081-1087 25 Xiu Z-M., Li T-L., Jin Z-H, Alvarez P. J (2009) Microbial reductive dechlorination of TCE with nano iron serving as electron donor Huan Jing Ke Xue 30 (6) 1791-1796 26 Geng, B., Jin, Z., Li, T., Qi, X. (2009) Kinetics of hexavalent chromium removal from water by chitosan-Fe0 nanoparticles Chemosphere 75 (6) 825-830 27 Chewing W. H., Szeto Y. S., McKay G. (2009) Enhancing the absorption capacities of acid dyes by chitosan nano particles Bioresources Technology 100 1143-1148 T E R I Report No. 2006ST21:D2 13 A review of NT developments as applicable to developing countries To overcome the disadvantages associated with pyrophoric nature of nano-sized ZVI that can cause it to ignite spontaneously, approaches to improve its stability have been investigated. Thus nano-sized air-stable ZVI particles have been prepared by ultrasonication of Fe(CO)5 in edible oil, followed by dispersing the iron nano particles in a carbon matrix and coating with ~ 2.5 nm thick non-crystalline carbon layer28. Dechlorination of tetrachloroethene using these carboncoated nanoparticles displayed considerably higher massnormalized reaction rates as compared to conventional bulk ZVI material. In another work, a nearly superparamagnetic adsorbent was prepared by covalent binding of polyacrylic acid (PAA) on the surface of Fe3O4 nano particles, followed by amino-functionalization29. Rapid and efficient adsorption of Cu(II) and Cr(VI) ions through chelation or ion exchange mechanisms was observed. Amino-modified ordered mesoporous silica (APS-MCM-41) has also been prepared and tested for the adsorption of 2-chlorophenol and 2,4,6trichlorophenol from aqueous solutions30. The high adsorption was attributed to the acid and alkaline interactions among the amino functional groups and chlorophenols. In an effort to improve the colloidal stability of CNTs, surface modification by acid treatment has been done31.The modified CNTs were successfully tested for U(VI) adsorption. A Fe―Al―Ce nanoadsorbent granulated by spraying a polymer latex onto sand in a fluidized bed has been prepared and tested for fluoride removal from drinking water32. The granule characteristics (stability, adsorption capacity) were a function of the coating amount. In the context of arsenic removal from groundwater, analytical methods that are rapid, sensitive and cheap are required for As (III) detection. Electrochemical technique (stripping voltammetry) is an inexpensive method characterized by sensitivity and detection limits comparable to atomic absorption (AA) and inductively coupled plasma (ICP) 28 Tiehm, A., Krasznitzer, S., Koltypin, Y., Gedanken, A. (2009) Chloroethene dehalogenation with ultrasonically produced air-stable nano iron Ultrasonics - Sonochemistry 16 (5) 617-621 29 Huang, S.H., Chen, D.H. (2009) Rapid removal of heavy metal cations and anions from aqueous solutions by an amino-functionalized magnetic nano-adsorbent Journal of Hazardous Materials 163 (1) 174-179 30 Anbia, M., Lashgari, M. (2009) Synthesis of amino-modified ordered mesoporous silica as a new nano sorbent for the removal of chlorophenols from aqueous media Chemical Engineering Journal 150 (2) 555-560 31 Schierz, A., Zanker, H. (2009) Aqueous suspensions of carbon nanotubes: Surface oxidation, colloidal stability and uranium sorption Environmental Pollution 157 (4) 1088-1094 32 Chen, L., Wu, H.X., Wang, T.J., Jin, Y., Zhang, Y., Dou, X.M. (2009) Granulation of Fe―Al―Ce nano-adsorbent for fluoride removal from drinking water by spray coating on sand in a fluidized bed Powder Technology 193 (1) 59-64 T E R I Report No.2006ST21:D2 14 A review of NT developments as applicable to developing countries spectroscopic techniques33. Advances in this field include the development of nanomaterial based sensors such as nano Aumodified electrodes on carbon or CNTs. There are several reports on the use of modified CNTs as an adsorbent coupled with high performance liquid chromatography (HPLC). Amino (NH(2)) groups functionalized CNT was covalently immobilized on a silica stationary phase; this material was employed successfully for the HPLC separation of polychlorinated biphenyl isomers and terpenes34. Multi walled CNTs have been tested for the adsorption of coexisting contaminants viz. 2,4,6trichlorophenol and Cu(II)35. Both as is and oxidized CNTs were tested. The oxidized CNTs, with higher surface area and presence of hydrophilic carboxylic groups, displayed enhanced adsorption of the single components; for the binary system however, the sorption of 2,4,6-trichlorophenol was suppressed due to formation of surface complexes of Cu(II). A sol-gel based CNT-coated solid-phase microextraction fiber with high thermal stability and superior solvent durability was prepared and tested for extraction of both polar (phenols) and non-polar (benzene, toluene etc.) compounds36. The extraction efficiency was observably better than that of commercial polydimethylsiloxane fiber and the fibre offers of possibility of application as a stationary phase in gas chromatography. In addition to CNTs, single-walled carbon nanohorn (SWCNH) has also been demonstrated as rapid, solid phase adsorbent for 4nitrophenol37. Catalysts The catalytic applications largely focus on the degradation of recalcitrant (or hard to degrade) micropollutants in aqueous streams. However, organic components present in municipal wastewater have also been targeted. For instance, electrocatalytic oxidation of organic components was carried out using nano TiO2 and Cu2O electrodes as well as non nano-scale 33 Mays, D.E., Hussam, A.(2009) Voltammetric methods for determination and speciation of inorganic arsenic in the environment-A review Analytica Chimica Acta 646 (1) 6-16 34 André, C . , Gharbi, T., Guillaume, Y-C (2009) A novel stationary phase based on amino derivatized nanotubes for HPLC separations: theoretical and practical aspects Journal of Separation Science 32 (10) 1757-1764 35 Chen, G.C., Shan, X.Q., Wang, Y.S., Wen, B., Pei, Z.G., Xie, Y.N., Liu, T., Pignatello, J.J. (2009) Adsorption of 2,4,6-trichlorophenol by multiwalled carbon nanotubes as affected by Cu(II) Water Research 43 (9) 2409-2418 36 Jiang, R. , Zhu, F., Luan, T., Tong, Y., Liu, H., Ouyang, G., Pawliszyn, J. (2009) Carbon nanotube-coated solid-phase microextraction metal fiber based on sol-gel technique Journal of Chromatography A 1216 (22) 46414647 37 Zhu, S., Niu, W., Li, H., Han, S., Xu, G. (2009) Single-walled carbon nanohorn as new solid-phase extraction adsorbent for determination of 4nitrophenol in water sample Talanta 79 (5) 1441-1445 T E R I Report No. 2006ST21:D2 15 A review of NT developments as applicable to developing countries electrodes (commercial TiO2 and graphite plate)38. COD removal was high with both types of electrodes; however, increase in the dissolved oxygen level (which is an added benefit of the electrocatalytic process), was higher with non nano-scale electrode. Nano TiO2 in the size range 8.8–9.6nm, doped with varying ratios of Ce3+ and Ag+ has been employed for ammonium and nitrite removal39. Through coupled oxidation and reduction both the components are removed together in this photocatalytic process. Compared to the performance with solar light, higher removal is obtained upon exposure to UV irradiation. Disinfection is another application and nanosilver is extensively used for this purpose. Crosslinked chitosan coated Ag-loading nano-SiO2 composite has high bactericidal activity against Escherichia coli and Staphylococcus aureus; this was attributed to the coordinated action of the crosslinked chitosan and the silver loaded nano-SiO240. Selective removal of halogenated organics from wastewater has been done using nano-scale Pd-on-magnetite catalyst (Pd/Fe3O4)41. The catalyst is highly active, magnetically reextractable and can tolerate high organic solvents concentration; however, it is sensitive to the presence of heavy metals (Pb, Hg) and sulphides and thus feeds containing these components need to be pre-treated prior to Pd-catalysed hydrodehalogenation. Catalytic phenol degradation has been conducted using β-MnO2 nanowires, prepared by reacting Mn(NO3)2 and ozone in a hydrothermal process42. These nanowires could also be readily separated from aqueous phase; thus the application of this 1D nanostructure in water treatment is promising. Catalytic oxidation of benzyl alcohol has been reported using H2O2 as oxidant and zinc hexacyanoferrate nanocube as catalyst43. Copper oxide nanoparticles with hydrogen peroxide oxidant resulted in rapid, almost complete 38 Chang, J.H., Yang, T.J., Tung, C.H. (2009) Performance of nano- and nonnano-catalytic electrodes for decontaminating municipal wastewater Journal of Hazardous Materials 163 (1) 152-157 39 Liu, L.F., Zhang, Y., Yang, F.L., Chen, G., Yu, J.C. (2009) Simultaneous photocatalytic removal of ammonium and nitrite in water using Ce3+-Ag+ modified TiO2 Separation and Purification Technology 67 (2) 244-248 40 Mei, N., Xuguang, L., Jinming, D., Husheng, J., Liqiao, W., Bingshe, X. (2009) Antibacterial activity of chitosan coated Ag-loaded nano-SiO2 composites Carbohydrate Polymers 78 (1) 54-59 41 Hildebrand, H., Mackenzie, K., Kopinke, F.D. (2009) Pd/Fe3O4 nanocatalysts for selective dehalogenation in wastewater treatment processesInfluence of water constituents Applied Catalysis B, Environmental 91 (1) 389-396 42 Dong, Y., Yang, H., He, K., Song, S., Zhang, A. (2009) β-MnO2 nanowires: A novel ozonation catalyst for water treatment Applied Catalysis B, Environmental 85 (3) 155-161 43 Ali, S.R., Bansal, V.K., Khan, A.A., Jain, S.K., Ansari, M.A. (2009) Growth of zinc hexacyanoferrate nanocubes and their potential as heterogeneous catalyst for solvent-free oxidation of.benzyl alcohol Journal of Molecular Catalysis. A Chemical 303 (1) 60-64 T E R I Report No.2006ST21:D2 16 A review of NT developments as applicable to developing countries degradation of the organic compounds alachlor and phenanthrene44. The degradation was affected by parameters like oxidant concentration and ionic strength but was unaffected over a wide pH range. Electrooxidation of methanol has been conducted using a composite Pt–CeO2/C catalyst; the catalyst itself was prepared in a simple and energy efficient one –step microwave assisted process45. For this application, binary and ternary composite catalysts of Pd, multiwalled CNTs and Ni have also been examined; the best results were obtained with Pd–1% MWCNT–1% Ni combination46. Carbon nanofibers impregnated with Pt, Pd and Ru catalysts were used for catalytic wet-air oxidation of a phenol containing aqueous solution in a continuous-flow trickle-bed reactor47. The results were inconsistent, with the oxidation of the carbon nanofibers support occurring under the conditions of this study (180–240 °C and 10.0 bar of oxygen partial pressure). The Pd impregnated nanofibre was however promising for the thermal decarboxylation of formic acid in an inert atmosphere. TiO2 masked Fe3O4 comprising nano-sized particles of both the compounds was investigated for the catalytic oxidation of 1,2dichloro benzene and thermal incineration of catalystembedded polymers48. Catalytic activity for CO oxidation was enhanced and was attributed to the presence of Fe3O4+δ that was formed during the coating process; further, incorporation of the TiO2 masked Fe3O4 particles improved the thermal stability of the polyethylene and polystyrene polymers during high temperature fabrication. A variety of catalysts have been investigated for oxidation of CO, some of which are described here. A hybrid Pt/TiO2/multi wall CNT nanomaterial was developed and tested for CO oxidation; here the CNTs act as support for the anatase TiO2 nanoparticles 44 Ben-Moshe, T., Dror, I., Berkowitz, B. (2009) Oxidation of organic pollutants in aqueous solutions by nanosized copper oxide catalysts Applied Catalysis B, Environmental 85 (3) 207-211 45 Zhao, J., Chen, W., Zheng, Y. (2009) Effect of ceria on carbon supported platinum catalysts for methanol electrooxidation Materials Chemistry & Physics 113 (2) 591-595 46 Singh, R.N., Singh, A., Anindita (2009) Electrocatalytic activity of binary and ternary composite films of Pd, MWCNT and Ni, Part II: Methanol electrooxidation in 1M KOH International Journal of Hydrogen Energy 34 (4) 2052-2057 47 Taboada, C.D., Batista, J., Pintar, A., Levec, J. (2009) Preparation, characterization and catalytic properties of carbon nanofiber-supported Pt, Pd, Ru monometallic particles in aqueous-phase reactions (2009) Applied Catalysis B, Environmental 89 (3) 375-382 48 Choi, J.S., Youn, H.K., Kwak, B.H., Wang, Q., Yang, K.S., Chung, J.S. (2009) Preparation and characterization of TiO2-masked Fe3O4 nano particles for enhancing catalytic combustion of 1,2-dichlorobenzene and incineration of polymer wastes Applied Catalysis B, Environmental 91(1) 210-216 T E R I Report No. 2006ST21:D2 17 A review of NT developments as applicable to developing countries incorporated with well dispersed Pt nanoparticles49. Almost complete CO to CO2 conversion is reported between 30°C to 100°C which is a significant improvement over the Pt/TiO2 catalyst wherein complete conversion occurs at nearly 150°C. CO oxidation has also been attempted with CNT-supported Cu catalysts synthesized by impregnation and the polyol process; the impregnation method resulted in a product with relatively lower activation energy . Yet another study employed nonalloyed Pt and Ru electrocatalysts prepared by the polygonal barrel-sputtering method for CO oxidation50. Gold nanoparticles deposited on iron oxide–hydroxide support that was prepared from waste iron ore tailings was capable of around 55% conversion; the catalyst was inactivated at300°C in the presence of oxygen51. Photocatalytic oxidation has also been employed on other gases. For example, acetaldehyde has been oxidized using TiO2 nano-particles, with and without mechanical blending with high-silica mordenite zeolite; the blended TiO2 displayed enhanced reactivity52. Photocatalytic degradation with visible light has been reported for microcystin-LR which is a selective inhibitor of protein phosphatase and is classified as a chemical hazard in drinking water. The N-F-TiO2 nanoparticle catalyst was prepared for this purpose by by sol–gel method using a non-ionic fluorosurfactant (Zonyl FS-300) as pore template and fluorine dopant and ethylenediamine as nitrogen source53. The highest degradation was obtained under acidic conditions; further the performance to superior to that obtained by doping with N or F alone. TiO2-nano silver composite photocatalyst has been prepared by acidic peptization of amorphous TiO2 followed by 60Co γ-ray irradiation; this has been tested for the photocatalytic degradation of methylene blue dye54. 49 Lin, K.N., Liou, W.J., Yang, T.Y., Lin, H.M., Lin, C.K., Chien, S.H., Chen, W.C., Wu, S.H. (2009) Synthesis of hybrid Pt/TiO2 (anatase)/MWCNTs nanomaterials by a combined sol-gel and polyol process Diamond & Related Materials 18 (2) 312-315 50 Inoue, M., Nishimura, T, Akamaru, S., Taguchi, A., Umeda, M., Abe, T.(2009) CO oxidation on non-alloyed Pt and Ru electrocatalysts prepared by the polygonal barrel-sputtering method Electrochimica Acta 54 (21) 4764-4771 51 Sakthivel, R., Das, B., Satpati, B., Mishra, B.K. (2009) Gold supported iron oxide-hydroxide derived from iron ore tailings for CO oxidation Applied Surface Science 255 (13) 6577-6581 52 Takeuchi, M., Deguchi, J., Hidaka, M., Sakai, S., Woo, K., Choi, P.P., Park, J.K., Anpo, M. (2009) Enhancement of the photocatalytic reactivity of TiO2 nano-particles by a simple mechanical blending with hydrophobic mordenite (MOR) zeolite Applied Catalysis B, Environmental 89 (3) 406410 53 Pelaez, M., de la Cruz, A.A., Stathatos, E., Falaras, P., Dionysiou, D.D. (2009) Visible light-activated N-F-codoped TiO2 nanoparticles for the photocatalytic degradation of microcystin-LR in water Catalysis Today 144 (1) 19-25 54 Wang, J., Zhao, H., Liu, X., Li, X., Xu, P., Han, X. (2009) Formation of Ag nanoparticles on water-soluble anatase TiO2 clusters and the activation of photocatalysis Catalysis Communications 10 (7) 1052-1056 T E R I Report No.2006ST21:D2 18 A review of NT developments as applicable to developing countries Photodegradation of methyl orange has been examined using holmium-doped TiO2 nanoparticles; the observed enhancement in photocatalytic activity was ascribed to the synergy created by large surface area, small crystallite size, lattice distortion and higher charge imbalance of holmium-doped TiO255 . Methyl orange degradation has also been investigated using a TiO2/NaHZSM-5 zeolite nano-composite photocatalyst; the reversible adsorption of the dye by the medium strong acid sites on the nano-zeolitic support was considered to be responsible for the enhanced degradation56. Degradation of rhodamine B has been studied with single crystalline anatase TiO2 nanorods synthesized in a nonaqueous medium at low temperature57 as well as with Ag@TiO2 and NiAg@TiO2 nanoparticles58. In both instances, the photocatalytic activity was superior to that obtained with TiO2 nanoparticles. TiO2 immobilized on granular activated carbons has been used for methyl orange degradation; in this work the composite photocatalyst was prepared by a novel dip-hydrothermal method using peroxotitanate as precursor59. The catalyst properties were affected by the activated carbon porosity and there was a synergy between activated carbon adsorption and TiO2 photocatalysis. In another study, a stable crosslinked chitosan/nano-CdS composite catalyst was prepared and used for the photocatalytic degradation of an azo dye (Congo Red) under visible light irradiation60. Decolorization was more effective under acidic conditions; also, it was affected by the presence of anions like NO3 and Cl-. Advanced oxidation process can be an attractive option for water treatment especially when coupled with sunlight for OH radical generation61. In this context various nano catalysts have been developed and tested. Photocatalytic disinfection of 55 Shi, J. W., Zheng, J.T., Wu, P. (2009) Preparation, characterization and photocatalytic activities of holmium-doped titanium dioxide nanoparticles Journal of Hazardous Materials 161 (1) 416-422 56 Guo, P., Wang, X., Guo, H. (2009) TiO2/Na-HZSM-5 nano-composite photocatalyst: Reversible adsorption by acid sites promotes photocatalytic decomposition Applied Catalysis B, Environmental 90 (3) 677-687 57 Jia, H., Zheng, Z., Zhao, H., Zhang, L., Zou, Z. (2009) Nonaqueous solgel synthesis and growth mechanism of single crystalline TiO2 nanorods with high photocatalytic activity Materials Research Bulletin 44 (6) 13121316 58 Chuang H-Y / Chen D-H (2009) Fabrication and photocatalytic activities in visible and UV light regions of Ag@TiO2 and NiAg@TiO2 nanoparticles Nanotechnology 20 (10) 105704 59 Wang, X., Liu, Y., Hu, Z., Chen, Y., Liu, W., Zhao, G. (2009) Degradation of methyl orange by composite photocatalysts nano-TiO2 immobilized on activated carbons of different porosities Journal of Hazardous Materials 169 (1) 1061-1067 60 Zhu, H., Jiang, R., Xiao, L., Chang, Y., Guan, Y., Li, X., Zeng, G. (2009) Photocatalytic decolorization and degradation of Congo Red on innovative crosslinked chitosan/nano-CdS composite Journal of Hazardous Materials 169 (1) 933-940 61 Malato, S., Fernandez-Ibanez, P., Maldonado, M.I., Blanco, J., Gernjak, W. (2009) Decontamination and disinfection of water by solar photocatalysis: Recent overview and trends Catalysis Today 147 (1) 1-59 T E R I Report No. 2006ST21:D2 19 A review of NT developments as applicable to developing countries potable water has been carried out using immobilised nanoparticle TiO2 films62. The presence of nitrate and sulphate, and to a greater extent, humic acid, reportedly had a negative impact on the disinfection rate. In another study, nano-TiO2, titania–silica aerogel and nanotextured TiO2 film were examined for photocatalytic oxidation of trichloroethylene combined with inactivation of Bacillus subtilis and Escherichia coli63. The aerogel and film displayed excellent bactericidal activity; it was concluded that nanoscale chemical and structural environment influences bactericidal activity. CNTs and their arrays can be directly employed as high contact surface catalyst support s. For example, an aligned nanotube array of controlled thickness has been prepared for this purpose by catalytic chemical vapour deposition of ferrocene and toluene mixture64. The same array could also be used as a removable precursor template in the preparation of β-SiC ceramic nanoporous membranes. It is now realized that the quality of CNTs viz. presence of metal or carbonaceous impurities, homogeneity, structural integrity etc. is an important aspect in catalytic applications since impurities or defects can radically alter the catalytic activity65. Membranes In an effort to address the water availability and quality issues, membrane technology is being used extensively for water / wastewater treatment including desalination. NT applications in this field continue to focus on improved / novel membrane materials. In addition to membranes, NT based filtration media are also being developed and tested. Nylon 6 based ultra-fine nonwovens produced by electrospinning can be used as HEPA and ULPA grade filter media66. Nanofibre based enhanced filtration media for air filtration is commercially available67. 62 Alrousan, D.M.A., Dunlop, P.S.M., McMurray, T.A., Byrne, J.A. (2009) Photocatalytic inactivation of E. coli in surface water using immobilised nanoparticle TiO2 films Water Research 43 (1) 47-54 63 Yeung, K.L., Leung, W.K., Yao, N., Cao, S. (2009) Reactivity and antimicrobial properties of nanostructured titanium dioxide Catalysis Today 143 (3) 218-224 64 Janowska, I., Hajiesmaili, S., Begin, D., Keller, V., Keller, N., Ledoux, M.J., Pham-Huu, C. (2009) Macronized aligned carbon nanotubes for use as catalyst support and ceramic nanoporous membrane template Catalysis Today 145 (1) 76-84 65 Tessonnier, J.P., Rosenthal, D., Hansen, T.W., Hess, C., Schuster, M.E., Blume, R., Girgsdies, F., Pfänder N., Timpe O., Su D.S.,, Schlögl R. (2009) Analysis of the structure and chemical properties of some commercial carbon nanostructures Carbon 47 (7) 1779-1798 66 Zhang, S., Shim, W.S., Kim, J. (2009) Design of ultra-fine nonwovens via electrospinning of Nylon 6: Spinning parameters and filtration efficiency Materials and Design 30 (9) 3659-3666 67 Wertz, J., Schneiders, I. (2009) Filtration media: Advantages of nanofibre coating technology Filtration and Separation 46 (4) 18-20 T E R I Report No.2006ST21:D2 20 A review of NT developments as applicable to developing countries Multi wall CNTs can be used to enhance the tensile strength, water flux and / or control the pore size of polymer porous membranes. This has been demonstrated in porous chitosan membranes incorporating multi wall CNTs, prepared using low and high molecular weight porogens68. A hollow cylindrical nanofilter with micrometer length multi wall CNTs was prepared, characterized and successfully tested for removal of MS2 viruses69. Nanosilver decorated porous ceramic composites have been developed and employed in drinking water treatment application, especially for reducing the coliform load70. Membranes have also been used as adsorbents e.g. porous polymethyl methacrylate /Na+–montmorillonite cationexchange membranes synthesized by entrapment method were tested for adsorption of the dye methyl violet71. Both adsorption and desorption were significantly high (> 85%) and the membrane could be regenerated over three consecutive cycles. In nanoporous membrane filtration applications, membrane fouling i.e. deposition of the rejected components on the membrane surface / within the pores, is a major limitation. As a result of fouling there is a drop in flux (flow rate per unit membrane area). This necessitates chemical cleaning for flux restoration. Repeated chemical cleaning is undesirable due to the corresponding process downtime; further, it reduces the membrane life span. Thus development of low fouling / antifouling membrane materials by conventional methods continues to be an important area of research72, 73. There are further instances of incorporation of nanomaterials for imparting antifouling properties. For example, PVDF (poly vinyledene di fluoride) ultrafiltration membrane modified by nano-sized alumina displayed lower fouling with various DOC 68 Tang, C., Zhang, Q., Wang, K., Fu, Q., Zhang, C. (2009) Water transport behavior of chitosan porous membranes containing multi-walled carbon nanotubes (MWNTs) Journal of Membrane Science 337 (1) 240-247 69 Mostafavi, S.T., Mehrnia, M.R., Rashidi, A.M. (2009) Preparation of nanofilter from carbon nanotubes for application in virus removal from water Desalination 238 (1) 271-280 70 Lv, Y., Liu, H., Wang, Z., Liu, S., Hao, L., Sang, Y., Liu, D., Wang J., Boughton, R.I. (2009) Silver nanoparticle-decorated porous ceramic composite for water treatment Journal of Membrane Science 331 (1) 50-56 71 Lin, R.Y., Chen, B.S., Chen, G.L., Wu, J.Y., Chiu, H.C., Suen, S.Y. (2009) Preparation of porous PMMA/Na+-montmorillonite cation-exchange membranes for cationic dye adsorption Journal of Membrane Science 326 (1) 117-129 72 Rahimpour, A., Madaeni, S.S. , Jahanshahi, M., Mansourpanah, Y., Mortazavian, N. (2009) Development of high performance nano-porous polyethersulfone ultrafiltration membranes with hydrophilic surface and superior antifouling properties Applied Surface Science 255 (22) 91669173 73 Rahimpour, A. / Madaeni, S.S. / Shockravi, A. / Ghorbani, S. (2009) Preparation and characterization of hydrophile nano-porous polyethersulfone membranes using synthesized poly(sulfoxide-amide) as additive in the casting solution Journal of Membrane Science 334 (1) 6473 T E R I Report No. 2006ST21:D2 21 A review of NT developments as applicable to developing countries (dissolved organic carbon) fractions present in raw water74. Tubular nanocomposite Al2O3–PVDF membranes were used for oily wastewater ultrafiltration; the presence of nano-sized alumina particles imparted antifouling properties with complete flux recovery upon chemical cleaning75. It is interesting to note that industrial alliances are taking place along similar lines viz. between Pentair Inc (a water treatment and storage specialist) with Nano Terra Inc (with expertise in surface engineering and nanotechnology)76. In another work, reduced protein adsorption (and consequently lower fouling) was reported with ultrafiltration membranes based on blends of polysulfone and functionalized multi-walled CNTs containing isocyanate and isophthaloyl chloride groups77. The membranes were prepared by the conventional phase inversion method and the CNT content influenced the membrane properties like water flux, surface hydrophilicity, pore size and structure. Nanocomposite membranes are increasingly being investigated for pervaporation and gas separation applications as well. Separation of water- ethanol mixture was accomplished using PDMS (polydimethylsiloxane) membranes containing polyphosphazene nanotubes78. The permeate flux and separation factor increased with decreasing nanotube diameter; also the separation was superior to that obtained with PDMS membrane. Matrimid® membranes incorporating sub-nano size β-cyclodextrin (β-CD) exhibit enhanced separation in isopropanol dehydration; this is attributed to the unique hydrophilic exterior and interior cavity structure of the β-CD molecules and creation of additional interface channels due to its interaction with the polymer matrix79. Hybrid polyvinylchloride-clay membranes have been synthesized and used for the pervaporation separation of aromatic-alkane (toluene–n–Heptane) mixtures80. Depending upon the clay 74 Ji-xiang Y., Wen-xin, S., Shui-li, Y., Yan, L. (2009) Influence of DOC on fouling of a PVDF ultrafiltration membrane modified by nano-sized alumina Desalination 239 (1) 29-37 75 Yan, L., Hong, S., Li, M.L., Li, Y.S. (2009) Application of the Al2O3– PVDF nanocomposite tubular ultrafiltration (UF) membrane for oily wastewater treatment and its antifouling research Separation and Purification Technology 66 (2) 347-352 76 http://www.filtsep.com/view/991/pentair-inc-and-nano-terra-incannounce-strategic-alliance/ accessed on 15 October 2009 77 Qiu, S., Wu, L., Pan, X., Zhang, L., Chen, H., Gao, C. (2009) Preparation and properties of functionalized carbon nanotube/PSF blend ultrafiltration membranes Journal of Membrane Science 342 (1) 165-172 78 Huang, Y., Zhang, P., Fu, J., Zhou, Y., Huang, X., Tang, X. (2009) Pervaporation of ethanol aqueous solution by polydimethylsiloxane/polyphosphazene nanotube nanocomposite membranes Journal of Membrane Science 339 (1) 85-92 79 Jiang, L.Y., Chung, T.S. (2009) β-Cyclodextrin containing Matrimid(R) sub-nanocomposite membranes for pervaporation application Journal of Membrane Science 327 (1) 216-225 80 Aouinti, L., Roizard, D., Hu, G.H., Thomas, F., Belbachir, M. (2009) Investigation of pervaporation hybrid polyvinylchloride membranes for T E R I Report No.2006ST21:D2 22 A review of NT developments as applicable to developing countries properties, the membrane could be customized to act either as a barrier material or as an enhanced flux toluene selective membrane. Membrane crosslinking which is done to improve the physical and chemical stability typically has the unwanted effect of decreasing membrane permeability; this can be overcome by nanoparticles incorporation. For example in the case of poly(4methyl-2-pentyne) crosslinked using 4,4′(hexafluoroisopropylidene) diphenyl azide (HFBAA) gas permeability was increased by addition of nanoparticles like FS, TiO2; in addition, improved selectivity was reported for separation of various binary gas mixtures (O2/N2, H2/N2, CO2/N2, CO2/CH4 and H2/CH4)81. Permeability of various gases (CO2, CH4 and N2) was tested using polybenzimidazole membranes with embedded silica nano particles prepared by thermal phase inversion method82. An increase in the nano silica content resulted in increase in CO2 and CH4 permeability but that of N2 decreased significantly. A nanoporous Pd membrane with high H2 selectivity was developed by electroless plating on the surface of a porous stainless steel disk modified with WO383. The permeability also did not decrease with time. Nanocomposite membranes with high reverse selectivity in the separation of small hydrocarbon (propane) from a light gas (nitrogen) have been developed by incorporating dendrimers (with high solubility for the heavy component) on mesoporous ceramic scaffold (to maintain high free volume)84. Polyamide nanocomposite membrane containing silica nanoparticles was prepared using porous polysulfone support material for reverse osmosis application85. The average pore radii, depending upon silica content, was between 0.34- 0.73 nm. The presence of nano-silica imparts thermal stability; further, flux and separation efficiency for organic solutes and sodium chloride are improved. the separation of toluene–n-heptane mixtures — case of clays as filler Desalination 241 (1) 174-181 81 Shao, L., Samseth, J., Hagg, M.B. (2009) Crosslinking and stabilization of nanoparticle filled PMP nanocomposite membranes for gas separations Journal of Membrane Science 326 (2) 285-292 82 Sadeghi, M., Semsarzadeh, M.A., Moadel, H. (2009) Enhancement of the gas separation properties of polybenzimidazole (PBI) membrane by incorporation of silica nanoparticles Journal of Membrane Science 331 (1) 21-30 83 Zahedi, M., Afra, B., Dehghani-Mobarake, M., Bahmani, M. (2009) Preparation of a Pd membrane on a WO3 modified Porous Stainless Steel for hydrogen separation Journal of Membrane Science 333 (1) 45-49 84 Yoo, S., Yeu, S., Sherman, R.L., Simanek, E.E., Shantz, D.F., Ford, D.M. (2009) Reverse-selective membranes formed by dendrimers on mesoporous ceramic supports Journal of Membrane Science 334 (1) 16-22 85 Jadav, G.L., Singh, P.S. (2009) Synthesis of novel silica-polyamide nanocomposite membrane with enhanced properties Journal of Membrane Science 328 (1) 257-267 T E R I Report No. 2006ST21:D2 23 A review of NT developments as applicable to developing countries Others In addition to the above, multifunctional nanomaterials have been explored for environmental applications. An example is mesoporous potassium-intercalated layered titanate prepared by reassembly of exfoliated titanate nanosheets and potassium cations86. This material is capable of functioning both as a photocatalyst as well as an adsorbent and was successfully tested for the photodegradation of methylene blue and adsorption of CO2. In another instance, anatase TiO2 nanofibre membrane prepared by electrospinning followed by annealing was reported to display enhanced photocatalytic efficiency (72%), compared to that of anatase TiO2 thin film (44%)87. The improvement was attributed to the large specific surface area of the nanofibre membranes. Combining various functions, a variety of nano based sensors have been reported. Based on enhanced electrochemiluminescence of CdTe quantum dots using CNT modified glass carbon electrode, a highly sensitive method for the determination of methimazole, a drug used for hyperthyroidism, is reported88. TiO2-coated piezoelectric quartz crystal electrode with photodeposited nano-Ag was used to develop a biosensor for detection of E. coli cells; detection levels of up to 8 cells /100 mL could be obtained89. Single-walled CNT aggregates are reported to be a good adsorbent for Bacillus subtilis spores90; thus they can be used for concentrating and removal of pathogens as well as in biosensors for detection of this contaminant. Detection of multiple metal ions viz. Zn (II), Cd (II) and Pb (II) in water samples has been done by a process involving simultaneous preconcentration/reduction of metal ions onto a multiwall CNT electrode followed by chemical stripping91. The results were comparable to that obtained with atomic absorption spectroscopy; this work also demonstrates the use of CNTs in potentiometric stripping analysis. Further, 86 Kim, T.W., Kim, I.Y., Im, J.H., Ha, H.W., Hwang, S.J. (2009) Improved photocatalytic activity and adsorption ability of mesoporous potassiumintercalated layered titanate Journal of Photochemistry & Photobiology, A: Chemistry 205 (2) 173-178 87 Zhang, X., Xu, S., Han, G. (2009) Fabrication and photocatalytic activity of TiO2 nanofiber membrane Materials Letters 63 (21) 1761-1763 88 Hua, L., Han, H., Chen, H. (2009) Enhanced electrochemiluminescence of CdTe quantum dots with carbon nanotube film and its sensing of methimazole Electrochimica Acta 54 (5) 1389-1394 89 Sun, H., Choy, T.S., Zhu, D.R., Yam, W.C., Fung, Y.S. (2009) Nanosilver-modified PQC/DNA biosensor for detecting E. coli in environmental water Biosensors and Bioelectronics 24 (5) 1405-1410 90 Upadhyayula, V.K.K., Deng, S., Smith, G.B., Mitchell, M.C. (2009) Adsorption of Bacillus subtilis on single-walled carbon nanotube aggregates, activated carbon and NanoCeram(TM) Water Research 43 (1) 148-156 91 Tarley, C.R.T., Santos, V.S., Baeta, B.E.L., Pereira, A.C., Kubota, L.T. (2009) Simultaneous determination of zinc, cadmium and lead in environmental water samples by potentiometric stripping analysis using multiwalled carbon nanotube electrode Journal of Hazardous Materials 169 (1) 256-262 T E R I Report No.2006ST21:D2 24 A review of NT developments as applicable to developing countries environment responsive nano materials such as acid functionalised polyaniline nanofibres which are redox active and possess optical switching capability can be employed in adaptive sensing applications92. Metal–CNT hybrids prepared by incorporating transition metals (Ti, Mn, Fe, Co, Ni, Pd or Pt) in single wall CNTs were used as the active sensing layer for ethanol vapor detection at room temperature93. KCl-doped ZnO nanofibers screen-printed on a ceramic substrate with a pair of Ag–Pd interdigitated electrodes have been used for humidity sensing94. Detection of up to 0.05% sulphur dioxide (SO2) gas has been reported using a field effect transistor comprising a network of single walled CNTs with a synthetic receptor95. The receptor for SO2 binding is square-planar NCN-pincer platinum (II) complex (N,C,N_terdentate coordinating monoanionic [C6H3(CH2NMe2)3-2,6]− ligand). Conductive polymer composite transducers based on CNT grafted poly(ε-caprolactone) has been reported for sensing of vapours (water, methanol, toluene, tetrahydrofuran and chloroform)96. A nano-CeO2 based gas sensor has been tested for detection of carbon disulfide (CS2); this is based on chemiluminescence emission when CS2 comes in contact with nano-CeO297. Under optimal conditions, CS2 detection limit of 3.7 ng mL−1 was reported; also the sensor performance was not noticeably affected by contaminants such as alcohol, aldehyde etc. High performance optical chemo-sensors for detection of VOCs (volatile organic compounds) have been developed using cadmium arachidate-single-walled CNT composites placed on optical fibers by the Langmuir–Blodgett deposition technique98. Compared to use of single walled CNT alone, the nano composite coating improved the robustness and the sensitivity of the sensors. 92 Lahiff, E., Woods, T., Blau, W., Wallace, G.G., Diamond, D. (2009) Synthesis and characterisation of controllably functionalised polyaniline nanofibres Synthetic Metals 159 (7) 741-748 93 Brahim S., Colbern S., Gump R., Moser A., Grigorian L (2009) Carbon nanotube-based ethanol sensors Nanotechnology 20 (23) 235502 94 Qi, Q., Zhang, T., Wang, S., Zheng, X. (2009) Humidity sensing properties of KCl-doped ZnO nanofibers with super-rapid response and recovery Sensors & Actuators: B. Chemical 137 (2) 649-655 95 Cid, C.C., Jimenez-Cadena, G., Riu, J. , Maroto, A. , Xavier Rius, F. , Batema, G.D. , van Koten, G. , Selective detection of SO2 at room temperature based on organoplatinum functionalized single-walled carbon nanotube field effect transistors Sensors & Actuators: B. Chemical 141 (1) 97-103 96 Castro, M., Lu, J., Bruzaud, S., Kumar, B., Feller, J.F. (2009) Carbon nanotubes/poly(ε-caprolactone) composite vapour sensors Carbon 47 (8) 1930-1942 97 Xuan, Y., Hu, J., Xu, K., Hou, X., Lv, Y. (2009) Development of sensitive carbon disulfide sensor by using its cataluminescence on nanosized-CeO2 Sensors & Actuators: B. Chemical 136 (1) 218-223 98 Consales, M., Crescitelli, A., Penza, M., Aversa, P., Veneri, P.D., Giordano, M., Cusano, A. (2009) CNT nano-composite optical sensors for VOC and gas trace detection Sensors & Actuators: B. Chemical 138 (1) 351361 T E R I Report No. 2006ST21:D2 25 A review of NT developments as applicable to developing countries Integrated processes employing nanomaterials have also been explored. For example, combined photocatalyticelectrochemical degradation of the commercial dye Basic Blue 26 was conducted using TiO2 nanoparticles immobilized on a glass substrate99. The enhanced degradation compared to that with photocatalysis alone was attributed to the formation of hydroxyl radicals (OH) in the electrochemical system. The process was also studied for the degradation of acid orange 7, an azo dye, using high density uniform arrays of aligned titania nanotubes100. A considerable synergistic effect was observed by combining photocatalysis with electrochemical treatment. For oxygen reduction in acid medium, an electrocatalytic system integrating multi-walled CNTs, cobalt porphyrin and tungsten oxide in the film coated onto the glassy carbon electrode substrate has been developed101. TiO2/multi-walled CNT composites deposited onto indium tin oxide conductive glass plates were used for the electro-photocatalytic degradation of phenol102. The effect of operation parameters like applied potential and pH was examined for this application; best results were obtained with TiO2 doped with 10% CNTs and calcined at 400 ◦C. Electrocatalytic oxidation of H2O2 has also been reported using nano TiO2–Au–KI film on a glassy carbon and indium tin oxide electrode103. Another scheme integrates sonication and catalysis as shown in the sonocatalytic degradation of the dye Acid Red B using nano sized ZnO powder and various inorganic oxidants (KClO4 > KClO3 > Ca(ClO)2)104. 99 Kim, C., Kim, J.T., Kim, K.S., Jeong, S., Kim, H.Y., Han, Y.S. (2009) Immobilization of TiO2 on an ITO substrate to facilitate the photoelectrochemical degradation of an organic dye pollutant Electrochimica Acta 54 (24) 5715-5720 100 Hou, Y., Li, X., Liu, P., Zou, X., Chen, G., Yue, P.L. (2009) Fabrication and photo-electrocatalytic properties of highly oriented titania nanotube arrays with {101} crystal face Separation and Purification Technology 67 (2) 135-140 101 Dembinska, B., Kulesza, P.J. (2009) Multi-walled carbon nanotubesupported tungsten oxide-containing multifunctional hybrid electrocatalytic system for oxygen reduction in acid medium Electrochimica Acta 54 (20) 4682-4687 102 Chen, L.C., Ho, Y.C., Guo, W.S., Huang, C.M., Pan, T.C. (2009) , Enhanced visible light-induced photoelectrocatalytic degradation of phenol by carbon nanotube-doped TiO2 electrodes Electrochimica Acta, 54 (15) 3884-3891 103 Thiagarajan, S., Su, B.W., Chen, S.M. (2009) Nano TiO2-Au-KI film sensor for the electrocatalytic oxidation of hydrogen peroxide Sensors & Actuators: B. Chemical 136 (2) 464-471 104 Wang, J., Jiang, Z., Zhang, Z., Xie, Y., Lv, Y., Li, J., Deng, Y., Zhang, X. (2009) Study on inorganic oxidants assisted sonocatalytic degradation of Acid Red B in presence of nano-sized ZnO powder Separation and Purification Technology 67 (1) 38-43 T E R I Report No.2006ST21:D2 26 A review of NT developments as applicable to developing countries Energy applications Adsorbents Research on carbon nanotube (CNT) related materials for hydrogen storage have focused on modifications for improved storage and ambient temperature storage. To overcome the theoretical limit of hydrogen storage in pure CNT due to weak Van Der Waals forces, coating of aluminium hydride on single wall CNT (SWCNT) has been examined. These showed a hydrogen storage capacity of 8.3 wt% with half coverage105. Similarly, borane covered SWCNT has also been studied and it showed storage capacity of 6.8 wt% for half coverage106. Impregnated CNTs have also been prepared and characterised. Nano TiO2 impregnated CNT showed a five fold increase in hydrogen storage capacity compared to pure CNT at room temperature107. The hydrogen storage capacity in silver modified CNT showed a 40% increase compared to pure CNT108. Other additives such as Pt-Pd109, also showed improvement in hydrogen storage capacity. The hydrogen storage capacity could also be increased by changing the microstructure and crystallinity by heat treatment in ammonia atmosphere110. Novel adsorbent based on porous carbon monoliths from corn grain have been studied for hydrogen adsorption. These were found to have adsorption capacities similar to superactivated carbon111. New ways to synthesize microporous carbon for hydrogen storage has been reported by combining template method and chemical activation. The carbons had surface area of more than 3000 m2/g and good cryogenic hydrogen adsorption112. Molecular dynamics simulation and experimental 105 Iyakutti K, Kawazoe Y, Rajarajeswari M, Surya V J (2009) Aluminum hydride coated single-walled carbon nanotube as a hydrogen storage medium International Journal of Hydrogen Energy 34 (1) 370-375 106 Surya V J, Iyakutti K, Rajarajeswari M, Kawazoe Y (2009) Functionalization of single-walled carbon nanotube with borane for hydrogen storage Physica E: Low-dimensional Systems and Nanostructures 41 (7) 1340-1346 107 Rather S U, Mehraj-ud-din N, Zacharia R, Hwang S W, Kim A R, Nahm K S (2009) Hydrogen storage of nanostructured TiO2-impregnated carbon nanotubes International Journal of Hydrogen Energy 34 (2) 961-966 108 Rather S U, Naik M u d, Hwang S W, Kim A R, Nahm K S (2009) Room temperature hydrogen uptake of carbon nanotubes promoted by silver metal catalyst Journal of Alloys and Compounds 475 (1) L17-L21 109 Hwang S W, Rather S u, Naik M u d, Soo C S, Nahm K S (2009) Hydrogen uptake of multiwalled carbon nanotubes decorated with Pt-Pd alloy using thermal vapour deposition method Journal of Alloys and Compounds 480 (2) L20-L24 110 Lin K Y, Chang J K, Chen C Y. Tsai W T (2009) Effects of heat treatment on materials characteristics and hydrogen storage capability of multi-wall carbon nanotubes Diamond & Related Materials 18 (2) 553-556 111 Balathanigaimani M S, Shim W G, Kim T H, Cho S J, Lee J W, Moon H (2009) Hydrogen storage on highly porous novel corn grain-based carbon monoliths Catalysis Today 146 (1) 234-240 112 Meisner G P, Hu O (2009) High surface area microporous carbon materials for cryogenic hydrogen storage synthesized using new templatebased and activation-based approaches Nanotechnology 20 (20) 2040239 T E R I Report No. 2006ST21:D2 27 A review of NT developments as applicable to developing countries studies on hydrogen storage in nanoporous carbons have shown that narrow pores have higher binding energy than wider pores. Thus storage capacities can be increased by tailoring the pores of the carbon113. By chemical vapour deposition of carbon on Pt impregnated zeolite, Yang et. al., have prepared microporous carbon molecular sieves with Pt dispersion. These sieves showed high surface area and good hydrogen capacity114. Catalysts Nano catalyst based on Ni-La-Fe on gamma alumina was developed for biomass steam gasification. The presence of the catalyst led to increase in hydrogen production and up to 99% efficiency in tar removal115. Magnetic nano alloys based on the system Fe1-xNix have been developed and were found to have high catalytic activity similar to Pt for hydrogen generation from NH3BH3 solution. Such catalysts are expected to be suitable for energy related applications such as fuel cells, batteries, electrochemical sensors116. Nano catalysts have also been used for photocatalytic hydrogen production where they offer optimum light absorption and efficiency117. Many studies have been reported related to fuel cells. Immobilization of Pt on carbon nanospheres has been achieved by functionalization of carbon with triethylenetetramine and coordination of Pt to the polymer chains. These catalysts showed greater activity for methanol oxidation compared to commercial catalysts118. Carbon cloth electrodes of microbial fuel cells showed improved performance on being modified with carbon nanotube119. Another catalyst that has been reported for fuel cell applications is based on the Pt-Sn system prepared using controlled surface reaction. This catalyst was found to be 113 Burress J, Kraus M, Beckner M, Cepel R, Suppes G, Wexler C, Pfeifer P (2009) Hydrogen storage in engineered carbon nanospaces Nanotechnology 20 (20) 204026 114 Yang Y X, Bourgeois L, Zhao C, Zhao D, Chaffee A, Webley P A (2009) Ordered micro-porous carbon molecular sieves containing well-dispersed platinum nanoparticles for hydrogen storage Microporous and Mesoporous Materials 119 (1) 39-46 115 Li J, Xiao B, Yan R, Xu X (2009) Development of a supported trimetallic catalyst and evaluation of the catalytic activity in biomass steam gasification Bioresource Technology 100 (21) 5295-5300 116 Yan J M, Zhang X B, Han S, Shioyama H, Xu Q (2009) Magnetically recyclable Fe–Ni alloy catalyzed dehydrogenation of ammonia borane in aqueous solution under ambient atmosphere Journal of Power Sources, 194 (1) 478-481 117 Zhu J, Zäch M (2009) Nanostructured materials for photocatalytic hydrogen production Current Opinion in Colloid & Interface Science 14 (4) 260-269 118 Kuo P L, Chen W F, Lin C Y (2009) Multichelate-functionalized carbon nanospheres used for immobilizing Pt catalysts for fuel cells Journal of Power Sources 194 (1) 234-242 119 Tsai H Y, Wu C C, Lee C Y, Shih E P (2009) Microbial fuel cell performance of multiwall carbon nanotubes on carbon cloth as electrodes Journal of Power Sources 194 (1) 199-205 T E R I Report No.2006ST21:D2 28 A review of NT developments as applicable to developing countries effective for ethanol electrooxidation120. Nitrogen incorporated iron impregnated CNT carpet was applied on polyelectrolyte for novel membrane electrode assembly for fuel cells121. Fullerene nanofibre loaded with Pt has also been used as an electrode for direct methanol fuel cells and gave improved performance122. Pd supported on MWCNT has been developed as anode catalysts for direct alcohol fuel cells to substitute expensive Pt and provide good dispersion in a conducting support. These catalysts tested with membrane electrode assemblies showed very good activity compared to Pt-Ru supported on multi wall CNT (MWCNT)123. Ru deposited Pt catalyst for fuel cell using a method yielding uniform sized Ru has been reported124. Reduction of Pt amount in the electrocatalyst has also been done by using Co-Pt and anatase on MWCNT support. In the presence of Co, it was found the Pt surface area and activity increased in spite of lower Pt amount125. PtVFe catalysts supported on carbon showed very good performance compared to commercial Pt-carbon catalyst in PEM fuel cell126. For the fuel cell cathode catalyst, nano silica has been added to improve water wettability. This improved electrode performance particularly at low humidity127. Novel support materials for polymer electrolyte membrane (PEM) fuel cells are also being examined in the recent years and 120 Garcia-Rodriguez S, Somodi F, Borbath I, Margitfalvi J L, Pena M A Fierro J L G, Rojas S (2009) Controlled synthesis of Pt-Sn/C fuel cell catalysts with exclusive Sn-Pt interaction Applied Catalysis B, Environmental 91 (1) 83-91, Sep 2009 121 Prehn K, Warburg A, Schilling T, Bron M, Schulte K (2009) Towards nitrogen-containing CNTs for fuel cell electrodes Composites Science and Technology 69 (10) 1570-1579 122 Wang Q, Zhang Y, Miyazawa K, Kato R, Hotta K, Wakahara T (2009) Improved fullerene nanofiber electrodes used in direct methanol fuel cells Journal of Physics: Conference Series 159 (1) 012023 123 Bambagioni V, Bianchini C, Marchionni A, Filippi J, Vizza F, Teddy J, Serp P, Zhiani M (2009) Pd and Pt–Ru anode electrocatalysts supported on multi-walled carbon nanotubes and their use in passive and active direct alcohol fuel cells with an anion-exchange membrane (alcohol = methanol, ethanol, glycerol) Journal of Power Sources 190 (2) 241-251 124 Zhu A L, Teo M Y, Kulinich S A (2009) A novel improvement on nanodeposition of Ru on Pt for fuel cell applications Applied Catalysis A, General 352 (1) 17-26 125 Paunovic P, Radev I, Dimitrov AT, Popovski O, Lefterova E, Slavcheva E, Jordanov SH (2009) New nano-structured and interactive supported composite electrocatalysts for hydrogen evolution with partially replaced platinum loading International Journal of Hydrogen Energy 34 (7) 28662873 126 Fang B, Luo J, Njoki P N, Loukrakpam R, Mott D, Wanjala B, Hu X, Zhong C J (2009) Nanostructured PtVFe catalysts: Electrocatalytic performance in proton exchange membrane fuel cells Electrochemistry Communications 11 (6) 1139-1141 127 Zhu A L, Teo M Y, Kulinich SA (2009) A novel improvement on nanodeposition of Ru on Pt for fuel cell applications Applied Catalysis A, General 352 (1) 17-26 T E R I Report No. 2006ST21:D2 29 A review of NT developments as applicable to developing countries reviewed in 2009128,129. These include doped diamonds, oxides, carbides which are conductive and various nano carbon structures. These can potentially avoid the corrosion problem associated with carbon black supports. However, ceramic supports have issues of lower surface area which results in poor metal dispersion and low electrochemical activity. Therefore research on high surface area ceramic supports and further testing of these supports is required. Several nano catalysts have been developed for bio diesel application. Zeolite supported oxide catalysts (ZnO-Al2O3, SnO-Al2O3) have been tested with sodium impregnation to investigate its effect on transesterification of soybean oil using methanol130. Nano gamma alumina impregnate with KF was used for transesterification of vegetable oil with methanol. Under optimised preparation and reaction conditions high bio diesel yield was obtained and attributed to high surface area to volume ratio of the nano catalyst131. Membranes Many studies on membranes for fuel cells have been reported. Modified nafion membranes have been developed for direct methanol fuel cells (DMFC). The membrane was modified with nano TiO2 particles in the anatase form. These modified membranes had reduced methanol crossover and increased power132. Nafion has also been modified by CNT-metal (Pt, Fe)clay composites. This offered better mechanical properties, self humidifying ability and barrier resistance133. Nano composite membrane comprising of nafion-silica-phosphotungstic acid has been prepared using sol gel synthesis. Fuel cell tests with this membrane showed higher current density compared to nafion membrane134. Nanocomposite, prepared by selfassembly of Sumecton SA (a synthetic saponite-like clay) with 128 Shao Y, Liu J, Wang Y, Lin Y (2009) Novel catalyst support materials for PEM fuel cells: current status and future prospects J. Mater. Chem 19 46 - 59 129 Antolini E, Gonzalez E R (2009) Ceramic materials as supports for lowtemperature fuel cell catalysts Solid State Ionics 180 (9-10) 746-763 130 Kim M, Yan S, Salley S O, Ng K Y S (2009) The effect of sodium on the catalytic activity of ZnO–Al2O3/ZSM-5 and SnO–Al2O3/ZSM-5 for the transesterification of vegetable oil with methanol Catalysis Communications 10 (14) 1913-1919 131 Boz N, Degirmenbasi N, Kalyon D M (2009) Conversion of biomass to fuel: Transesterification of vegetable oil to biodiesel using KF loaded nanoγ-Al2O3 as catalyst Applied Catalysis B, Environmental 89 (3) 590-596 132 Tuan N , Nha N T, Tuyen N H (2009) Low-temperature synthesis of nano-TiO2 anatase on nafion membrane for using on DMFC Journal of Physics: Conference Series 187 (1) 012040 133 Li M K S, Gao P, Yue P L, Hu X (2009) Synthesis of exfoliated CNTmetal-clay nanocomposite by chemical vapor deposition Separation and Purification Technology 67 (2) 238-243 134 Mahreni A, Mohamad A B, Kadhum A A H, Daud W R W, Iyuke S E (2009) Nafion/silicon oxide/phosphotungstic acid nanocomposite membrane with enhanced proton conductivity Journal of Membrane Science 327 (1)32-40 T E R I Report No.2006ST21:D2 30 A review of NT developments as applicable to developing countries 12-phosphotungstic acid heteropolyacid, and blended with chemically modified styrene/ethylene-co-butylene/styrene block copolymer has also been developed for PEM fuel cell135. Nano particles have also been incorporated in other applications. Ni nano dots have been added to amorphous silica membranes for hydrogen separation at high temperature136. Plybenzimidazole membrane has been modified with silica nano particles for gas separation applications. Addition of silica increased the CO2 permeability and its selectivity over nitrogen137. Carbon – MWCNT composite gas separation layer on alumina support was prepared by pyrolyzing MWCNT containing polyimide. Incorporation of MWCNT led to improvement in CO2/N2 separation factor138. Solar Photovoltaic applications Nanotechnology has been used in solar photovoltaic (PV) applications to improve efficiency and reduce cost. Nanomaterials have been used in the next generation solar cells such as organic, thin film, dye sensitized and hybrid ones. Examples of nanotechnology based interventions include photovoltaic cells and organic light-emitting devices based on quantum dots as well as carbon nanotubes in composite film coatings for solar cells. Increase in efficiency in the conventional Si cells is also achieved by introducing nanomaterial based antireflection layers for higher light yield. The recent developments in the use of nanotechnology for this application are summarized below. Organic solar cells from nano thin film polymers comprising phenylenevinylene (PV) and p-phenyleneethylene (PE) have been prepared139. Hybrid solar cells using polymeric layer covered with a thin film of nanocrystal PbSe has been developed to increase efficiency and protect the polymeric layer from UV 135 Vuillaume P Y, Mokrini A, Siu A, Theberge K, Robitaille L (2009) Heteropolyacid / saponite-like clay complexes and their blends in amphiphilic SEBS European Polymer Journal 45 (6) 1641-1651 136 Kenta Y, Yumi H I, Seiji T, Tsukasa H, Tomohiro S, Shogo S, Nobuo T, Pratibha L G (2009) The three-dimensional morphology of nickel nanodots in amorphous silica and their role in high-temperature permselectivity for hydrogen separation, Nanotechnology 20 (31) 315703 137 Sadeghi M, Semsarzadeh M A, Moadel H (2009) Enhancement of the gas separation properties of polybenzimidazole (PBI) membrane by incorporation of silica nano particles Journal of Membrane Science 331 (1) 21-30 138 Tseng H H, Kumar I A, Weng T H, Lu CY, Wey M Y (2009) Preparation and characterization of carbon molecular sieve membranes for gas separation—the effect of incorporated multi-wall carbon nanotubes Desalination 240 (1) 40-45 139 Tung N T, Nghia N D (2009) Preparation of nano-thin films from conducting polymer by chemical vapor deposition method and its application for light emitting diodes (LED) and organic solar cells Journal of Physics: Conference Series 187 (1) 012006 T E R I Report No. 2006ST21:D2 31 A review of NT developments as applicable to developing countries radiation140. Film of oxidised single wall or multi wall CNT has been coated on indium tin oxide electrode for hole extraction in organic solar cells141. The metallic anode has been substituted by nano TiO2 – G PEDOT (glycerol modified poly(3,4ethylenedioxythiophene)) film due to the simplicity of making polymeric anodes using film forming techniques142. Quantum dots and CNTs have been added to improve performance of polymeric solar cells143. Nano thin film solar cells based on CdS/copper indium diselenide (CIS or CuInSe2) and Cu2S/CdS solar cells have been studied to increase band gap and efficiency144. Nano CdS belts have been used for Schottky junction PV devices145. The first dye sensitised nanostructured solar cell which was based on colloidal titanium dioxide films was introduced in 1991146. These films were sandwiched between a transparent electrode acting as anode, which is based on a conducting glass, and a platinum electrode, which acts as a catalytic conductor. An electrolyte placed between the film and the platinum electrode carries the electrons. In these cells, most of the light absorption takes place in dye molecules. Since the invention, dye-sensitized nanocrystalline solar cells have been fabricated from nanoparticles of several semiconductors147,148,149,150,151,152,153,154and different architectures 140 Kim S J, Kim W J, Cartwright A N, Prasad P N (2009) Self-Passivating hybrid (organic/inorganic) tandem solar cell Solar Energy Materials and Solar Cells 93 (5) 657-661 141 Hatton R A, Blanchard N P, Tan L W, Latini G, Cacialli F, Silva S R P (2009) Oxidised carbon nanotubes as solution processable, high work function hole-extraction layers for organic solar cells Organic Electronics 10 (3) 388-395 142 Xie F X, Liang C J, He Z Q, Tao Y L (2008) Polymer Photovoltaic Cell Using TiO2/G-PEDOT Nanocomplex Film as Electrode International Journal of Photoenergy 2008 1-7 143 Landi B J, Castro S L, Ruf H J, Evans C M, Bailey S G, Raffaelle R P (2005) CdSe quantum dot-single wall carbon nanotube complexes for polymeric solar cells Solar Energy Materials and Solar Cells 87 (1) 733-746 144 Visweswaran J (2005) Fabrication and Characterization of CIS/CdS and Cu2S/CdS Devices for Applications in Nano Structured Solar Cells, Masters thesis, University of Kentucky, USA 145 Ye Y, Dai L, Wu P C, Liu C, Sun T, Ma R M, Qin G G (2009) Schottky junction photovoltaic devices based on CdS single nanobelts Nanotechnology 20 (37) 375202 146 O’Regan B, Gratzel M. A (1991) low-cost, high-efficiency solar cell based on dyesensitized colloidal TiO2 films. Nature; 353:737–40. 147 Corma A, Atienzar P, Garcia H, Chane-Ching JY. (2004) Hierarchically mesostructureddoped CeO2 with potential for solar-cell use Nat Mater; 3:394–7 148 Singh RS, Rangari VK, Sanagapalli S, Jayaraman V, Mahendra S, Singh VP. (2004) Nano-structured CdTe, CdS and TiO2 for thin film solar cell applications. Sol Energy Sol Cells; 82:315–30 149 Singh VP, Singh RS, Thompson GW, Jayaraman V, Sanagapalli S, Rangari VK. (2004) Characteristics of nanocrystalline CdS films fabricated by sonochemical, microwave and solution growth methods for solar cell applications. Sol Energy Mater Sol Cells;81:293–303 T E R I Report No.2006ST21:D2 32 A review of NT developments as applicable to developing countries such as nanotubes, photonic crystals or photonic sponges instead of nanoparticles155,156, which considerably increase their efficiency. Polymer gel electrodes with nano TiO2 as filler have been prepared for dye sensitized solar cells (DSSC)157. Oxygen plasma treated nano TiO2 film increased the efficiency of DSSC by reducing oxygen vacancy and improving electron transport158. Coating a film of TiO2-nano Au or Ag on the working electrode also improved the efficiency159. DSSCs based on nano ZnO for holding the dye and ionic liquid gel have been developed160. Composite electrodes have been developed for dye sensitized solar cells comprising of graphite and CNT. This composite electrode was found to have better performance and lower resistance and cost compared to conductive glass electrodes161. Counter electrode made of SWCNT film as well as MWCNT film have been used in dye sensitized solar cell162,163. The solution based colloidal route to making nanoparticles is 150 Mathew X, Enriquez JP, Sebastian PJ, McClure JC, Singh VP. (2000) Charge transport mechanism in a typical Au/CdTe Schottky diode. Sol Energy Mater Sol Cells; 63:355–65 151 Making cheaper solar cells. Technology review. MIT; 2007 152 Neale NR, Frank AJ. (2007) Size and shape control of nanocrystallites in mesoporous TiO2 films J Mater Chem;17:3216–21 153 Katoh R, Furube A, Kasuya M, Fuke N, Koide N, Han L. (2007) Photoinduced electron injection in black dye sensitized nanocrystalline TiO2 films J Mater Chem;17:3190–6 154 Rodriguez I, Ramiro-Manzano F, Atienzar P, Martinez JM, Meseguer F, Garcia H, et al. (2007) Solar energy harvesting in photoelectrochemical solar cells. J Mater Chem;17:3205–9 155 Ramiro-Manzano F, Atienzar P, Rodriguez I, Meseguer F, Garcia H, Corma A. (2007) Apollony photonic sponge based photoelectrochemical solar cells Chem Commun;3:242–4 156 Rodriguez I, Atienzar P, Ramiro-Manzano F, Meseguer F, Corma A, Garcia H. (2005) Photonic crystals for applications in photoelectrochemical processes: photoelectrochemical solar cells with inverse opal topology Photonics Nanostruct;3:148–54 157 Kang M S, Ahn KS, Lee J W (2008) Quasi-solid-state dye-sensitized solar cells employing ternary component polymer-gel electrolytes Journal of Power Sources 180 (2) 896-901 158 Kim Y, Yoo B J, Vittal R, Lee Y, Park N G, Kim K J (2008) Lowtemperature oxygen plasma treatment of TiO2 film for enhanced performance of dye-sensitized solar cells, Journal of Power Sources 175 914–919 159 Chou C S, Yang R Y, Yeh C K, Lin Y J (2009) Preparation of TiO2/Nano-metal composite particles and their applications in dyesensitized solar cells Powder Technology 194 (1) 95-105 160 Wei D, Unalan H E, Han D, Zhang O, Niu L, Amaratunga G, Ryhanen T (2008) A solid-state dye-sensitized solar cell based on a novel ionic liquid gel and ZnO nanoparticles on a flexible polymer substrate Nanotechnology 19 (42) 424006 161 Yen M Y, Yen C Y, Liao S H, Hsiao M C, Weng C C, Lin Y F, Ma C C M, Tsai M C, Su A, Ho K K, Liu P L (2009) A novel carbon-based nanocomposite plate as a counter electrode for dye-sensitized solar cells Composites Science and Technology 69 (13) 2193-2197 162 Zhu H, Zeng H, Subramanian V, Masarapu C, Hung K H, Wei B (2008) Anthocyanin-sensitized solar cells using carbon nanotube films as counter electrodes Nanotechnology 19 (46) 465204 163 Ramasamy E, Lee W J, Lee D Y, Song J S (2008) Spray coated multiwall carbon nanotube counter electrode for tri-iodide (I3-) reduction in dye-sensitized solar cells Electrochemistry Communications 10 (7) 10871089 T E R I Report No. 2006ST21:D2 33 A review of NT developments as applicable to developing countries being seen as a promising low cost method for the photo absorbing layer of the solar cells164. Quantum dots have been used in solar cells. The quantum dots are nanoparticles made of direct bandgap semiconductor crystals of materials like Cadmium-selenide (CdSe) or Leadselenide (PbSe) etc. Quantum dot thin film solar cells are based on a silicon or conductive transparent oxide (CTO), like Indiumtin-oxide (ITO) substrate with a coating of nanocrystals165. Quantum dots are extremely efficient light emitters because they can emit as many as three electrons per every solar photon absorbed; while Si cells produce one electron per photon absorbed Moreover, Si based system mostly operates between 10-16% practically achievable efficiency and radiate back the remaining as waste heat, whereas theoretical conversions achieved for quantum dots could be as high as 65%. Current Si solar cells act only in the green region, thus capturing only a fraction of the available light energy. It has currently been shown that the lead selenide (PbSe ) quantum dots can absorb in the infrared, allowing for the development of PV cells far superior in converting wider fractions of light to usable energy166. Quantum well devices like quantum dots, and quantum wires, and other carbon nanotubes embedded devices primarily researched for space applications have shown efficiencies as high as 45%. Phosphorus doped silicon quantum dots have been deposited on crystalline silicon substrate for use in tandem cells for higher efficiency167. Boron doped silicon quantum dots have also been studied168. CdS quantum dots have been deposited on TiO2 for quantum dot sensitized solar cells169,170. Solar concentrators made with quantum dots (CdSe/ZnS) embedded on plastic or glass have been examined for building applications171. 164 Hillhouse H W, Beard M C (2009) Solar cells from colloidal nanocrystals: Fundamentals, materials, devices, and economics Current Opinion in Colloid & Interface Science 14 (4) 245-259 165 Ross RT, Nozik AJ. (1982) Efficiency of hot-carrier solar energy converter. J Appl Phys; 53:3813–8 166 http://www.buffalo.edu 167 Park S, Cho E, Song D, Conibeer G, Green M A (2009) n-Type silicon quantum dots and p-type crystalline silicon heteroface solar cells Solar Energy Materials and Solar Cells 93 (6) 684-690 168 Hao X J, Cho E C, Flynn C, Shen Y S, Park S C, Conibeer G, Green M A (2009) Synthesis and characterization of boron-doped Si quantum dots for all-Si quantum dot tandem solar cells Solar Energy Materials and Solar Cells 93 (2) 273-279 169 Chang C H, Lee Y L (2007) Chemical bath deposition of CdS quantum dots onto mesoscopic TiO films for application in quantum-dot-sensitized solar cells Applied Physics Letters 91 053503 170 Shen Y J, Lee Y L (2008) Assembly of CdS quantum dots onto mesoscopic TiO2 films for quantum dot-sensitized solar cell applications Nanotechnology 19 (4) 045602 171 Gallagher S J, Norton B, Eames P C (2007)Quantum dot solar concentrators: Electrical conversion efficiencies and comparative concentrating factors of fabricated devices Solar Energy 81 (6) 813-821 T E R I Report No.2006ST21:D2 34 A review of NT developments as applicable to developing countries The 4th generation PV technology, commonly known as composite PV Technology, mixes conductive polymers or mesoporous metal oxides with nanoparticles to make a single multispectrum layer. Several of these layers while stacked could lead efficiency up to 86.5%172. Nanosolar, Nanosys, Konarka Technologies, Inc., etc are few companies which are engaged in 4th generation PV research currently173. Others Nanotechnology has also been used in thermoelectric applications, battery and super capacitors. In thermoelectric applications, nanomaterials offer lower thermal conductivity and higher power. Some of the recent materials investigated include ZnO doped with nano scaled lanthanides174, nano grained bulk bismuth antimony telluride175,176,177 boron and nitrogen doped multiwalled CNT178, silicon nanowires179,180. Energy storage devices such as batteries and supercapacitors benefit from nanotechnology on account of their energy density and charge discharge rate. Many studies have looked at nano materials for lithium ion battery181. This includes incorporation of inorganic nanoparticles in the electrolyte to improve conductivity and use of nanomaterials in the electrodes to improve storage capacity and performance. Lithium manganese oxide in the nano form has been dispersed on CNT for battery/capacitor electrode and showed good performance182. Nano LiFePO4 coated with carbon has been 172 ibid Ibid 174 Otal E H, Schaeuble N, Aguirre M H, Canepa H R, Walsöe de Reca N E (2009) Thermoelectric effect in nano-scaled lanthanides doped ZnO Journal of Physics: Conference Series 167 (1) p.012040 175 Yucheng L, Bed P, Yi M, Dezhi W, Mildred S D, Gang C, Zhifeng R (2009) Structure study of bulk nanograined thermoelectric bismuth antimony telluride Nano letters 9 (4) 1419-1422 176 Xie W, Tang X, Yan Y, Zhang O, Tritt T M (2009) Unique nanostructures and enhanced thermoelectric performance of melt-spun BiSbTe alloys Applied Physics Letters, 94(10) id. 102111 177 Li Y, Jiang J, Xu G, Li W, Zhou L, Li Y, Cui P (2009) Synthesis of micro/nanostructured p-type Bi0.4Sb1.6Te3 and its thermoelectrical properties Journal of Alloys and Compounds 480 (2) 954-957 178 Kunadian I, Andrews R, Menguc M P, Qian D Thermoelectric power generation using doped MWCNTs Carbon 47 (3) 589-601 179 Shi L, Yao D, Zhang G, Li B (2009) Size dependent thermoelectric properties of silicon nanowires Applied Physics Letters 95 (6) 063102 180 Zhang , Zhang O, Bui C T, Lo G O, Li B (2009) Thermoelectric performance of silicon nanowires Applied Physics Letters 94 (21) id. 213108 181 Serrano E, Rus G, Garcýa-Martýnez J (2009) Nanotechnology for sustainable energy Renewable and Sustainable Energy Reviews 13 (2009) 2373–2384 182 Ma S B, Nam K W, Yoon W S, Bak S M, Yang X Q, Cho B W, Kim K B (2009) Nano-sized lithium manganese oxide dispersed on carbon nanotubes for energy storage applications Electrochemistry Communications 11 (8) 1575-1578 173 T E R I Report No. 2006ST21:D2 35 A review of NT developments as applicable to developing countries prepared with new precursor for lithium ion battery cathode183. Composite anode comprising carbon and nano silicon has been studied for lithium battery and showed good performance184. Other materials that have been examined for lithium battery electrodes include carbon coated CoSb3 anode185, nano LiMnPO4 prepared by a novel method for cathode186, CoO thin films for anode187, carbon coated nano porous TiO2188, nano SnO2/Mg2SnO4 as anode189, carbon silicon composite nano fiber for anode190. In alkaline secondary battery, doping of Mn3O4 electrode with nano-NaBiO3 led to charge / discharge capability191. Nano carbons such as CNTs192, carbon nano fibre, fullerene have been explored as a replacement to activated carbon electrodes in electrochemical double layer capacitors193. In case of pseudo capacitors, use of nano transition metal oxide electrodes have been examined194. 183 Koleva V, Zhecheva E, Stoyanova R (2009) A new phosphate-formate precursor method for the preparation of carbon coated nano-crystalline LiFePO4 Journal of Alloys and Compounds 476 (1) 950-957 184 Si Q, Hanai K, Imanishi N, Kubo M, Hirano A, Takeda Y, Yamamoto O (2009) Highly reversible carbon-nano-silicon composite anodes for lithium rechargeable batteries Journal of Power Sources 189 (1) 761-765 185 Mi C H, Cao Y X, Zhang X G, Li HL (2009) In situ synthesis of a CoSb3/nano-carbon-web anode for Li-ion batteries Solid State Communications 149 (19) 781-783 186 Wang D, Buqa H, Crouzet M, Deghenghi G, Drezen T, Exnar I, Kwon N H, Miners J H, Poletto L, Grätzel M (2009) High-performance, nanostructured LiMnPO4 synthesized via a polyol method Journal of Power Sources, 189 (1) 624-628 187 Do J S, Dai R F (2009) Cobalt oxide thin film prepared by an electrochemical route for Li-ion battery Journal of Power Sources 189 (1) 204-210 188 Fu L J, Yang L C, Shi Y, Wang B, Wu Y P (2009) Synthesis of carbon coated nanoporous microcomposite and its rate capability for lithium ion battery Microporous and Mesoporous Materials 117 (1) 515-518 189 Xiao T, Tang Y, Jia Z, Feng S (2009) Synthesis of SnO2/Mg2SnO4 nanoparticles and their electrochemical performance for use in Li-ion battery electrodes Electrochimica Acta 54 (8) 2396-2401 190 Ji L, Zhang X (2009) Fabrication of porous carbon/Si composite nanofibers as high-capacity battery electrodes Electrochemistry Communications 11 (6) 1146-1149 191 Pan J, Sun Y, Wang Z, Wan P, Fan M (2009) Mn3O4 doped with nanoNaBiO3: A high capacity cathode material for alkaline secondary batteries Journal of Alloys and Compounds 470 (1)75-79 192 Shah R, Zhang X, Talapatra S (2009) Electrochemical double layer capacitor electrodes using aligned carbon nanotubes grown directly on metals Nanotechnology 20 (39) 395202 193 Zhang Y, Feng H, Wu X, Wang L, Zhang A, Xia T, Dong H, Li X, Zhang L (2009) Progress of electrochemical capacitor electrode materials: A review International Journal of Hydrogen Energy 34 (11) 4889-4899 194 Liu F J, Hsu T F, Yang C H (2009) Construction of composite electrodes comprising manganese dioxide nanoparticles distributed in polyaniline– poly(4-styrene sulfonic acid-co-maleic acid) for electrochemical supercapacitor Journal of Power Sources 191 (2) 678-683 T E R I Report No.2006ST21:D2 36 A review of NT developments as applicable to developing countries Summary Table summarizes the focus of international NT developments and applications in the environment and energy sector over the last 5 years. Table 1 : International NT developments and applications over the last 5 years Nanomaterial function Adsorbent Catalyst Membrane Others (hybrid) Sector Environment Energy • Water purification • Hydrogen storage • Pollutants sequestration for improved analysis • Water / wastewater • Hydrogen production treatment (photocatalysis, • Fuel cells oxidation of colour causing • Aromatics cracking (refinery compounds, reduction of / biorefinery) metals / contaminants) • Biodiesel • Water purification • CO2 separation (disinfection / micropollutant • Fuel cell (DMFC, PEMFC) removal) • Air enrichment • Process improvement (liquid-liquid separation, desalination) • Electrodes (for sensors) • Fuel cells (Functional • Wastewater treatment membranes) (mineralization of recalcitrant • Solar PV compounds) • Energy storage In environment applications, nanotechnology has provided the following main advantages / capability Improved capacity and rapid reaction (adsorbents for pollutants removal) Higher process efficiency (catalysts / electrodes for photocatalytic / electrochemical degradation) Lower cost (lower noble metal catalyst requirements) Customized properties (functionalized adsorbents, antifouling membranes, specific sensor materials) The challenges in these applications relate to the ensuring nanomaterials quality (especially in the case of CNTs), controlling nanomaterial properties (particle and pore size, surface functionality, if applicable), system integration (especially in remediation applications combining biotechnology and nanotechnology), health and environmental impacts. In energy applications, nanotechnology has provided the following main advantages / capability Improved capacity (e.g. in adsorbents for hydrogen storage, T E R I Report No. 2006ST21:D2 37 A review of NT developments as applicable to developing countries electrodes in energy storage batteries / capacitors) Higher efficiency (catalysts, solar cells) Lower cost (replacement of costly precious metal catalysts, replacement of costly silicon solar cells, lower material requirement due to higher efficiency) Customized properties (reduced cross over in fuel cell membranes, lower thermal conductivity in thermoelectric materials) The challenges in these applications are varied and include new materials (e.g. thermoelectric applications), integration of components (e.g. solar cells), characterization techniques (e.g thermoelectric materials), control of nano material properties (pore size, particle size etc. in all applications), health and environmental impacts. T E R I Report No.2006ST21:D2 38 A review of NT developments as applicable to developing countries T E R I Report No. 2006ST21:D2 Advances in agriculture, food and health applications of nanomaterials Agriculture and food processing The primary issue faced by least developed / developing countries in the agriculture and food sector is that of food security. The world population is projected to reach 7.6 billion in 2020. Further, almost the entire population growth over the period 1996-2020 is estimated to take place in the developing countries. The growing population is, in addition, facing environmental threats including climate change that would affect food productivity. In this context, it is imperative to ensure intensification of agriculture, coupled with efficient food handling, processing and distribution. In addition to biotechnology solutions, nanotechnology is expected to play an important role in this sector. The current market for nanotechnology products in the food industry is estimated to be around US$ 1 billion; this is projected to increase to over US$20 billion in the next decade195. The largest market for food nanotechnology is estimated to be in Asia, particularly China. The field of food nanotechnology has expanded significantly over the past few years. Of the over 1000 nano based consumer products available, nearly 70% products are reportedly in the category of ‘‘Health and Fitness’’ and ‘‘Food and Beverage’’ 196. Apart from large multinationals (Kraft, Unilever, Nestle etc.), there are several smaller players with niche products (Annexure II). As per a study by the Helmut Kaiser Consultancy Group197, it is predicted that by 2015, NT will be used in 40% of the food industries198. Overall, NT applications in food and agriculture sector encompass development of new functional materials and products as well as methods and instrumentation to ensure food safety and bio-security199,200. These products typically exploit the large surface area to volume ratio of nanomaterials for various purposes201. The research and development activities are primarily targeted towards: 195 Chau C-F, Wu S-H, Yen G-C. (2007) The development of regulations for food nanotechnology. Trends Food Science & Technology 18 269–80. 196 http://www.nanotechproject.org/ 197 http://nano.foe.org.au/node/198 198 http://www.hkc22.com/nanofood.html 199 http://www.tahan.com/charlie/nanosociety/course201/nanos/AJ.pdf 200 Sozer N, Kokini J L (2009) Nanotechnology and its applications in the food sector. Trends in Biotechnology, 27 (2) 82-89. 201 Chen H, Weiss J, Shahidi F. (2006) Nanotechnology in nutraceuticals and functional foods. Food Technology 60 30–36. Chen L, Remondetto GE, Subirade M. (2006) Food protein-based materials as nutraceutical delivery systems Trends in Food Science & Technology 17 272–83. T E R I Report 2006ST21:D2 40 A review of NT developments as applicable to developing countries Improving food processing: This includes developments related to smart packaging materials to optimize product shelf-life, sensors to monitor feed safety, efficient and targeted delivery of nutraceuticals (extracts of foods with medicinal effect), on demand preservatives, customized foods. Enhancing agricultural productivity: This includes developments relating to disease detection and treatment in plants, sensors and delivery systems to ensure optimal nutrients availability to crops at the required time, more efficient delivery systems for fertilizers, pesticides, herbicides etc. thereby preventing excess dosing. In addition, NT applications in the energy and environment sectors (such as increased use of renewable energy sources, remediation of polluted water and soils) would also contribute towards providing an improved environment for agricultural activities. Nanomaterial preparation: This includes the use of plants as factories for nanoparticles production, preparation of nanomaterials from biomass based constituents like cellulose etc. Of the above, food related materials, processing and safety applications are the most extensive (Figure 3). The following sections summarize the NT developments in the agriculture and food sector in the last 5 years. Sanguansri P, Augustin M A. (2006) Nanoscale materials development — a food industry perspective. Trends Food Science & Technology 17 547–56. Garti N. (2005) Food goes nano. INFORM 6 588–589. Luo, P. G., & Stutzenberger, F. J. (2008). Nanotechnology in the detection and control of microorganisms. In A. I. Laskin, S. Sariaslani, & G. M. Gadd (Eds.). Advances in Applied Microbiology London: Elsevier 63 145–181 London: Elsevier. T E R I Report No. 2006ST21:D2 41 A review of NT developments as applicable to developing countries Figure 3 NT applications in food202 (adapted from Weiss et al. 2006) Packaging Conventional plastics, used widely in food packaging, are difficult to degrade thereby creating a serious problem of solid waste disposal. In this context, biomass based materials have been explored for the development of eco-friendly food packaging203, 204. The challenge is to overcome performance related issues (e.g. poor mechanical strength, brittleness, poor gas and moisture barrier), processing problems (e.g. low heat distortion temperature), and high cost associated with biopolymer based packaging. Incorporation of nanomaterials in biopolymers (usually neutral polysaccharides such as starch, cellulose and its derivatives205, polyesters such as 202 Adapted from Weiss J., Takhistov, P., McClements J (2006) Functional Materials in Food Nanotechnology Journal of Food Science 71(9) R107R116 .http://members.ift.org/NR/rdonlyres/FA9DE19E-1AFF-4B94-9012CDAC3C45B0FF/0/Nanotech.pdf 203 Siracusa, V., Rocculi, P., Romani, S., Rosa, M.D. (2008) Biodegradable polymers for food packaging: a review Trends in Food Science & Technology 19 (12) 634-643 204 Farris S, Schaich K M, Liu L S, Piergiovanni L, Yam L K (2009) Development of polyion-complex hydrogels as an alternative approach for the production of bio-based polymers for food packaging applications: a review Trends in Food Science & Technology 20 (8) 316332. 205 Darder, M., Aranda, P., & Ruiz-Hitzky, E. (2007). Bionanocomposites: A new concept of ecological, bio-inspired, and functional hybrid materials. Advanced Materials 19 1309–1319. T E R I Report No.2006ST21:D2 42 A review of NT developments as applicable to developing countries polyhydroxyalkanoates, poly(lactic acid)206 as well as plant oils, gelatin, chitosan207 ) provides the necessary reinforcement, improving both mechanical strength and barrier properties208; in addition, cost-price-efficiency is also improved209,210. A recent review on nanocomposites provides an overview of the subject211. Nanocomposites with conventional polymers such as nylon 6 have also been prepared with the aim of obtaining lighter, stronger plastics with better heat resistance and barrier properties212. Nanoclay reinforced synthetic polymers such as polyethylene, polypropylene etc. are being used for food packaging in view of their better strength and enhanced barrier properties213,214. Yet another aim of nanoparticles addition has been to obtain polymer degradation as well as stabilization215. The following nanomaterials have been primarily employed in food packaging applications216. Nanoclays: Though polymer–clay nanocomposite formulations have been known for nearly three decades217, research into their application for food packaging picked up in the late 1990s218. Clays and silicates are layered inorganic solids that are readily available at low cost; further they are easy to 206 Bordes P, Pollet E, Avérous L (2009) Nano-biocomposites: Biodegradable polyester/nanoclay systems Progress in Polymer Science 34 (2) 125-155. 207 Ray S S, Bousmina M (2005) Biodegradable polymers and their layered silicate nanocomposites: In greening the 21st century materials world Progress in Materials Science 50 (8) 962-1079. 208 Choudalakis G, Gotsis A D (2009) Permeability of polymer/clay nanocomposites: A review European Polymer Journal 45 (4) 967-984. 209 Sorrentino, A., Gorrasi, G., & Vittoria, V. (2007). Potential perspectives of bionanocomposites for food packaging applications. Trends in Food Science & Technology 18(2) 84–95. 210 Rhim, J. W., & Ng, P. K. W. (2007). Natural biopolymer-based nanocomposite films for packaging applications. Critical Reviews in Food Science and Nutrition 47(4) 411–433. 211 Camargo P.H.C., Satyanarayana K. G., Wypych F. (2009) Nanocomposites: synthesis, structure, properties and new application opportunities Materials Res. 12, 1-39 212 Brody, A. L. (2007). Nanocomposite technology in food packaging. Food Technology 61(10) 80–83. 213 Dadbin S., Noferesti M., Frounchi M. (2008) Oxygen barrier LDPE/LLDPE/ Organoclay nanocomposites films for food packaging 274 22-27 214 Schirmer S., Ratio J., Froio D., Thellen C., Lucciarini J. (2008) Nanocomposite polypropylene film for food packaging application Technical papers, Regional tech conf – SPE 3 1365-1360 215 Kumar A P, Depan D, Tomer N S, Singh R P (2009) Nanoscale particles for polymer degradation and stabilization—Trends and future perspectives Progress in Polymer Science 34 (6) 479-515. 216 de Azeredo H M C (2009) Nanocomposites for food packaging applications. Food Research International 42 (9) 1240-1253. 217 Collister, J. (2002). Commercialisation of polymer nanocomposites. In R. Krishnamoorti & R. A. Vaia (Eds.), Polymer nanocomposites: Synthesis, characterisation and modelling. Washington: American Chemical Society. 218 Ray, S., Easteal, A., Quek, S. Y., & Chen, X. D. (2006). The potential use of polymer–clay nanocomposites in food packaging. International Journal of Food Engineering 2(4) art. 5. T E R I Report No. 2006ST21:D2 43 A review of NT developments as applicable to developing countries process and can result in significant improvement in properties. The most extensively investigated clay is montmorillonite, a hydrated alumina-silicate layered clay219. Addition of nanoclays in polymer formulations results in several benefits viz. enhanced mechanical properties220, 221, 222, 223, 224, superior barrier properties because of the high tortuosity imparted by these materials225,226; thus, permeability of oxygen and water vapor can be significantly reduced227, 228, 229, 230, 231. In addition, increased glass transition232 and thermal degradation temperatures233,234 have also been observed. The only reported 219 Weiss, J., Takhistov, P., & McClements, D. J. (2006). Functional materials in food nanotechnology. Journal of Food Science 71(9) R107– R116. 220 Avella, M., De Vlieger, J. J., Errico, M. E., Fischer, S., Vacca, P., & Volpe, M. G. (2005). Biodegradable starch/clay nanocomposite films for food packaging applications. Food Chemistry 93 467–474. 221 Chen, B., & Evans, J. R. G. (2005). Thermoplastic starch–clay nanocomposites and their characteristics. Carbohydrate Polymers 61 455–463. 222 Mangiacapra, P., Gorrasi, G., Sorrentino, A., & Vittoria, V. (2006). Biodegradable nanocomposites obtained by ball milling of pectin and montmorillonites. Carbohydrate Polymers 64 516–523. 223 Russo, G. M., Nicolais, V., Di Maio, L., Montesano, S., & Incarnato, L. (2007). Rheological and mechanical properties of nylon 6 nanocomposites submitted to reprocessing with single and twin-screw extruders. Polymer Degradation and Stability 92(10) 1925–1933. 224 Cyras, V. P., Manfredi, L. B., Ton-That, M. T., & Vázquez, A. (2008). Physical and mechanical properties of thermoplastic starch/montmorillonite nanocomposite films. Carbohydrate Polymers 73 55–63. 225 Mirzadeh, A., & Kokabi, M. (2007). The effect of composition and draw-down ratio on morphology and oxygen permeability of polypropylene nanocomposite blown films. European Polymer Journal 43(9) 3757–3765. 226 Adame, D., & Beall, G. W. (2009). Direct measurement of the constrained polymer region in polyamide/clay nanocomposites and the implications for gas diffusion. Applied Clay Science 42 545–552. 227 Cava, D., Giménez, E., Gavara, R., & Lagaron, J. M. (2006). Comparative performance and barrier properties of biodegradable thermoplastics and nanobiocomposites versus PET for food packaging applications. Journal of Plastic Film and Sheeting 22 265–274. 228 Jawahar, P., & Balasubramanian, M. (2006). Preparation and properties of polyesterbased nanocomposite gel coat system. Journal of Nanomaterials, 4 [article ID 21656]. 229 Koh, H. C., Park, J. S., Jeong, M. A., Hwang, H. Y., Hong, Y. T., Ha, S. Y.,(2008). Preparation and gas permeation properties of biodegradable polymer/layered silicate nanocomposite membranes. Desalination 233 201–209. 230 Lotti, C., Isaac, C. S., Branciforti, M. C., Alves, R. M. V., Liberman, S., & Bretas, R. E. S. (2008). Rheological, mechanical and transport properties of blown films of high density polyethylene nanocomposites. European Polymer Journal 44 1346–1357. 231 Thellen C, Schirmer S, Ratto J A, Finnigan B, Schmidt D (2009) Coextrusion of multilayer poly(m-xylylene adipimide) nanocomposite films for high oxygen barrier packaging applications Journal of Membrane Science 340 (1-2) 45-51. 232 Petersson, L., & Oksman, K. (2006). Biopolymer based nanocomposites: comparing layered silicates and microcrystalline cellulose as nanoreinforcement. Composites Science and Technology 66 2187–2196. 233 Bertini, F., Canetti, M., Audisio, G., Costa, G., & Falqui, L. (2006). Characterization and thermal degradation of polypropylene– T E R I Report No.2006ST21:D2 44 A review of NT developments as applicable to developing countries concern with polymer-nanoclay formulations is the decreased transparency235. Cellulose nanofiber: This is a low cost and readily available nanomaterial obtained from the natural polymer cellulose236. This has been used to improve thermomechanical and barrier properties in biopolymers like starch without affecting the biodegradability237. Cellulose nanoreinforcements also improve moisture barrier238, 239, 240 and enhance thermal stability241, 242. Carbon nanotubes (CNTs): CNTs have been incorporated in various polymers such as polyvinyl alcohol243, polypropylene244 and polyamide245; the focus has been on improving the mechanical properties. montmorillonite nanocomposites. Polymer Degradation and Stability 91 600–605. 234 Cyras, V. P., Manfredi, L. B., Ton-That, M. T., & Vázquez, A. (2008). Physical and mechanical properties of thermoplastic starch/montmorillonite nanocomposite films. Carbohydrate Polymers 73 55–63. 235 Yu, Y. H., Lin, C. Y., Yeh, J. M., & Lin, W. H. (2003). Preparation and properties of poly(vinyl alcohol)–clay nanocomposite materials. Polymer 44(12) 3553–3560. 236 Hubbe, M. A., Rojas, O. J., Lucia, L. A., & Sain, M. (2008). Cellulosic nanocomposites : a review. Bioresources 3(3) 929–980. 237 Lima, M. M. D., & Borsali, R. (2004). Rodlike cellulose microcrystals: structure, properties, and applications. Macromolecular Rapid Communications 25(7) 771–787. 238 Paralikar, S. A., Simonsen, J., & Lombardi, J. (2008). Poly(vinyl alcohol)/cellulose nanocrystal barrier membranes. Journal of Membrane Science 320(1–2) 248–258 239 Sanchez-Garcia, M. D., Gimenez, E., & Lagaron, J. M. (2008). Morphology and barrier properties of solvent cast composites of thermoplastic biopolymers and purified cellulose fibers. Carbohydrate Polymers 71 235–244. 240 Svagan, A. J., Hedenqvist, M. S., & Berglund, L. (2009). Reduced water vapour sorption in cellulose nanocomposites with starch matrix. Composites Science and Technology 69(3–4) 500–506. 241 Oksman, K., Mathew, A. P., Bondeson, D., & Kvien, I. (2006). Manufacturing process of cellulose whiskers/polylactic acid nanocomposites. Composites Science and Technology 66(15) 2776–2784. 242 Petersson, L., Kvien, I., & Oksman, K. (2007). Structure and thermal properties of poly(lactic acid)/cellulose whiskers nanocomposite materials. Composites Science and Technology 67 2535–2544. 243 Bin, Y., Mine, M., Koganemaru, A., Jiang, X., & Matsuo, M. (2006). Morphology and mechanical and electrical properties of oriented PVA– VGCF and PVA–MWNT composites. Polymer 47 1308–1317. 244 Prashantha, K., Soulestin, J., Lacrampe, M. F., Krawczak, P., Dupin, G., & Claes, M. (2009) Masterbatch-based multi-walled carbon nanotube filled polypropylene nanocomposites: assessment of rheological and mechanical properties. Composites Science and Technology 69(1112) 1756-1763 245 Zeng, H., Gao, C., Wang, Y., Watts, P. C. P., Kong, H., Cui, X., et al. (2006). In situ polymerization approach to multiwalled carbon nanotubesreinforced nylon 1010 composites: mechanical properties and crystallization behavior. Polymer 47 113–122 T E R I Report No. 2006ST21:D2 45 A review of NT developments as applicable to developing countries Others: Other nanomaterials used in polymer nanocomposites include silica nanoparticles 246, starch nanocrystals 247, 248 , chitin249, chitosan nanoparticles 250. As reinforcements like clays and cellulose nanofibers possess hydrophilic surfaces, obtaining a uniform dispersion with organic polymers could be a challenge. For instance, in low density polyethylene-cellulose fiber nanocomposites, the cellulose fibers display low interfacial compatibility, low moisture resistance/barrier, and inter-fiber aggregation by hydrogen bonding251. Also, high surface hydrophilicity could result in high water absorption in the nanocomposite, which is a disadvantage in packaging applications252. Thus, several workers have examined surface modification of hydrophilic nanomaterials. For cellulose nanoreinforcements, these include acylation with fatty acids253, surfactant addition254,255, and grafting between polymeric matrix and nanomaterial256. Similarly surface modification of CNTs by introducing carboxylic acid groups has also been attempted to enhance 246 Tang S, Zou P, Xiong H, Tang H (2008) Effect of nano-SiO2 on the performance of starch/polyvinyl alcohol blend films Carbohydrate Polymers 72 (3) 521-526. 247 Kristo, E., & Biliaderis, C. G. (2007). Physical properites of starch nanocrystalreinforced pullulan films. Carbohydrate Polymers 68 146– 158. 248 Chen, Y., Cao, X., Chang, P. R., & Huneault, M. A. (2008). Comparative study on the films of poly(vinyl alcohol)/pea starch nanocrystals and poly(vinyl alcohol)/ native pea starch. Carbohydrate Polymers 73 8–17. 249 Sriupayo, J., Supaphol, P., Blackwell, J., & Rujiravanit, R. (2005). Preparation and characterization of a-chitin whisker-reinforced chitosan nanocomposite films with or without heat treatment. Carbohydrate Polymers 62 130–136. 250 De Moura, M. R., Aouada, F. A., Avena-Bustillos, R. J., McHugh, T. H., Krochta, J. M., & Mattoso, L. H. C. (2009). Improved barrier and mechanical properties of novel hydroxypropyl methylcellulose edible films with chitosan/tripolyphosphate nanoparticles. Journal of Food Engineering 92 448–453. 251 Freire, C. S. R., Silvestre, A. J. D., Pascoal Neto, C., Gandini, A., Martin, L., & Mondragon, I. (2008). Composites based on acylated cellulose fibers and lowdensity polyethylene: effect of the fiber content, degree of substitution and fatty acid chain length on final properties. Composites Science and Technology 68(15–16) 3358–3364. 252 de Rodriguez G, Lis N; Thielemans, W; Dufresne (2006). A Sisal cellulose whiskers reinforced polyvinyl acetate nanocomposites. Cellulose 13(3) 261-270 253 Freire, C. S. R., Silvestre, A. J. D., Pascoal Neto, C., Gandini, A., Martin, L., & Mondragon, I. (2008). Composites based on acylated cellulose fibers and low density polyethylene: effect of the fiber content, degree of substitution and fatty acid chain length on final properties. Composites Science and Technology, 68(15–16) 3358–3364. 254 Ljungberg, N., Bonini, C., Bortolussi, F., Boisson, C., Heux, L., & Cavaillé, J. Y. (2005). New nanocomposite materials reinforced with cellulose whiskers in atactic popypropylene: effect of surface and dispersion characteristics. Biomacromolecules 6(5) 2732–2739. 255 Petersson, L., Kvien, I., & Oksman, K. (2007). Structure and thermal properties of poly(lactic acid)/cellulose whiskers nanocomposite materials. Composites Science and Technology 67 2535–2544. 256 Mokoena, M. A., Djokovic´, V., & Luyt, A. S. (2004). Composites of linear low density polyethylene and short sisal fibres: the effects of peroxide treatment. Journal of Materials Science 39 3403–3412. T E R I Report No.2006ST21:D2 46 A review of NT developments as applicable to developing countries intermolecular interactions with the polymer matrix257. In general, the properties are affected by the degree of dispersion of the nanomaterial in the polymer matrix. For example, barrier properties in films with exfoliated nanoparticles (complete dispersion of the nanoparticle between the polymeric chains) are reportedly superior to that with intercalated nanoparticles. Therefore, it is important to optimize the experimental parameters in the nanocomposite preparation258; further plasticizers can also be successfully used to increase the degree of exfoliation259. In addition to its reinforcing function, nanomaterials in packaging material can also impart “smart” properties e.g. antimicrobial activity, oxygen scavenging and several others. Antimicrobial films for food packaging mostly incorporate nanosilver260, 261 which is a well established broad spectrum antimicrobial262; nanosilver is also reported to extend shelf life of fruits and vegetables 263,264. Cellulose absorbent pads used in retail food packaging as liners to absorb exudates from meat etc. can be impregnated with nanosilver to maintain aseptic conditions265; further, nanosilver loaded onto cellulose based filter paper grafted with acrylamide has also been reported266. In addition to nanosilver, other options are CNTs which have the ability to puncture microbial cells267, antimicrobial peptides like 257 Kim, J. Y., Han, S., II, & Hong, S. (2008). Effect of modified carbon nanotube on the properties of aromatic polyester nanocomposites. Polymer 49 3335–3345. 258 de Abreu D A P, Losada P P, Angulo I, Cruz J M (2007) Development of new polyolefin films with nanoclays for application in food packaging, European Polymer Journal 43 (6) 2229-2243. 259 Tang X, Alavi S, Herald T J (2008) Effects of plasticizers on the structure and properties of starch–clay nanocomposite films Carbohydrate Polymers 74 (3) 552-558 260 Damm, C., Münstedt, H., & Rösch, A. (2007). Long-term antimicrobial polyamide 6/silver-nanocomposites. Journal of Materials Science 42(15) 6067–6073. 261 Damm, C., Münstedt, H., & Rösch, A. (2008). The antimicrobial efficacy of polyamide 6/silver-nano- and microcomposites. Materials Chemistry and Physics 108 61–66. 262 Rai M, Yadav A, Gade A (2009) Silver nanoparticles as a new generation of antimicrobials Biotechnology Advances 27 (1) 76-83 263 An, J., Zhang, M., Wang, S., & Tang, J. (2008). Physical, chemical and microbiological changes in stored green asparagus spears as affected by coating of silver nanoparticles-PVP. LWT – Food Science and Technology 41(6) 1100–1107. 264 Li, H., Li, F., Wang, L., Sheng, J., Xin, Z., Zhao, L., et al. (2009). Effect of nano-packing on preservation quality of Chinese jujube (Ziziphus jujuba Mill. var. inermis (Bunge) Rehd). Food Chemistry 114(2) 547–552. 265 Fernández A, Soriano E, Carballo G L, Picouet P, Lloret E, Gavara R, Muñoz P H (2009) Preservation of aseptic conditions in absorbent pads by using silver nanotechnology Food Research International 42 (8) 11051112. 266 Tankhiwale R, Bajpai S K (2008) Graft copolymerization onto cellulose-based filter paper and its further development as silver nanoparticles loaded antibacterial food-packaging material Colloids and Surfaces B: Biointerfaces 69 (2) 164-168. 267 Kang, S., Pinault, M., Pfefferle, L. D., & Elimelech, M. (2007). Singlewalled carbon nanotubes exhibit strong antimicrobial activity. Langmuir 23 8670–8673. T E R I Report No. 2006ST21:D2 47 A review of NT developments as applicable to developing countries nisin268,269, enzymes like lysozyme (which have been tested in multilayer nanofilm of poly(L-glutamic acid) and lysozyme prepared by layer-by-layer assembly270) and silver ions adsorbed in nano-structured calcium silicate271. Multifunctional materials like zinc oxide with applications in gas sensors and antibacterial materials272 have also been investigated e.g. a pea starch-zinc oxide nanoparticle bionanocomposite has been prepared and characterized273. Maintaining low oxygen levels in packaged foods is yet another application. This is required to prevent food spoilage either due to direct oxidation (e.g. browning of fruits, rancidity in vegetable oils) or indirectly by aerobic microorganisms. For this purpose, oxygen scavengers such as titania nanoparticles274 have been incorporated into the packaging material. In another food preservation application, nano-structured calcium silicate with around 300 wt% of alkane phase change material has been examined for packaging of perishable food material during transportation275 In the development of novel functional foods, to ensure stability of bioactive compounds, micro- and nanoencapsulation either in the packaging and/or within foods is an attractive technique276. Functional substances that can be incorporated in packaging include phytochemicals (non-nutritive plant chemicals, typically polyphenolic compounds with antioxidant activity), vitamins, dietary fiber, prebiotics (typically 268 Haynie, D. T., Zhang, L., Zhao, W., & Rudra, J. S. (2006). Proteininspired multilayer nanofilms: science, technology and medicine. Nanomedicine: Nanotechnology, Biology, and Medicine 2 150–157. 269 Li, B., Rozas, J., & Haynie, D. T. (2006). Structural stability of polypeptide nanofilms under extreme conditions. Biotechnology Progress 22 111–117. 270 Rudra, J. S., Dave, K., & Haynie, D. T. (2006). Antimicrobial polypeptide multilayer nanocoatings. Journal of Biomaterials Science Polymer Edition 17(11) 1301-1315. 271 Johnston J H, Borrmann T, Rankin D, Cairns M, Grindrod J E, Mcfarlane A (2008) Nano-structured composite calcium silicate and some novel applications Current Applied Physics 8 (3-4) 504-507. 272 Chandramouleeswaran, S., Mhaske1, S. T., Kathe, A. A., Varadarajan, P. V., Virendra, P., & Vigneshwaran, N. (2007). Functional behaviour of polypropylene/ZnO soluble starch nanocomposites. Nanotechnology 18 385702–385709. 273 Ma X, Chang P R, Yang J, Yu J (2009) Preparation and properties of glycerol plasticized-pea starch/zinc oxide-starch bionanocomposites Carbohydrate Polymers 75 (3) 472-478 274 Xiao-e, L., Green, A. N. M., Haque, S. A., Mills, A., & Durrant, J. R. (2004). Light-driven oxygen scavenging by titania/polymer nanocomposite films. Journal of Photochemistry and Photobiology A: Chemistry 162 253–259. 275 Johnston J H, Grindrod J E, Dodds M, Schimitschek K (2008) Composite nano-structured calcium silicate phase change materials for thermal buffering in food packaging Current Applied Physics 8 (3-4) 508-511. 276 Lopez-Rubio A, Gavara R, Lagaron J M (2006) Bioactive packaging: turning foods into healthier foods through biomaterials Trends in Food Science & Technology 17 (10) 567-575 T E R I Report No.2006ST21:D2 48 A review of NT developments as applicable to developing countries carbohydrates such as lactulose and inulin that are not digested in the small intestine and thus serve as substrate for the flora in the colon). Further, to address enzyme linked health issues (such as lactose intolerance or high cholesterol levels), incorporation of appropriate enzymes (lactase, cholesterol reductase) in the packaging materials has been reported277. Sensors From the viewpoint of food safety and biosecurity, there is considerable interest in the development of nanosensors that can respond to environmental changes (e.g., temperature, humidity, oxygen levels), degradation products or microbial contamination278. The main advantage of nanosensors is that it significantly reduces detection time279. A variety of nanosensors are used in food applications viz. array biosensors (for detection of food borne contaminants), electronic nose (for wine discrimination)280, nanoelectromechanical systems (NEMS) (for pathogen detection), silicon-based microfluidic devices (laboratory-on-a-chip technology), carbon nanotube based sensors etc. In addition, NT based sensors for detection and quantification of food components have also been reported281,282, 283. Nanosensors can be placed directly into the packaging material; alternatively, they could be stand-alone measurement systems based on microfluidics devices284. Conducting polymer nanocomposites (CPC) involving conducting particles incorporated into an insulating polymer matrix have been used to detect and identify food borne pathogens285 and food spoilage286. To detect the presence of 277 Fernández, A., Cava, D., Ocio, M. J., & Lagaron, J. M. (2008). Perspectives for biocatalysts in food packaging. Trends in Food Science & Technology 19(4) 198–206 278 Bouwmeester, H., Dekkers, S., Noordam, M. Y., Hagens, W. I., Bulder, A. S., de Heer, C., et al. (2009). Review of health safety aspects of nanotechnologies in food production. Regulatory Toxicology and Pharmacology 53(1) 52–62. 279 Bhattacharya, S.; Jang J., Yang, L., Akin D., Bashir, R (2007) Biomems and nanotechnology based approaches for rapid detection of biological entitities. Journal of Rapid Methods & Automation in Microbiology 15 1– 32 280 Garcia, M. et al. (2006) Electronic nose for wine discrimination. Sensors and Actuators. B 113 911–916 281 Valdes M. G., Valdes A. C. G., Garcia J. A. C., Diaz Garcia M. e. (2009) Analytical nanotechnology for food analysis (in press) 282 D’Orazio G., Cituentes A., Fanali S., (2008) Chiral nano-liquid chromatography –mass spectrometry applied to amino acids analysis for orange juice profiling Food Chemistry 108 1114-1121 283 Tang D., Sauceda J. C., Lin Z., Ott S., Basova E., Goryacheva I., Biselli S., Lin J., Niessner R., Knopp D. (2009) Magnetic nanogold microspheres based lateral flow immunodipstick for rapid detection of aflatoxin BZ in food Biosensors and Bioelectronics 25 514-518. 284 Baeummer, A. (2004) Nanosensors identify pathogens in food. Food Technology 58 51–55 285 Arshak, K., Adley, C., Moore, E., Cunniffe, C., Campion, M., & Harris, J. (2007). Characterisation of polymer nanocomposite sensors for quantification of bacterial cultures. Sensors and Actuators B 126 226–231. T E R I Report No. 2006ST21:D2 49 A review of NT developments as applicable to developing countries oxygen in packed foods, oxygen sensors incorporating titania nanoparticles287 or nanocrystalline SnO2288 have been used for the photosensitive reduction of methylene blue dye. The dye remains colorless upon exposure to UV irradiation with any subsequent exposure to oxygen restoring the color. The application of nanosensors can be further extended to detect product tampering and product tracking through the processing289. Since nanostructures (nanobeads, nanofibres) generated by electrospinning290 can entrap bioactive molecules to yield high activities, they have been used for incorporating enzymes291 in biosensors. Sensors with the ability to detect pathogenic organisms and their toxins are especially of interest. Often, such sensors tend to combine nanomaterials with biological systems / components. Immunofluorescent nanoparticles prepared by conjugating dye-doped silica nanoparticles with antibodies for E. coli were capable of rapid detection of this bacterium in ground beef292. Another example is nanocantilevers that detect biological-binding interactions (e.g. antigen-antibody, enzymesubstrate, cofactor-receptor etc.) through physical and/or electromechanical signaling293,294. These devices have been successfully used for contaminant detection in food products295, 296 286 Joseph, T., & Morrison, M. (2006). Nanotechnology in agriculture and food. <http:// www.nanoforum.org/nf06~modul~showmore~folder~99999~scid~377~. html?action=longview_publication>. 287 Lee, S. K., Sheridan, M., & Mills, A. (2005). Novel UV-activated colorimetric oxygen indicator. Chemistry of Materials 17(10) 2744–2751. 288 Mills, A., & Hazafy, D. (2009). Nanocrystalline SnO2-based, UVBactivated,colourimetric oxygen indicator. Sensor and Actuators B: Chemical 136(2) 344–349. 289 Nachay, K. (2007). Analyzing nanotechnology. Food Technology 61(1) 34–36. 290 Torres-Giner, S., Gimenez, E., & Lagaron, J. M. (2008) Characterization of the morphology and thermal properties of zein, prolamine nanostructures obtained by electrospinning. Food Hydrocolloids 22(4) 601-614 291 Ren, G. L., Xu, X. H., Liu, Q., Cheng, J., Yuan, X. Y., Wu, L. L (2006). Electrospun poly(vinyl alcohol)/glucose oxidase biocomposite membranes for biosensor applications. Reactive & Functional Polymers 66(12) 1559-1564. 292 Zhao, X, Hilliard, L. R, Mechery, S. J., Wang, Y., Bagwe, R. P., Jin, S., Tan, W. A (2004) Rapid bioassay for single bacterial cell quantitation using bioconjugated nanoparticles. Proc. Natl. Acad. Sci. U.S.A. 101(42) 15027-15032. 293 Hall, R.H. (2002) Biosensor technologies for detecting microbiological food borne hazards. Microbes Infect. 4 425–432 294 Kumar, C.S.S.R. (2006) Nanomaterials for Biosensors. Wiley-VCH Weinheim 295 Ramirez Frometa, N. (2006) Cantilever biosensors. Biotecnologia Aplicada 23 320–323 296 Gfeller, K.Y. et al. (2005) Micromechanical oscillators as rapid biosensor for the detection of active growth of Escherichia coli. Biosensensors & Bioelectronics 21 528–533 T E R I Report No.2006ST21:D2 50 A review of NT developments as applicable to developing countries Delivery systems Nanomaterial based formulations (e.g. micelles, liposomes, nanoemulsion etc.) have been explored extensively for the delivery of nutraceuticals and functional foods. Nanoencapsulation can be carried using existing, approved food additives like carrageenan, chitosan, gelatin, polylactic acid, alginate etc. Nanoparticle formulations for improving the bioavailability (fraction of a dose that is available at the site of action in the body) of active ingredients (nutrients, nutraceuticals) is an important area of research297. The focus is on ingredients with poor water-solubility and little has been done on the uptake of water soluble minerals (like calcium and iron) and antioxidants (such as isoflavones). Nanoparticle formulations have also been examined for controlled / target release of active ingredients. For soluble but poorly absorbed nutrients and nutraceuticals, it is expected that bioavailability can be improved using selfassembled protein and lipid micro- and nanoparticle systems that are appropriately targeted to active sites. Nanoparticle delivery systems that make use of lipids, proteins and polysaccharides as additives have led to the development of new functionalities. The current focus in the development of nanoparticle based nutrient and nutraceutical delivery systems is on improving the dissolution mechanisms of particles in the intestine and subsequent absorbing through the intestinal wall. However, there is little understanding about side-effects e.g. unwanted transportation / deposition of active ingredients / intermediates, unforeseen increase in absorption of other substances present in the food matrix. For long duration preservation of foods, controlled release of the preservative is desired. To achieve this, a nanohybrid involving the intercalation of D-gluconate (a food additive and an acidity regulator), into the interlamellae of zinc–aluminumlayered double hydroxide, was prepared and characterized298. In addition, nanoencapsulation of flavour enhancers and cooking oils is also reported299. 297 Acosta E (2009) Bioavailability of nanoparticles in nutrient and nutraceutical delivery Current Opinion in Colloid & Interface Science 14 (1) 3-15. 298 Ghotbi M Y, bin Hussein M Z, Yahaya A H, Rahman M Z A (2009) LDH-intercalated d-gluconate: Generation of a new food additiveinorganic nanohybrid compound Journal of Physics and Chemistry of Solids 70 (6) 948-954. 299 Peter S., Given J. (2009) Encapsulation of flavours in emulsion for beverages, Current opinion in colloid and interface science 14 43-47 T E R I Report No. 2006ST21:D2 51 A review of NT developments as applicable to developing countries Processing The use of nanoporous materials (especially membranes in the ultrafiltration and nanofiltration range) for separation in the food industry is well accepted300 and new applications / process schemes are being developed301,302. Related research activities in this field are focused on improving membrane properties and operations for a variety of applications; as such, this topic is quite diverse and not dealt with here. There are few novel applications of nanomaterials in the food processing field. For instance, to provide continued protection against microbial contamination, nanosilver impregnated elastomer (rubber) seals have been recommended in food processing equipments like pumps, valves, mixing vessels etc303. Nano supported catalysts for applications like hydrogenation of edible oils have been used; such applications exploit the high surface area of these materials304. Agriculture NT applications in agriculture are intricately linked to developments in biotechnology (e.g. improved seeds and planting material) and materials (e.g. sensors, delivery systems for controlled release of chemicals etc.). The materials related developments are quite broad and encompass various sectoral applications; in fact, there are limited reports on NT research exclusively in agriculture. NT has been examined for the development of soil erosion resistant agents. For instance, PAM (polyacrylamide) nanofibers have been prepared by electrospinning technique and further developed into PAM/PAN (polyacrylonitrile) nanofibroses hybrid fabric305. PAM in granular form is a super absorber of water; with the enhancement in the surface area per unit mass provide by the nanofibres, the water absorption of the fabric was 4.3–3.6 times higher than that of the commercial PAM granular like shape. Other materials with super absorbent properties like chitosan 300 Girard, B., Fukumoto, L R (2000) Membrane processing of fruit juices and beverages: a review. Critical reviews in food science and nutrition 40(2) 91-157 301 Aider M, de Halleux D, Bazinet L (2008) Potential of continuous electrophoresis without and with porous membranes (CEPM) in the biofood industry: review Trends in Food Science & Technology 19(7) 351-362 302 Coutinho C M, Chiu M C, Basso R C, Ribeiro A P B, Gonçalves L A G, Viotto L A (2009) State of art of the application of membrane technology to vegetable oils: A review Food Research International 42(5-6) 536-550 303 Peel N (2008) Sealing for the food and beverage industry Sealing Technology 9 11-14. 304 Hussain S. T., Zia F., Mazhar A. (2009) Modified nanosupported catalyst for selective catalytic hydrogenation of edible oils Eur. Food Res. Technol 228 799-806 305 Ali A A (2008) New generation of super absorber nano-fibroses hybrid fabric by electro-spinning Journal of Materials Processing Technology 199(1-3) 193-198 T E R I Report No.2006ST21:D2 52 A review of NT developments as applicable to developing countries based nanocomposites can also be examined for water conservation and retention306, 307. There are some studies on the synthesis and assessment of nanocomposites with potential applications in sensors for agricultural applications. For instance, chitosan-poly(acrylic acid) composite membrane with a 3D network nano-structure has been successfully tested for ammonia detection308 and silica based nanochannels have been used for urea detection309. Nanosensors to detect specific sequences in genetically modified seeds have also been developed310. The antimicrobial property of nanosilver has been exploited in post-harvest storage. It was observed that the life of cut Gerbera jamesonni flowers was extended by pulse treatment by 2-5 nm diameter nanosilver solution311. Nanomaterials from plants / food sources Value added nanomaterials and products from biomass sources is another area of interest. For example, cellulose nanofibers of 100 nm diameter have been prepared by electrospinning of cellulose (C6H10O5)n 312. Cellulose constitutes around 90% of cotton; thus scrap cotton that accounts for nearly one-fourth of the material wasted during cotton processing can be used as the raw material for this purpose. Cellulose nanofibres have potential applications in air filtration, protective clothing, biodegradable nanocomposites, biodegradable cellulose mats for absorption / release of fertilizers and pesticides etc. The preparation of nanocomposites based on natural polymers from plant / animal sources is another well researched area (as described in the section on packaging). Other examples include electroactive polymers for a variety of applications including biosensors313. 306 Depan D., Kumar B., Singh R. P. (2008) Preparation and characterization of novel hybrid of chitosan –g- PDMS and sodium montmorrilonite J. Biomed Mater res Part B: Appl Biomate 84B 184-190 307 Xu Y., Ren X., Hanna M. A. (2006) Chitosan/clay nanocomposite film preparation and characterization J. Appl. Polym. Sci 99 1684-1691 308 Wang J., Chen C., Kuo Y. (2008) Chitosan–Poly (acrylic acid) nanofiber networks prepared by the doping induction of succinic acid and its ammonia – response studies Polymers for Advanced Technologies 19 1343-1352 309 Chen Y., Wang X., Hong M., Erramilli S., Mohanty P. (2008) Surface modified silicon nano-channel for urea sensing Sensors and Actuators B Chemical 133 593-598 310 Wang M., Du X., Liu I., Sun Q., Jiang X. (2008) DNA biosensor prepared by electrodeposited Pt nanoparticles for the detection of specific deoxyribonucleic acid sequence in genetically modified soybean Chinese J. Anal. Chem 36 890-894 311 Liu J., He S., Zhang Z., Cao J., Lv P., He S., Cheng G., Joyce D.C. (2009) Nano-silver pulse treatments inhibit stem-end bacteria on cut gerbera cv. Ruikou flowers, Postharvest Biology and Technology 54 (1) 59-62 312 Frey M W (2008) Electrospinning Cellulose and Cellulose Derivatives Polymer Reviews 48(2) 378 - 391 313 Ma X., Yu J., Wang N. (2008) Glycerol plasticized – starch/multiwall carbon nanotube composites for electroactive polymers Compos. Sci. Technol. 68 268-273. T E R I Report No. 2006ST21:D2 53 A review of NT developments as applicable to developing countries Plants can also be exploited as factories for nanomaterial production. For instance, using different plant species growing under extreme conditions viz. a xerophyte (Bryophyllum sp.), a mesophyte (Cyprus sp.) and a hydrophyte (Hydrilla sp.), silver nanoparticles have been prepared, characterized and the synthesis mechanism examined314. Plant silica bodies have been explored for NT applications as well315 since silica nanoparticles have wide biotechnological and biomedical applications in biosensors, drug delivery and imaging. The route appears attractive in view of the ready availability of crop residues, high silica purity, and the fact that microencapsulation and microcrystalline quartz with special optical characteristics may be obtained. Nanotubes can also be obtained from food material. For example, nanotubes prepared by partial hydrolysis of the milk protein α-lactalbumin have high viscosity and can be used as a thickening agent316, 317.In addition, the 8 nm in diameter cavity in these α-lactalbumin nanotubes are suited to nutraceutical encapsulation. Health applications The health applications of nanotechnology are expected to have a big impact and the main areas receiving a lot of attention are drug delivery, nano diagnostics and regenerative medicine. The advantages of nanotechnology in these areas are higher sensitivity, ability to reach specific sites, possibilities for biomimetics and personalized therapy. In the case of drug delivery, nanotechnology offers the means to send the drugs to targeted sites, and have the drug release in a controlled manner. These can lead to delivery of drugs that are otherwise difficult to administer, reduce side effects due to lower dosage and site specific administration, minimize or prevent drug degradation by using pathways other than gastrointestinal. Drug release can occur in a sustained manner (by diffusion out of carrier or of carrier) or in response to a stimuli such as temperature, pH etc. In future, applications such as drug delivery combined with analysis of drug overdose, release 314 Jha A K, Prasad K, Prasad K, Kulkarni A P (2009) Plant system: Nature's nanofactory Colloids and Surfaces B: Biointerfaces 73 (2) 219223 315 Neethirajan S, Gordon R, Wang L (2009) Potential of silica bodies (phytoliths) for nanotechnology Trends in Biotechnology 27 (8) 461-467. 316 Ipsen, R. and Otte, J. (2007) Self-assembly of partially hydrolysed alactalbumin. Biotechnology Advances 25 602–607 317 Graveland-Bikker, J.F. and de Kruif, C.G. (2006) Unique milk protein based nanotubes: food and nanotechnology meet. Trends Food Sci. Technol. 17 196–203 T E R I Report No.2006ST21:D2 54 A review of NT developments as applicable to developing countries of drugs after reaching diseased cell are envisaged. It is expected that efficient drug delivery may be available mainstream by 2015. Among the diseases to benefit from nanotechnology in drug delivery, cancer is rated high since many options will be available for treatment methods. In the field of diagnostics nanotechnology offers high sensitivity as well as reliability. The devices can be miniaturized thus smaller sample amounts are required and several analysis can be done in parallel. This will lead to a high throughput both in terms of extent of analysis possible from a single sample and number of samples that can be analyzed. Nanotechnological interventions can be in the form of biosensors that signal features about molecules in solution; integrated devices (biochips) that enable analysis of several signals, imaging tools, markers/contrast agents that enable early detection and therapy monitoring. In the case of biochips, nanotechnology offers high miniaturization and novel architectures; similarly nanotechnology can provide biosensors with new functions (e.g. through coatings) thereby broadening their applications. The high resolution offered in improved analysis techniques (microscopic, spectroscopic) as a result of nanotechnology development will also contribute towards basic research in understanding workings of disease and drugs. In molecular imaging, nanotechnology is also envisaged to act as both monitoring and delivering agents combining delivery and analysis (theranostics). In biophotonics, nanotechnology offers means to more effectively target photosensitizers and can contribute towards therapies like Photo Dynamic Therapy. The use of nanotechnology in regenerative medicine is facilitated by nanobiomimetic strategy. They enable design of suitable materials that can initiate the required regenerative event by releasing suitable signals at the required rate. This is applicable in various sites such as such as heart, bone, brain tissue. Nanotechnology allows fabrication of nano sized macromolecules with required properties. Advances in nano fabrication methodologies have led to preparation of materials with different shapes (e.g. nanoporous scaffolds, nanowires, dendrimers etc.). The applications include coating on implants to improve bonding with tissue and / or minimize rejection, improvement in mechanical properties to prevent fatigue failures, improved electrical properties for maintaining performance over a longer duration in case of neural prostheses. Most of the products are expected to enter mainstream by 2015 and beyond. However, some products are in the advanced stage. This includes Phase 3 clinical trial of paliperidone T E R I Report No. 2006ST21:D2 55 A review of NT developments as applicable to developing countries palmitate in an injectable nanoformulation which overcomes the insolubility issues with the previous version (Johnson & Johnson); FDA approval for nano based harmone replacement therapy (Novavax). While nanotechnology offers many advantages, a detailed understanding of the toxicity and other risks is required. It is also important to have manufacturing that is reproducible, economical and characterization techniques that are standardized. It requires interdisciplinary cooperation and research including legal and ethical aspects. Cost is also important to make these accessible. The investment in R&D needs to be recovered therefore impact should be huge and also offset the costs and time associated with approvals. Drug delivery Many inorganic, polymeric nanoparticles, polymeric micelles, liposomes are being used for this application. Other nanoparticles are also being studied to widen the scope and functions. Nano particles are also being considered for nose to brain delivery of drug318. Polymeric nanoparticles have also been prepared for oral drug delivery which could have advantages for chemotherapy319. Azole antifungals have been encapsulated in nanoparticles of polyactide-co-glycolide or alignate for oral consumption. The nano encapsulation enhanced the bioavailability of the drug320. Polymeric micelles of 2-methacryloyloxyethyl phosphorylcholine (MPC) copolymerized with 2(diethylamino)ethyl methacrylate (DEA) and 2(diisopropylamino)ethyl methacrylate (DPA) have been developed and showed good size, stability and drug release321. Polyeurathane based systems have also been developed. Polyallylamine nanoparticles loaded with the antibiotic cefamandole nefate and encapsulated in carboxylated polueurathane showed controlled release and extended antimicrobial activity322. Nano fibrous collagen microspheres 318 Mistry A, Stolnik S, Illum L (2009) Nanoparticles for direct nose-tobrain delivery of drugs International Journal of Pharmaceutics 379 (1) 146-157 319 Bisht S, Feldmann G, Koorstra JB, Mullendore M, Alvarez H, Karikari C, Rudek M A, Lee C K, Maitra A, Maitra A (2008) In vivo characterization of a polymeric nanoparticle platform with potential oral drug delivery capabilities Molecular Cancer Therapeutics 7 (12) 38783888. 320 Pandey R, Ahmad Z, Sharma S, Khuller G K (2005) Nanoencapsulation of azole antifungals: potential applications to improve oral drug delivery International Journal of Pharmaceutics 301 (1-2) 268-276. 321 Salvage J P, Rose S F, Phillips G J, Hanlon G W, Lloyd A W, Ma I Y, Armes S P, Billingham N C, Lewis, A.L (2005) Novel biocompatible phosphorylcholine-based self-assembled nanoparticles for drug delivery Journal of Controlled Release 104 (2) 259-270. 322 Crisante F, Francolini I, Bellusci M, Martinelli A, D'Ilario L, Piozzi A (2009) Antibiotic delivery polyurethanes containing albumin and T E R I Report No.2006ST21:D2 56 A review of NT developments as applicable to developing countries have been prepared for protein drug delivery. The retention and release of drug from these microspheres was improved by photochemical crosslinking323. Nanoparticles of copolymer beta amino ester – polyethylene glycol were studied for cytoplasmic drug delivery for cancer. These nanoparticles were able to enter the cancer cells and release the drug324. Water soluble amphiphilic poly N vinylpyrrolidones have also been studied as an efficient drug carrier325. Another amphiphilic material that has been studied is micelles from co polymer polyphosphazene grafted with poly ethylene glycol. Studies with doxorubicin loading showed sustained drug release. These carriers are expected to contribute towards improved drug sensitivity326. In order to provide a steric barrier to nano sized, functionalised liposome drug carriers, they have been covered with poly ethylene glycol. These drug carriers have been prepared for targeting colon cancer cells and show potential for providing the drug directly to colon cells327. Polymeric micelles that were worm shaped were prepared by blend of polylactic acid and amphiphile. The shape is expected to have an advantage in the penetration of tissue and controlled drug release328. Biodegradable L-tyrosine-polyphosphate nanospheres have been prepared for intracellular drug delivery. These nano spheres were not toxic and degraded in seven days329. Chitosantripolyphosphate nanoparticles have been prepared for delivery of gene / protein macromolecules. The characteristics of the nanoparticles were found to be dependent on the chitosan polyallylamine nanoparticles, European Journal of Pharmaceutical Sciences 36 (4) 555-564. 323 Chan O C M, So K F, Chan B P (2008) Fabrication of nano-fibrous collagen microspheres for protein delivery and effects of photochemical crosslinking on release kinetics Journal of Controlled Release 129 (2) 135143 324 Shen Y, Tang H, Zhan Y, Van Kirk E A, Murdoch W J (2009) Degradable Poly(β-amino ester) nanoparticles for cancer cytoplasmic drug delivery Nanomedicine: Nanotechnology, Biology, and Medicine 5 (2) 192-201 325 Kuskov A N. Shtilman M I, Goryachaya A V, Tashmuhamedov R I, Yaroslavov A A, Torchilin V P, Tsatsakis A M, Rizos A K (2007) Selfassembling nanoscaled drug delivery systems composed of amphiphilic poly-N-vinylpyrrolidones Journal of Non-Crystalline Solids, 353 (41), 3969-3975 326 Zheng C, Qiu L, Yao X, Zhu K (2009) Novel micelles from graft polyphosphazenes as potential anti-cancer drug delivery systems: Drug encapsulation and in vitro evaluation International Journal of Pharmaceutics 373 (1) 133-140 327 Garg A, Tisdale A W, Haidari E, Kokkoli E (2009) Targeting colon cancer cells using PEGylated liposomes modified with a fibronectinmimetic peptide International Journal of Pharmaceutics 366 (1) 201-210 328 Kim Y, Dalhaimer P, Christian D A, Discher D E (2005) Polymeric worm micelles as nano-carriers for drug delivery Nanotechnology, 16 (7) S484-S491 329 Ditto A J, Shah P N, Lopina S T, Yun Y H (2009) Nanospheres formulated from L-tyrosine polyphosphate as a potential intracellular delivery device International Journal of Pharmaceutics 368 (1-2) 199-206 T E R I Report No. 2006ST21:D2 57 A review of NT developments as applicable to developing countries tripolyphosphate weight ratio and other processing parameters330. Self nano emulsified drug delivery systems (SNEDDS) have been characterized by ultrasonic resonator technology and it was found that it was a reliable measure for physical properties and as an indication of the stability331. Study has also looked at different SNEDDS prototype preparation using different oil, surfactant and co-surfactant ratios for protein drug delivery orally332. Calcium deficient nano hydroxyapatite has also been studied as nano carriers for drug release. These nano carriers were prepared by two different techniques and their uptake and release behavior was studied using bovine serum albumin (BSA). The amount of BSA uptake depended method of preparation of the nano hydroxyapatite. The release of BSA under one preparation condition took place with bursting due to desorption of BSA. In other preparation conditions the release took place gradually and was associated with dissolution of nano hydroxyapatite333. Nano calcium carbonate particle have shown promise as drug carriers. The nano particles incorporated with betamethasone phosphate showed better release compared to only betamethason phosphate solution. This nanoparticle is expected to be suitable for hydrophilic drugs and proteins334. Calcium phosphate nano particles have been used to encapsulate chemotherapeutic drugs. These nanoparticles can be used for imaging and drug delivery by loading both flourophores and the drug335. Nano composites of hydroxyapatite-chitosan-konjac glucomannan were prepared for potential use as implantable drug delivery systems. It was found that the biodegrability and drug delivery rates could be 330 Gan Q, Wang T, Cochrane C, McCarron P (2005) Modulation of surface charge, particle size and morphological properties of chitosan-TPP nanoparticles intended for gene delivery Colloids and Surfaces B: Biointerfaces 44 (2) 65-73 331 Shah R B, Zidan A S, Funck T, Tawakkul M A, Nguyenpho A, Khan M A (2007) Quality by design: Characterization of self-nano-emulsified drug delivery systems (SNEDDs) using ultrasonic resonator technology International Journal of Pharmaceutics, 341 (1) 189-194 332 Venkata Ramana Rao S, Shao J (2008) Self-nanoemulsifying drug delivery systems (SNEDDS) for oral delivery of protein drugs International Journal of Pharmaceutics 362 (1) 2-9 333 Liu T Y, Chen S Y, Liu D M, Liou S C (2005) On the study of BSAloaded calcium-deficient hydroxyapatite nano-carriers for controlled drug delivery Journal of Controlled Release 107 (1) 112-121 334 Ueno Y, Futagawa H, Takagi Y, Ueno A, Mizushima Y (2005) Drugincorporating calcium carbonate nanoparticles for a new delivery system Journal of Controlled Release 103 (1) 93-98 335 Kester M, Heakal Y, Fox T, Sharma A, Robertson G P, Morgan TT, Altinoğlu E I, Tabaković A, Parette M R, Rouse SM, Ruiz-Velasco V, Adair J H (2008) Calcium phosphate nanocomposite particles for in vitro imaging and encapsulated chemotherapeutic drug delivery to cancer cells Nano Letters 8 (12) 4116-4121 T E R I Report No.2006ST21:D2 58 A review of NT developments as applicable to developing countries controlled by controlling the ratio of the constituents of the composite336. Magnetic clay based drug delivery systems have been prepared. These were prepared by using iron oxide loaded magnetic clay to obtain organic inorganic nanostructures (aspirin-clay)337. Guo et. al., have reported a low cost method of preparing single crystal magnetite nano particles which are mesoporous and superparamagnetic. These particles were promising for drug delivery with their high drug uptake and appropriate release338. Magnetic ferrosponges have been prepared using magnetic nano particles and gelatin. These had nano pores that were interconnected and showed expansion and contraction with magnetic field. Thus these are expected to be suitable for drug release controlled by magnetism339. Magnetic iron nanoparticles with cisplatin adsorbed in them were studied for drug release in magnetic heating treatments for cancer. It was observed that cisplatin desorbed from the nanoparticle in response to hypothermal or thermal ablative heating340. Mesoporous silica drug carriers have been prepared with different pore and particle size to control drug release. Water soluble captopril was used to study the loading and release kinetics. It was found that the loading increased with increasing surface area. The release was dependent on the pore diameter and particle morphology341. Fullerene based nanocarriers have also been prepared (called Buckysomes) for delivering hydrophobic anticancer drugs and were found to have good efficacy and no cytotoxicity342. Nano Fe3O4 has been used to accumulate and improve drug uptake in leukemia cells. Drug sensitive and resistant cells 336 Zhou G, Li Y, Zhang L, Zuo Y, Jansen J A (2007) Preparation and characterization of nano-hydroxyapatite/chitosan/konjac glucomannan composite Journal of Biomedical Materials Research Part A 83 (4) 931-939 337 Carja G, Chiriac H, Lupu N (2007) New magnetic organic-inorganic composites based on hydrotalcite-like anionic clays for drug delivery Journal of Magnetism and Magnetic Materials 311 (1) 26-30 338 Guo S, Li D, Zhang L, Li J, Wang E (2009) Monodisperse mesoporous superparamagnetic single-crystal magnetite nanoparticles for drug delivery Biomaterials 30 (10) 1881-1889 339 Hu S H, Liu T Y, Liu D M, Chen S Y (2007) Nano-ferrosponges for controlled drug release Journal of Controlled Release 121 (3) 181-189 340 Kettering M, Zorn H, Bremer-Streck S, Oehring H, Zeisberger M, Bergemann C, Hergt R, Halbhuber K J, Kaiser W A, Hilger I (2009) Characterization of iron oxide nanoparticles adsorbed with cisplatin for biomedical applications Physics in Medicine and Biology 54 (17) 51095121 341 Qu F, Zhu G, Huang S, Li S, Sun J, Zhang D, Qiu, S (2006) Controlled release of Captopril by regulating the pore size and morphology of ordered mesoporous silica Microporous and Mesoporous Materials 92 (1), 1-9 342 Partha R, Mitchell L R, Lyon J L, Joshi P P, Conyers J L (2008) Buckysomes: fullerene-based nanocarriers for hydrophobic molecule delivery ACS Nano 2 (9) 1950-1958 T E R I Report No. 2006ST21:D2 59 A review of NT developments as applicable to developing countries showed enhanced update of doxorubicin in the presence of nano Fe3O4343. Nano particles have also been studied for inhibiting multi drug resistance in tumor cells. In vitro studies on drug resistant leukemia cells have shown that nano TiO2 along with UV irradiation led to increased accumulation of anticancer drug and thereby changes in the cell membrane344. In related application, Damm et. al. examined polyamide 6 – silver nanocomposites and microcomposites for their antibacterial property using E coli. Antibacterial activity is required for polymers used in application such as sutures, artificial tendons medical packaging etc. They found that the nanocomposite showed a much better response compared to the microcomposite. This was attributed to the rate of silver release which was found to be an order of magnitude higher in case of the nanocomposite compared to the microcomposite345. Diagnostics Hollow nano particles have been prepared for use as ultrasound contrasting agents and for drug delivery. The mechanical properties of these particles were studied and found to depend on shell thickness to particle radius ratio346. Silicon quantum dots with luminescence have potential for medical imaging. To overcome the problem of photoluminescence instability and attaching of hydrophilic molecules, silicon quantum dots have been encapsulated in phospholipids miscelles and tested as labels for pancreatic cancer cells347. Electrodes based on gold nanomaterials have been studies as immunosensors by means of electrochemical impedence spectroscopy. Electrodes modified with gold nanorods showed better performance than those modified with gold nanoparticles348. Electrochemical impedence spectroscopy has also been used with conducting nano polymer alpha carboxy pyrrole appended to polypyrrole. 343 Zhang R, Wu C, Wang X, Sun Q, Chen B, Li X, Gutmann S, Lv G (2009) Enhancement effect of nano Fe3O4 to the drug accumulation of doxorubicin in cancer cells Materials Science and Engineering C, 29 (5) 1697-1701 344 Song M, Zhang R, Dai Y, Gao F, Chi H, Lv G, Chen B, Wang X (2006) The in vitro inhibition of multidrug resistance by combined nanoparticulate titanium dioxide and UV irradition Biomaterials 27 (23) 4230-4238 345 Damm C, Munstedt H, Rosch A (2008) The antimicrobial efficacy of polyamide 6/silver-nano- and microcomposites Materials Chemistry and Physics, 108 (1), 61-66 346 Hadinoto K (2009) Mechanical stability of hollow spherical nanoaggregates as ultrasound contrast agent International Journal of Pharmaceutics 374 (1-2) 153-161 347 Erogbogbo F, Yong K T, Roy I, Xu G, Prasad P N, Swihart M T (2008) Biocompatible luminescent silicon quantum dots for imaging of cancer cells ACS Nano 2 (5) 873-878 348 Wasowicz M, Viswanathan S, Dvornyk A, Grzelak K, Kludkiewicz B, Radecka H (2008) Comparison of electrochemical immunosensors based on gold nano materials and immunoblot techniques for detection of histidine-tagged proteins in culture medium Biosensors and Bioelectronics 24 (2) 284-289 T E R I Report No.2006ST21:D2 60 A review of NT developments as applicable to developing countries These biosensors were found to be highly stable and reproducible349. Gold nanoparticles have been used as contrasting agents for optical coherence tomography. These consisted of silica core with a gold shell and provided greater intensity and brightness in the locations where they were present350. Gold nanorods conjugated with antibody have been studied as contrast agents in photoacoustic imaging for prostrate cancer detection. By controlling the aspect ratio, the penetration depth could be increased with improved sensitivity351. Ferrofluids from dextran coated magnetite nanoparticles have been examined for MRI application. It was found that the signal from normal areas decreases on injection of ferrofluid while in case of tumor, the signal did not decrease thus making it identifiable352. Magnetite dextran nanocomposite have been prepared for making magnetic fluid for biomedical applications. The magnetite nanoparticles were coated with dextran to facilitate the preparation of water based magnetic fluid353. Magnetic nanoparticles combined with chemotherapeutic drug were encapsulated in poly(hexadecylcyanoacrylate) nanoparticles and coated with polycationic polyethylenimine for combined imaging and drug delivery. This system displayed good efficacy and was non toxic354. Polyanaline is another material suitable for diagnostic applications due to its properties. In order to improve its processability, it has been prepared in the form of particles 349 Shamsipur M, Kazemi S H, Mousavi M F (2008) Impedance studies of a nano-structured conducting polymer and its application to the design of reliable scaffolds for impedimetric biosensors Biosensors and Bioelectronics 24 (1) 104-110 350 Zagaynova E V, Shirmanova M V, Kirillin M Y, Khlebtsov B N, Orlova A G, Balalaeva I V, Sirotkina M A, Bugrova M L, Agrba P D, Kamensky V A (2008) Contrasting properties of gold nanoparticles for optical coherence tomography: phantom, in vivo studies and Monte Carlo ... Physics in Medicine and Biology 53 (18) 4995-5009 351 Agarwal A, Huang S W, O’Donnell M, Day K C, Day M, Kotov N,Ashkenazi S (2007) Targeted gold nanorod contrast agent for prostate cancer detection by photoacoustic imaging, Journal of Applied Physics 102, 064701 352 Hong R Y, Feng B, Chen L L, Liu G H, Li H Z, Zheng Y, Wei D G (2008) Synthesis, characterization and MRI application of dextran-coated Fe3O4 magnetic nanoparticles Biochemical Engineering Journal 42 (3) 290-300 353 Hong R Y, Li J H, Qu J M, Chen L L, Li H Z (2009) Preparation and characterization of magnetite/dextran nanocomposite used as a precursor of magnetic fluid Chemical Engineering Journal 150 (2) 572580. 354 Seo S B, Yang J, Hyung W, Cho E J, Tong-Il Lee, Song Y J, Yoon H G, Suh J S, Huh Y M, Haam S (2007) Novel multifunctional PHDCA/PEI nano-drug carriers for simultaneous magnetically targeted cancer therapy and diagnosis via magnetic resonance imaging Nanotechnology 18 (47) 475105. T E R I Report No. 2006ST21:D2 61 A review of NT developments as applicable to developing countries dispersed in hydrogel. These are expected to find applications as optoelectronic devices355. Glucose biosensors using nano platinum clusters and nano silica particles have been examined. The biosensor was sensitive and stable over a wide pH range356. Sensors based on glucose/galactose binding protein combined with flourophores have been prepared and flouresence lifetime imaging was used as the analytical technique and is expected to be suitable for glucose monitoring in diabetes management357. Glucose sensors have also been prepared with carbon paste electrodes containing nanostructured manganese oxide octahedral molecular sieves as mediator and glucose oxidase as biocomponent. These sensors were reliable, stable with easy and low cost construction and renewal358. Magnetic chitosan nanoparticles have been developed as photosensitizer for PDT. It has the advantage of being nontoxic, biodegradable and soluble in water. These can be monitored and targeted by MRI for PDT. These particles showed good results in both in vitro and in vivo studies359. Another group has also studied chitosan nanoparticles as carriers for photosensitizer. Glycol chitosan nano particle was used as a carrier for photosensitizer, protophorphyrin IX (PpIX). A high drug loading was possible and the release was sustained. The efficacy was better in case of the nano carrier encapsulated photosentisizer compared to the free one360. BSA nanospheres functionalized with magnetic nano particles has been developed as novel material for DPT combined with hypothermia. In vitro tests did not reveal any cytotoxicity361. 355 Dispenza C, Leone M, Presti C Lo, Librizzi F, Spadaro G, Vetri V (2006) Optical properties of biocompatible polyaniline nano-composites, Journal of Non-Crystalline Solids 352 (36) 3835-3840 356 Yang H, Zhu Y (2007) Glucose biosensor based on nano-SiO2 and ''unprotected'' Pt nanoclusters Biosensors and Bioelectronics 22 (12) 2989-2993 357 Saxl T, Khan F, Matthews D R, Zhi Z L, Rolinski O, Ameer-Beg S, Pickup J (2009) Fluorescence lifetime spectroscopy and imaging of nanoengineered glucose sensor microcapsules based on glucose/galactosebinding protein Biosensors and Bioelectronics 24 (11) 3229-3234 358 Cui X, Liu G, Lin Y (2005) Amperometric biosensors based on carbon paste electrodes modified with nanostructured mixed-valence manganese oxides and glucose oxidase Nanomedicine: Nanotechnology, Biology, and Medicine 1 (2) 130-135 359 Sun Y, Chen Z, Yang X, Huang P, Zhou X, Du X (2009) Magnetic chitosan nanoparticles as a drug delivery system for targeting photodynamic therapy Nanotechnology 20 (13) 135102 360 Lee S J, Park K, Oh Y K, Kwon S H, Her S, Kim I S, Choi K, Lee S J, Kim H, Lee S G (2009) Tumor specificity and therapeutic efficacy of photosensitizer-encapsulated glycol chitosan-based nanoparticles in tumor-bearing mice Biomaterials 30 (15) 2929-2939 361 Rodrigues M M A, Simioni A R, Primo F L, Siqueira-Moura M P, Morais P C, Tedesco A C (2009) Preparation, characterization and in vitro cytotoxicity of BSA-based nanospheres containing nanosized magnetic particles and/or photosensitizer Journal of Magnetism and Magnetic Materials 321 (10) 1600-1603 T E R I Report No.2006ST21:D2 62 A review of NT developments as applicable to developing countries Covalently linked photosentisizer on organically modified silica nanoparticles has been reported. Compared to physical encapsulation this has the advantage of not releasing the drug during circulation362. Another novel material is dendrimer phthalocyanine encapsulated in polymeric miscelle. The use of such nano carriers led to improved efficacy and efficiency363. Another novel design uses photosentisizer covalently linked to an aptamer which is then placed on the surface of single-walled carbon nano tube. The nano tube had the advantage that it would quench the singlet oxygen; this would be restored only in the presence of target which would disrupt the aptamer binding with the nano tube. Thus this offers target molecule regulation as well as improved performance and specificity364. Nano colloid has also been prepared for carrying photosensitizer using 3aminopropyltriethoxysilane. This showed good water solubility and photostability365. Regenerative medicine Nanomaterials for orthopaedic applications have been reviewed366, 367. Hybrid constructs have been developed to overcome the biocompatibility issues of synthetic materials and strength issues of constructs with only proteins. These structures were fibrous and consisted of extracellular matrix protein and polycaprolactone. These showed very good properties for regeneration application368. Fibrin gels on the nanoscale level have been prepared using magnetic force to guide the fibrin fibril self assembly. This technique had the advantage of preparing large scaffolds with little starting 362 Ohulchanskyy T Y, Roy I, Goswami L N, Chen Y, Bergey E J, Pandey R K, Oseroff A R, Prasad P N (2007) Organically modified silica nanoparticles with covalently incorporated photosensitizer for photodynamic therapy of cancer Nano Letters 7 (9) 2835-2842 363 Nishiyama N, Nakagishi Y, Morimoto Y, Lai P S, Miyazaki K, Urano K, Horie S, Kumagai M, Fukushima S, Cheng Y, Jang W D, Kikuchi M, Kataoka K (2009) Enhanced photodynamic cancer treatment by supramolecular nanocarriers charged with dendrimer phthalocyanine Journal of Controlled Release 133 (3) 245-251 364 Zhi Z, Zhiwen T, Joseph A P, Ronghua Y, Hui W, Weihong T (2008) Regulation of singlet oxygen generation using single-walled carbon nanotubes Journal of the American Chemical Society 130 (33) 1085610857 365 Zhou L, Dong C, Wei S.H, Feng Y Y, Zhou J H, Liu J.H (2009) Watersoluble soft nano-colloid for drug delivery Materials Letters 63 (20) 16831685 366 Balasundaram, G., Webster, T.J. (2007)An overview of nano-polymers for orthopedic applications Macromolecular Bioscience 7(5)635-642. 367 Stylios, G., Wan, T., Giannoudis, P. (2007) Present status and future potential of enhancing bone healing using nanotechnology Injury 38 (SUPPL. 1)S63-S74. 368 Schenke-Layland K, Rofail F, Heydarkhan S, Gluck J M, Ingle N P, Angelis E, Choi C H, MacLellan W R, Beygui R E, Shemin R J, Heydarkhan-Hagvall S (2009) The use of three-dimensional nanostructures to instruct cells to produce extracellular matrix for regenerative medicine strategies Biomaterials 30 (27) 4665-4675 T E R I Report No. 2006ST21:D2 63 A review of NT developments as applicable to developing countries material. The fibrils have application in tissue engineering369. Novel composites of nano hydroxyapatite with chitosan and carboxymethyl cellulose were prepared and characterized. The composite had interconnected porosity, good mechanical properties, biocompatibility and has potential for bone tissue engineering370. Nano hydroxyapatite chitosan scaffolds have also been prepared with in situ formation of nano particles. The nano particles led to improved mechanical properties and the scaffold had good bioactivity371. Porous nanocomposites based on nano hydroxyapatite in a matrix of poly-2hydroxyethylmethacrylate (PHEMA)/polycaprolactone (PCL) were prepared and characterized. This showed bioactivity and potential for use as scaffolds for bone repair372. Other nano hydroxyapatite based scaffolds have been examined including with poly(lactide-co-glycolide) acid (PLGA) and blended PLGA/Collagen nanofibers373; poly D,L-lactide374; polyamide375, titania376, collagen377. Chitosan (obtained by deacetylation of chitin) can be made into nanowhiskers for application in scaffolds378. Nanocomposites have also been developed for 369 Eben A, Efraim F, Joy M P, Mara P, Donald I E (2006) Magneticallyguided self-assembly of fibrin matrices with ordered nano-scale structure for tissue engineering Tissue Engineering 12 (11) 3247-3256 370 Jiang L, Li Y, Xiong C (2009) Preparation and biological properties of a novel composite scaffold of nano-hydroxyapatite /chitosan /carboxymethyl cellulose for bone tissue engineering Journal of Biomedical Science 16 (1) 65-65 371 Di C J, Yingjun W, Xiaofeng C (2009) In situ fabrication of nanohydroxyapatite in a macroporous chitosan scaffold for tissue engineering Journal of biomaterials science Polymer Edition 20 (11) 1555-1565 372 Jie H, Wan L Y, Wei F X, Serena B M, Roger A B, Neil R, William B (2007) Development of nano-sized hydroxyapatite reinforced composites for tissue engineering scaffolds.Journal of Materials Science. Materials in Medicine 18 (11) 2151-2157 373 Michelle N, Susan L, Avinash J P, Ziyuan C, Casey K C, Ramakrishna S (2009) The fabrication of nano-hydroxyapatite on PLGA and PLGA/collagen nanofibrous composite scaffolds and their effects in osteoblastic behavior for bone tissue engineering Bone 45 (1) 4-16 374 Jie R, Peng Z, Tianbin R, Shuying G, Kefeng P (2008) Poly (D,Llactide)/nano-hydroxyapatite composite scaffolds for bone tissue engineering and biocompatibility evaluation Journal of Materials Science Materials in Medicine 19 (3) 1075-1082 375 Huanan W, Yubao L, Yi Z, Jihua L, Sansi M, Lin C (2007) Biocompatibility and osteogenesis of biomimetic nanohydroxyapatite/polyamide composite scaffolds for bone tissue engineering Biomaterials 28 (22) 3338-3348 376Pushpakanth, S., Srinivasan, B., Sreedhar, B., Sastry, T.P. (2008) An in situ approach to prepare nanorods of titania-hydroxyapatite (TiO2-HAp) nanocomposite by microwave hydrothermal technique Materials Chemistry and Physics 107 (2-3)492-498. 377Pek, Y.S., Gao, S., Arshad, M.S.M., Leck, K.-J., Ying, J.Y. (2008) Porous collagen-apatite nanocomposite foams as bone regeneration scaffolds Biomaterials 29 (32)4300-4305 378 Lertwattanaseri T., Ichikawa N., Mizoguchi T., Tanka Y., Chirachanchai S. (2009) Microwave technique for efficient deacetylation of chitin nanowhiskers to a chitosan nanoscaffold Carbohydrate Research 344 331-335 T E R I Report No.2006ST21:D2 64 A review of NT developments as applicable to developing countries surgical applications 379, bone cements380, nerve repair381 and dental / bone implant material382 etc. Summary NT applications in the food and agriculture sector are targeted at improving food processing and storage (covering smart packaging, delivery systems for nutraceuticals / bioactive compounds, sensors for food quality monitoring), enhancing agricultural productivity and exploiting plants for nanomaterials production. There are several NT applications in the food sector that are already in the market. This trend appears to be driven by the significant market for nutraceuticals / bioactive products that, unlike pharmaceutical products, do not require exhaustive field testing and regulatory approvals. There is growing concern on lack of information on the risks associated with nanomaterials in the food sector (e.g. degradation, durability and toxicity of polymer– nanoparticulate systems in packaging, leaching of nanosilver in various food related consumer goods like nanocoated cookware etc.). The use of nanotechnology in health offers many advantages in aspects of drug delivery, diagnostics as well as regeneration. These include enhanced sensitivity, lower dosage requirement, targeted therapeutics, combined therapeutics and diagnostics, reduced side effects etc. Many of the applications are expected to enter the mainstream by 2015 or beyond. Given the high investment required for research and the cost and time required for getting clearances, profitability of the product is important in NT application in the health sector. In the health sector as well, the risks involved are not clear with a variety of materials and applications opening up. 379 Balázsi, C., Bishop, A., Yang, J., Sedlácková, K., Wéber, F., Gouma, P.I. (2008) Biopolymer-hydroxyapatite nanocomposite from eggshell for prospective surgical applications Materials Science Forum 589 61-65. 380 Liu-Snyder, P., Webster, T.J. (2008) Developing a new generation of bone cements with nanotechnology Current Nanoscience 4(1)111-118. 381 Lin, Y.-L., Jen, J.-C., Hsu, S.-h., Chiu, I.-M. (2008)Sciatic nerve repair by microgrooved nerve conduits made of chitosan-gold nanocomposites Surgical Neurology 70 (SUPPL. 1)S9-S18. 382 Wang, W., Watari, F., Omori, M., Liao, S., Zhu, Y., Yokoyama, A., Uo, M., Kimura, H., Ohkubo, A. (2007) Mechanical properties and biological behaviour of carbon nanotube/polycarbosilane composites for implant materials Journal of Biomedical Materials Research - Part B Applied Biomaterials 82 (1) 223-230. T E R I Report No. 2006ST21:D2 65 A review of NT developments as applicable to developing countries A NNEXURE I: List of Commercial Nanomaterials producers Asia Company Country Beijing Chamgo Nano-Tech China Products Manufactures antimicrobial fibers and plastics and nanocomposite materials. Manufacturer of nanodispersions and polymers for coatings and surface treatments in the textile and construction material industry Producer of tungsten and tungsten carbide nanopowders. Pecializes in nitride and carbide series of nanoparticle ceramic powders. URL http://www.chamgonano.com/ http://www.nanotubeseu.com/ http://www.huperoptik.com/ China Producer of carbon nanotubes. Develops and manufactures nano-ceramic coatings. Focused on development, manufacture and application of nanomaterials and adhesives. Producer of wide range of nanoparticles, coating supplements and finishing agents. Produces metal nanoparticles. China Producer of nanoparticles. http://www.chengying.com/ China Producer of carbon nanotubes. http://www.nanotubes.com.cn/ http://www.sunnano.com/ http://www.titanpe.com/ Chin Shiang Light Ray Co China Chongyi Zhangyuan Tungsten Co. HeFei Kaier Nanometer Technology Development Co. HeJi Hüper Optik China China China NaBond China Shanghai Huzheng Nano Technology Shenzen Junye Nano Material Co. Shenzhen Chengyin Technology Shenzhen NanoTechnologies Port Sun Nanotech TitanPE Technology (Shanghai) EnvironmentalCare China China China Supplier of carbon nanotubes. Produces nano photocatalysts. Hong Kong United Nanotechnologies India Nanocid Iran B.G. Polymers Israel Nano-Size Israel NutraLease Israel Sol-Gel Technologies Israel ABC Nanotech Nano Co. Nanomag Nano-Vision Tech Korea Korea Korea Korea Manufactures nano-TiO2 catalytic surface coating http://www.environmentalcare.com. materials. hk/fotocide.htm Manufactures nanoparticle-based coatings. http://www.unitednanotechnologies. com/ Produces silver nanoparticles for antimicrobial http://www.nanocid.com applications. Develops, manufactures and markets unique http://www.bgpol.co.il/ water-based acrylic nano-polymers and pigments. Specializes in research, development and http://www.nano-size.com/ production of exceptionally high specific surface area powders, nanoparticle dispersions and ultra fine grinding. Develops nano-encapsulation technology for http://www.nutralease.com/ delivery applications for nutraceuticals and drugs. Encapsulation, at room temperature, of active http://www.sol-gel.com/ ingredients in micro- and nano-sized glass (silica) matrices as well as nanospheres utilizing a chemical process called sol-gel. Silver and silica nanoparticles and nano coatings http://www.abcnanotech.com/ Producer of photocatalytic nanopowders. http://www.nanoin.com/ Producer of nanoparticles. http://www.nanomag.co.kr/eng/ Producer of various nanomaterials such as http://www.nanovistech.com/ particles, fibers and carbon nanotubes. China T E R I Report No.2006ST21:D2 http://www.zy-tungsten.com/ http://www.hfkiln.com/ http://www.nabond.com/ http://www.hznano.com/en/ http://www.junyenano.com/ 66 A review of NT developments as applicable to developing countries Company Altimate EnviroCare Services Inspiraz Technology Country Singapore Singapore NanoMaterials Technology s. Singapore Singular ID Singapore Advanced Nano Products South Korea Ecopro South Korea FinePolymer, Inc. South Korea Iljin Nanotech South Korea Nano-Infinity Nanotech Co. Taiwan Sino Technology Corporation Teco Nanotech Taiwan Products Manufactures nano-TiO2 based photocatalytic surface coatings. Manufactures antiviral, antimicrobial and hydrophobic coatings based on silver, carbon and photocatalyst nanoparticles. Development and commercialization of production technologies for nanomaterials in the pharmaceutical, electronics and chemical sectors. Provides individually tailored tagging solutions designed to combat counterfeiting and forgeries. The technology offers unique, irreproducible tags with nanoscale magnetic regions that act like fingerprints to identify each tagged item. Manufacturing and supplying the chemically processed nanocrystalline materials and their chemical precursors for coating and powder processing applications. URL http://www.altimateenvirocare.com/ http://www.inspiraz.com.sg/ http://www.nanomt.com/ http://www.singular-id.com/ http://www.anapro.com/ Manufactures carbon nanoparticles that are an http://www.ecopro.co.kr/ alternative to activated charcoal catalysts. Produces nanosilver masterbatches and other nanosilver related products. Producer of carbon nanotubes. http://hnt.hanwha.co.kr/ Manufacturer of nanoparticles and finished http://www.nano-infinity.com.tw/ nanoparticle cleaning and deodorant products. Nanoscale coating materials. http://www.nanosino.biz/ Taiwan Producer of carbon nanotubes and equipment systems for synthesis and testing http://wwwe.teconano.com.tw/ Company Microniser Country Ausralia URL http://www.micronisers.com/i Advanced Nanotechnology Limited (Advanced Nano) CeramiSphere Australia Australia DatatraceDNA Australia Nanotec Australia Nanotechnology products and services Star Pharma Australia Products Producer of nanoparticles for use in the plastics, personal care, textile, coatings, veterinarian and pharmaceutical industries. Advanced nanomaterials and nanomaterials products Commercializes a nano and micron sized ceramic spheres technology that provides encapsulation and controlled release of active molecules for a variety of applications including drug delivery, cosmeceuticals and speciality chemicals. Nanoparticle-based security technology for anticounterfeiting, identification and authentication applications. Developer, marketer and distributor of nanotechnology surface protection treatments. Nanotechnology products and services for the construction industry Develops dendrimer nanotechnology products for pharmaceutical, life science and other applications. Produces nanopowders of complex metal oxides. Austrailia Very Small Particle Company Australia Australia T E R I Report No. 2006ST21:D2 http://www.antaria.com/ http://www.ceramisphere.com.au/ http://www.datatracedna.com/ http://www.nanotec.com.au/ http://www.nanovations.com.au/ http://www.starpharma.com/ http://www.vspc.com/ 67 A review of NT developments as applicable to developing countries Europe Company Country PlasmaChem Surface- and Germany Nano-Technology Nanothinx S.A. Greece MBN Nanomaterialia Italy Lenntech Water Treatment & Air Purification n-Tec Netherlands Norway BioAlliance Pharma Paris NanoCarbLab Nanogap Russia Spain Nanoenergy Technologies Sweden Nanosensor - Switzerland Mo6 The Netherlands Yüksek Teknoloji Malzemeleri Arastirma ve Gelistirme Eurochem Auto Chemicals Turkey U.K General Applications U.K Intrinsiq Materials Ltd U.K Products Manufacturer and supplier of a wide range of industrial nanomaterials and nanotechnology-based medical devices. Develops methods for the large-scale, high-yield and low-cost production of carbon nanotubes. Producer of nanopowders such as nanostructured metal alloys, ceramics and metal-ceramics nanocomposites, polymeric alloys, fillers and nanostructured additives. Offers nanofiltration systems. URL http://www.plasmachem.de/ Producer of carbon nanotubes, carbon cones and related carbon nanomaterials. Manufactures a nanoparticle-based drug delivery platform. Producer of carbon nanotubes. roducer of nanoparticles and clusters of zero-valence metal atoms, with sizes in the range of ~ 2 to 50 atoms (~ 0.3nm to 2nm). Develops a thermoelectric coolchip having a high efficiency, 10-15 times higher than so-called Peltierelements working on the same basic principle. The coolchip, which consists of different semiconductor materials, built using nanotechnology. Manufactures scanning probes for scanning probe microscopy. The company Mo6 was formed with the aim to commercialize synthesis of transition metal chalcogenide (TMC) nanomaterials and develop new applications based on this important new class of nanomaterials. Produces nanopowders. http://www.n-tec.no/ Manufactures the Nano8 range of nanoparticle surface coatings. Creates insulating materials based on aerogel particles coated in nanoscale layers of metal or polymer. A leading European manufacturer of novel materials for applications in the Clean Tech and Wellness sectors. The company originally started as Qinetiq Nanomaterials, a spinout of international defence and security technology company QinetiQ Plc. http://www.eurochem.co.uk/ http://www.nanotubesx.com/ http://www.mbn.it/ http://www.lenntech.com/ http://www.bioalliancepharma.c om/ http://nanocarblab.com/ http://www.nanogap.es/ http://www.nanofreeze.se/ http://www.nanosensors.com/ http://www.mo6.com/ http://www.nano-tekno.com/ http://www.generalapplications. com/ http://www.intrinsiqmaterials.co m/ Iota Nanosolutions U.K Developer of organic nanodispersion technologies for industrial applications. http://www.iotanano.com/ JR Nanotech U.K Producer of various metal nanoparticles. http://www.jrnanotech.com/ Keeling & Walker U.K Manufacturer of a range of nanoparticulate powders and dispersions. http://www.keelingwalker.co.uk / T E R I Report No.2006ST21:D2 68 A review of NT developments as applicable to developing countries Company Liquids Research Country U.K Products URL Offers a wide range of ferrofluids in which the magnetic http://www.liquidsresearch.com nanoparticles are one of a variety of ferrites or transition / metals, such as iron and cobalt. Mel Chemicals U.K Metal Nanopowders Nanoco Technologies U.K U.K Oxonica U.K Q-Flo U.K Queensgate Instruments U.K Surrey Nanosystems U.K Thomas Swan ATDBio U.K UK dispersia ltd UK NanoFluorescent Materials Ukraine Producer of zirconium nanoparticles and nano stabilized zirconia materials. Production of metal powders at the sub-100nm scale. Manufactures fluorescent quantum dots from semiconductor and metallic materials. Develop nanocrystalline materials for commercial use, such as nanoparticle phosphors for flat screen displays, catalysts, chemical reactants, and quantum dots. Commercialize research findings in the areas of advanced nano-enabled materials, specifically in the area of carbon nanotube materials and their applications. NanoPositioning and nanosensor solutions for OEM development and automation applications. NanoGrowth CNT materials growth technologies for carbon nanotubes and silicon nanowire growth on substrates within a CMOS process window. Produces carbon nanotubes. Provides labelled and chemically modified oligonucleotide scaffolds for nanotechnology applications. Dispersia creates and produces advanced heat transfer fluids for thermal management and process intensification based on proprietary nanoparticle technologies. Inorganic semiconductor fluorophores nanodots and nanorods for high-sensitive fluorescence analysis. http://www.zrchem.com/nano.h tm http://www.nanocotechnologies .com/ http://www.oxonica.com/ http://www.q-flo.com/ http://www.nanopositioning.co m/ http://www.surreynanosystems. com/ http://www.thomas-swan.co.uk/ http://www.atdbio.com/ http://www.dispersia.co.uk/ http://www.nanofm.com/ U.S.A Company AcryMed Country USA Advanced Diamond Technologies (ADT) Agile Nano USA USA Ahwahnee Technologies USA Inc. Air Products Inc. USA Altair Nanotechnologies, Inc. USA Ambit Corporation USA American Elements USA Products SilvaGard®, a silver nanoparticle antimicrobial surface treatment for medical devices Nanocrystalline diamond (3-5 nm grains) for various applications (probes, seals etc.) Produces Agilezorb™, a nanotechnology-based compressible energy absorbing liquid. Agilezorb absorbs energy on a near molecular scale instead of relying on the mechanical properties of solid materials. Offers carbon nanotubes material and productiona and application knowhow. Manufactures nanoparticle dispersions. Manufacturer of proprietary nanomaterials and nano-based products Positioning technology and systems for carbon nanotube and nanowire applications. Manufacturer of advanced and engineered materials including ultra high purity refining (99.9999%) and nanoparticles. T E R I Report No. 2006ST21:D2 URL http://www.acrymed.com/ http://www.thindiamond.com/ http://www.agilenano.com/ http://www.ahwahneetech.com/ http://www.airproducts.com/ http://www.altairnano.com/ http://www.ambitcorp.com http://www.americanelements.com/ 69 A review of NT developments as applicable to developing countries Company Angstrom Medica Country USA Antibodies Incorporated - USA Apex Nanomaterials USA ApNano Materials USA Apogee Technology USA Applied Microstructures USA Applied Nanomat Inc. USA Applied NanoWorks USA Applied Thin Films USA Argonide Nanomaterials USA Aspen Aerogels USA Authentix BioForce Nanosciences USA USA BioNanomatrix - USA Biophan Technologies USA Canano Technologies Carbolex Carbon Nanotechnologies Incorporated Carbon Solutions Inc. USA USA USA Catalytic Materials USA Celsia Technologies USA USA Products A life-sciences biomaterials company that harnesses nanotechnology for orthopedic applications. Its flagship product is a patented biomimetic nanostructured material similar in composition to human bone. A provider of biomedical quantum dots (antibodies). Manufacturer of single-walled carbon nanotubes at kilogram scale. Commercializes proprietary technology for nanospheres and nanotubes made from inorganic compounds. Applies advanced MEMS and nanotechnologies to develop value add sensing solutions for the measurement industry. Manufactures nanoscale films for applications in the microelectronics and biotech industries. Develop semiconducting nano-structures for advanced nanodevices in the fields of energy, electronics, sensors, and medical devices. Provides nanomaterials and analytical services to meet both university and industrial research needs. Developing thin film technologies to serve defense, energy, aerospace, and other industrial needs. Manufacturer and supplier of specialized nano materials and ceramics. Composites, Catalysts, Bio-medical, Microelectronic and Aerospace applications. Manufacturer of aerogels for thermal insulation products. Authentication and anti-counterfeit technology. Developer of ultra-miniaturized nanoarray technologies. Molecular analysis systems are capable of providing nanometer scale, single molecule resolution. Applications in proteomics, diagnostics, and therapeutics. A bionanotech designer and maker of nanostructured chips, devices and systems for fast and low-cost analysis of native state genomic, epigenomic and proteomic information with sensitivity at the single cell / single molecule level. Develops nanotechnology drug delivery systems based on novel nanomaterials that provide precise control over location and timing of drug delivery. Provides custom engineered nanopowders. Manufacturer of carbon nanotubes. Producer of carbon nanotubes. URL http://www.pioneersurgical.com http://www.antibodiesinc.com/ http://www.apexnanomaterials.com http://www.apnano.com/ http://www.apogeemems.com http://www.appliedmst.com/ http://www.appliednanomat.com/ http://www.appliednanoworks.com/ http://www.atfinet.com/ http://www.argonide.com/ http://www.aerogel.com/ http://www.authentix.com/ http://www.bioforcenano.com/ http://www.bionanomatrix.com/ http://www.biophan.com/ http://www.cananopowders.com/ http://www.carbolex.com/ http://www.unidym.com/ Research, development and commercialization of http://www.carbonsolution.com/ single-walled carbon nanotubes, its chemistry and application to carbon based nanotechnology Producer of carbon nanotubes, carbon nanofibers http://www.catalyticmaterials.com/ and carbon nanochips. Research, development and commercialization of http://www.celsiatechnologies.com/ next-generation cooling solutions that are built on an exclusive patent portfolio in the field of thermofluid nanotechnology. T E R I Report No.2006ST21:D2 70 A review of NT developments as applicable to developing countries Company Cheap Tubes Inc Country USA ChelaTech USA Class100Nanofibers - USA Cleantechnology International CogniTek USA USA Crystalplex USA DA Nanomaterials USA Diamond-Fusion International USA 3DM USA Donaldson Company Ecology Coatings USA USA Eikos USA eMembrane USA Emergency Filtration Products USA eSpin Technologies USA Evident Technologies USA Products A supplier of high quality, low cost carbon nanotubes for research and industry. We ship worldwide. The company commercializes patented nanomaterial-based ion exchange technology to deliver cheaper, faster, and more recovery of precious, commodity and specialty metals from ores. Synthesis of biopolymer, inorganic and hybrid nanofibers. The nanofibers are fabricated on a state of the art laboratory equiped with an ISO Class 5 (Class 100) room. Supplier of high quality nanostructured carbon material such as solid carbon nanosphere chains. Expertise is in the conversion of nanoscale materials into enhanced fluids, phase change materials, and polymeric composites into respectively nanofluids, nano-PCMs and nanocomposites. Develops and commercializes innovative fluorescent markers for use in basic life science research, pharmaceutical research, diagnostics and histology. The technology is based on proprietary composition-tunable nanocrystals (quantum dots). A joint venture between DuPont and Air Products develops and manufactures colloidal silica sols and particles for electronic applications. The company's coating process works at nanoscale levels, approximately 30 nanometers. The change of the molecular composition of the silica-based surface created by bonding nanoparticles enables the full efficiency of the coating process at an atomic scale. The firm commercializes a family of selfassembling nanoscale scaffolds called PuraMatrix. 3DM’s materials assemble upon injection into nanofibers, serving as a scaffold for tissue regeneration. Manufactures nanofiber filter media. Develops and manufactures solvent-free, UV curable, advanced materials. Includes details of technologies and applications, together with information for investors. Develops unique carbon nanotube formulations for coatings. The Company's proprietary platform technology is nano-grafting of combinatorial polymer brushes for filter membranes. Manufacturer of NanoMask®, a facemask utilizing nanoparticle enhanced filters to address potentially harmful airborne contaminants. Manufactures polymeric nanofibers. Manufacturer of quantum dots and developer of quantum dot applications. T E R I Report No. 2006ST21:D2 URL http://www.cheaptubes.com/ http://www.chelatech.biz/ http://www.class100nanofibers.com/ http://www.cleantechnano.com/ http://www.cognitek.com/ http://www.crystalplex.com/ http://www.nanoslurry.com/ http://www.dfinanotechnology.com/ http://www.puramatrix.com/ http://www.donaldson.com/ http://www.ecologycoatings.com/ http://www.eikos.com/ http://www.emembrane.com/ http://www.emergencyfiltration.com/ nanomask.html http://www.espintechnologies.com/c ontact.htm http://www.evidenttech.com/ 71 A review of NT developments as applicable to developing countries Company First Nano Country USA Five Star Technologies USA Foster USA Fractal Systems USA General Nanotechnology USA Green Millennium - USA Greenyarn USA Headwaters Nanokinetics USA Helix Material Solutions USA High Performance Coatings USA Hybrid PLastics USA Hyperion Catalysis USA Idaho Space Materials USA Immunicon USA Industrial Nanotech USA Inframat Advanced Materials USA Products First Nano develops solutions for nanotube and nanowire synthesis. Developing a range of conductive dispersions for use in electrode inks and pastes targeted to the most demanding applications. Includes carbon nanofiber dispersions, carbon nanotube dispersions and nanosilver dispersions. Develops a family of nanocomposite materials designed to increase mechanical performance in medical applications. Research and development on conductive polymers, nanomaterials and nanocomposites for electronic and electrochemical applications, including sensors and power sources. Makes Probe 3D and SmartFocus Software: used by major manufacturers in Atomic Force and Confocal Microscopy systems, and in semiconductor wafer profiling equipment. GN's imaging software is useful for SPM and optical microscopy, including laser and Nipkow disk confocal imaging. Photo-catalyst nanomaterial and solution provider in the domain of environmental coating services and business integration. Manufactures antibacterial and antimicrobial textile fibers coated with bamboo-carbon nanoparticles. Develops and manufactures nanotechnology catalysts for use in chemical and pharmaceutical manufacturing; fuel cells; NOx and VOC emissions reduction; water treatment/remediation; fillers and coatings; precious metal catalyst regeneration and other applications. Producer of carbon nanotubes. Manufactures coating materials that offer increased durability and corrosion resistance by the incorporation and use of the nanomaterials. Pioneered and continues to specialize in the design, manufacture, and application of Nanostructured® Chemical Tools derived from a class of chemicals known as Polyhedral Oligomeric Sil sesquioxanes (POSS®). Carbon nanotube development and commercialization. Producer of single-walled carbon nanotubes in research quantities. Developed and integrated several patented technologies for the isolation, manipulation and analysis of rare cells. Patented magnetic nanoparticles, called ferrofluids, are at the heart of rare cell isolation for their kits and marker reagents. Nanoparticle based insulation and coating materials. Produces a wide range of nanoparticles such as oxides, carbides, nitrides and metals. T E R I Report No.2006ST21:D2 URL http://www.firstnano.com/ http://www.fivestartech.com/ http://www.fostercorporation.com/ http://www.fractalsystemsinc.com/ http://www.gennano.com/ http://www.greenmillennium.com/ http://www.greenyarn.com/ http://www.htigrp.com/nano.asp http://www.helixmaterial.com/ http://www.hpcoatings.com/products /nanotechnology.aspx http://www.hybridplastics.com/ http://www.fibrils.com/ http://www.idahospace.com/ http://www.immunicon.com/ http://www.industrial-nanotech.com/ http://www.advancedmaterials.us 72 A review of NT developments as applicable to developing countries Company InMat Country USA Innovalight USA Integran JenLaur USA USA Kanematsu USA USA Liekki USA Liquida - USA Litmus Nanotechnology USA Lumiphore USA Luna Nanoworks USA Mach I USA Mad City Labs USA Marketech International USA Material Methods USA materials Modification USA Materials Technologies Research MTR Limited Mayaterials Inc. USA USA Meliorum Technologies USA M.E.R. Corporation USA Products Develops products in the field of nanocomposite coatings that improve the barrier properties of polymers and elastomers. Has developed a silicon nanocrystalline ink for the production of low-cost solar power modules. Provider of nanostructured material technologies. Produces metallofullerenes and metallofullerene composites. Manufactures a range of nanomaterials such as powders, coatings, polymers, colloids or resins. Supplier of highly doped fibers designs, manufactures and markets high performance fibers as well as fiber components and subassemblies (optical engines) for fiber amplifiers and lasers using its unique and proprietary Direct Nanoparticle Deposition (DND) technology. Develops a template manufacturing proces that utilizes technologies adopted from the microelectronics industry for the fabrication of engineered shape and size-specific nanomaterials. Specializes in the production of ultra pure high quality nanostructure materials such as carbon nanotubes and carbon nanofibers. Develops and markets biological detection systems based on luminescent lanthanide complexes, which provide a unique combination of sensitivity, reliability, flexibility and high throughput. Produces carbon nanomaterials such as nanotubes and fullerenes, including fullereneenclosed metal atoms. Produces nanoparticles for applications in advanced materials and aerospace industries. Manufacturer of nanopositioning systems with subnanometer precision. Offers custom fabricated finished components from advanced materials as well as semi-finished stock including nanofoams and nanopowders. Manufactures and markets separation and energy devices and components built on nano-structured materials. Provides innovative solutions in materials science based on nanocrystalline metals and ceramics. Producer of fullerenes. URL http://www.inmat.com/ http://www.innovalight.com/ http://www.integran.com/ http://www.jenlaurltd.com/ http://www.kanematsuusa.com/ http://www.liekki.com/ http://www.liquidia.com/ http://www.litmusgti.com/ http://www.lumiphore.com/ http://www.lunananoworks.com/ http://www.machichemicals.com/ http://www.madcitylabs.com/ http://www.mkt-intl.com/ http://www.materialmethods.com/ http://www.matmod.com/ http://www.mtr-ltd.com/ The company commercializes nanocoating and http://www.talmaterials.com/ nanocomposite technologies. The firm's business objectives are to provide the academic and commercial communities with large-scale quantities of these materials and to help companies realize commercial products based on them through contract research and intellectual property development. Producer of semiconductor, metal and oxide http://www.meliorum.com/ nanomaterials. Research and development of advanced materials, http://www.mercorp.com/mercorp/ including fullerenes and carbon nanotubes T E R I Report No. 2006ST21:D2 73 A review of NT developments as applicable to developing countries Company MicroTechNano Country USA Molecular Diamond Technologies USA Molecular Nanosystems USA MTI Corporation USA Nano Pulp and Paper USA NanoBioMagnetics USA NanoBlox USA NanoBreeze USA Nano-c Nanocerox USA USA Nanocomp Technologies USA nanoComposix USA Nanocopeia USA Nanocs USA NanoDynamics USA NanoEner - USA Nanoexa USA NanoGram - USA Products Producer of carbon nanotubes, nanoparticles and nanowires. Produces diamondoids, tiny diamond fragments which come in a wide variety of shapes and are very rigid and stable. These properties, plus their minute size, make diamondoids potentially useful building blocks for molecular-size machines, or nanotechnology. Uses patent-protected site-selective chemical vapor deposition technology to develop solutions for the field of electronics. Producer of nanoparticles, crystals and manufacturer of precision machines for crystal and materials processing. Applies nanotechnology processes and applications to pulp and paper production. Pioneering an emerging area of nanomedicine referred to as organ-assisting-device (OAD) technologies. Creates materials known as Ultra-Dispersed Diamond (UDD), Nanocrystalline diamond or Nanodiamond (the Nanoblox) for industrial and biomedical uses. Manufactures nano-TiO2 photocatalyst material for use in its air purifiers. Producer of carbon nanotubes and fullerenes. Produces mixed-metal oxide spherical nanopowders. Production technology for carbon nanotubes and application focused, nanotube based products. Specializes in the fabrication of multi-component nanoparticles that are tailored for specific applications. Commercializes its proprietary process for creating advanced coatings and drug formulations through its ability to nanoformulate compounds and/or apply those novel formulations as coatings onto the surfaces of medical devices. Producer of carbon nanotubes and gold and silver nanoparticles. Produces high performance materials including metal and ceramics nanoparticles and carbon nanotubes. Pioneers high-efficiency nanomaterials deposition technologies for the production of different types of electrodes and other structural materials in several milliseconds. Develops nanotechnology software design tools that enable modeling and simulation of nano materials. Develop and commercialize new nanoscale materials for optical, electronic and energy storage applications and products : nanomaterials synthesis, laser process, LDR, RMS, manufacturing. T E R I Report No.2006ST21:D2 URL http://www.microtechnano.com/ http://moleculardiamond.chevron.co m/ http://www.monano.com/ http://mtixtl.com/ http://www.nanopulpandpaper.com/ http://www.nanobmi.com/ http://www.nanobloxinc.com/ http://www.nanobreeze.com/ http://www.nano-c.com/ http://www.nanocerox.com/ http://www.nanocomptech.com http://www.nanocomposix.com http://www.nanocopoeia.com/ http://www.nanocs.com/ http://www.nanodynamics.com/ http://www.nanoener.com/ http://www.nanoexa.com/ http://www.nanogram.com/ 74 A review of NT developments as applicable to developing countries Company NanoH2O - Country USA NanoHorizons USA NanoLab Inc. USA Nanomaterials Company USA Nanomaterials Discovery Corporation NanoMech Nanomix USA USA USA Nanophase USA NanoPrism Technologies USA Nanoprobes USA Nanoridge USA Nanorisk USA NanoSafeguard USA Nanoscale Corporation USA NanoSelect USA NanoSolar USA NanoSonic USA Nanostellar Nanostructured and Amorphous Materials USA USA Products Enhances current polymer-based membranes with nanostructured material that allows additional 'degrees of freedom' in the control of membrane properties. Engineering company with a focus on silver nanoparticles. Produces carbon nanotubes using the CVD growth process. The process produces arrays of aligned carbon nanotubes on substrates. Specializes in the production of nanomaterials (nanoparticles and nanopowders) having complex composition and exacting particle size and particle size distribution and tailored surface characteristics. Develops nanostructured materials using highthroughput combinatorial electrochemical methods. Nanostructured coatings and coating systems. Develops nanotechnology based sensors and hydrogen storage systems. Engineers and produces nanocrystalline materials (ceramic and metallic materials in powder form) using several techniques including Physical Vapor Synthesis and Discrete Particle Encapsulation. A developer of ferro- and magneto-rheological fluids with dispersed nanoparticles in both aqueous and non-aqueous media specially designed for implementation in various specific highperformance applications in life sciences and the biomedical field. Manufacturer of nanoparticle immunogold labeling and immunoassay tests. Technologies focused on applications of carbon nanotubes and other nanoparticles for production and sales of advanced nanomaterials. Website and newsletter addressing the issues of risk associated with engineered nanoparticles. Manufactures nanoparticle-based surface treatment products for a wide range of materials. roducer of nanoscale metal oxides, granules and suspensions. Developing chemical and biological sensors to monitor the quality and safety of our municipal water supply systems. Focused on certain optoelectronically relevant materials and include semiconductor quantum dots and nanoparticles as well as nanotemplates with precise three-dimensional order. Develops molecular self-assembly processes that allow the controlled synthesis of material structure at the nanometer level and the manufacturing of new materials with designed novel and useful engineering constitutive behaviors. Engineered nanomaterials for emissions control. Manufacturer and supplier of nanoscale metal oxides, nitrides, carbides, diamond, carbon nanotubes for research and industry. T E R I Report No. 2006ST21:D2 URL http://www.nanogram.com/ http://www.nanohorizons.com http://www.nano-lab.com/ http://www.nanomaterialscompany.c om/ http://www.nanomaterialsdiscovery. com/ http://www.nanomech.biz/ http://www.nano.com/ http://www.nanophase.com/ http://www.nanoprism.net/ http://www.nanoprobes.com/ http://www.nanoridge.com/ http://www.nanorisk.org/ http://www.nanosafeguard.com/ http://www.nanmatinc.com/ http://www.nanoselect-sensors.com/ http://www.nanosolar.com/ http://www.nanosonic.com/ http://www.nanostellar.com/ http://www.nanoamor.com/ 75 A review of NT developments as applicable to developing countries Company Nanosyn Country USA NanoTechLabs USA Nanotex USA NanoVec ts. USA Nanoviricide USA Nansulate NaturalNano USA USA nCoat USA NEI Corporation USA Nextreme Thermal Solutions USA nGimat - USA NN-Labs USA Noble Polymers USA Novacentrix USA Nucryst USA Nyacol Nano Technologies USA Optodot Corporation USA Pacific Fuel Cell USA Pacific Industrial Development Corporation USA Products Design, synthesis, and analysis of small molecule organic compounds for the pharmaceutical industry. Development and production of military and commercial products that have performance benefits through the incorporation of nanotechnology. Nanotechnology engineered textile fibers and fabrics. Developing next generation nanobiomolecular vaccines and therapeutics against infectious diseases, cancer and biothreats. Utilizing nanoscale materials and processes to develop anti-viral drugs against a wide range of human and animal viruses. Coating products from Industrial Nanotech, Inc. Develops and markets proprietary technologies and products that provide novel properties to a variety of materials such as industrial polymers, plastics and composites. Core product: Halloysite nanotubes. nano-level processes and nano-formulated materials to develop surface coatings. Develops, manufactures and distributes nanoscale materials to create significant performance improvements in high-volume manufactured goods. Manufactures solid-state heat pumps fabricated from a nano-structured thin film. Manufactures engineered nanomaterials in the following areas: nanopowders, thin film coatings, and devices. Production of colloidal nanocrystals and research into nanocrystal-based technologies such as LEDs, solar cells and biolabels. Develops and manufactures high-performance nanocomposite resin compounds and plastics solutions. Develops a portfolio of nanoscale metal inks for printable electronics applications. Develops, manufactures and commercializes medical products based on nanocrystalline silver technology. Colloidal dispersions and inorganic oxides for applications involving translucency, transparency, flame-retardants, abrasion resistance, catalyst binders and refractory binders. Developed two material platforms for energy, security and communications applications: nanoporous membranes and organic semiconductor materials. Utilizes nanotechnology to manufacture fuel cell components. Ffocused on producing specialty chemicals and performance nanomaterials for a wide array of environmentally focused products. T E R I Report No.2006ST21:D2 URL http://www.nanosyn.com/ http://nanotechlabs.com/ http://www.nano-tex.com/ http://www.nanovec.com/ www.nanoviricides.com http://www.nansulate.com/ http://www.naturalnano.com/ http://www.ncoat.com/ http://www.neicorporation.com/ http://www.nextremethermal.com/ http://www.ngimat.com/ http://www.nn-labs.com/ http://www.noblepolymers.com/ http://www.nanoscale.com/ http://www.nucryst.com/ http://www.nyacol.com/ http://www.optodot.com/ http://www.pfce.net/http://www.hoov ers.com/pacific-fuel-cell/ http://www.pidc.com/ 76 A review of NT developments as applicable to developing countries Company PChem Associates Country USA QuantumSphere USA Rave Nanomachining USA Reactive Nanotechnologies USA Reade Advanced Materials USA Salvona USA Seal-Guard USA SES Research Silco International USA USA Smart Engineering Tools Solaris Nanosciences USA USA Southwest Nanotechnologies Stanford Materials USA USA Strem Chemicals USA Synkera Technologies, Inc. USA Telemolecular USA Term USA Third-Order Nanotechnologies Triton Biosystems USA USA USA Uluru USA Products Patented nanomaterial technology for printed electronics. Manufacturer of nano catalysts for applications in portable power, renewable energy, electronics, defense and other markets demanding advanced materials. Nanomachining solutions for ultra microfinishing and advanced photomask repair systems. Develops and manufactures NanoFoil™, fabricated by vapor depositing thousands of alternating nanoscale layers of aluminum and nickel, to precisely control the instantaneous release of heat energy for reaction initiation and joining applications. Distributor of metal, ceramic, and composite nanostructures down to 5 nm. Developed several controlled-release nanosphere delivery systems for use in industries involving health care, personal care, food, beverage, fabric and household products. Manufactures nanoparticle-based resins for surface protection. Producer of fullerenes and carbon nanotubes. Producer of high quality and ultra pure colloidal silica and customizable silica sols. Fullerene producer. Develops and commercializes core-shell nanostructures and nanomaterials for solar cell applications. Manufacturer of carbon nanotubes URL http://www.nanopchem.com/ Supplier of rare earth, non-ferrous, advanced ceramic materials and carbon nanotubes. Manufacturer of metal nanoclusters, nanocolloids, nanopowders and magnetic fluids. Develops and markets a range of products based on nanotechnology and microfabrication techniques, including chemical sensors, ceramic membranes, and nanocomposites. Overview of company, technologies, and products. Produces synthetic DNA nanocircles and PGLA biodegradable nanoparticles for applications in human tissue regeneration. Supplier of fullerenes. Designs and produces high-end electro-optic polymeric materials. Magnetic nanomaterials and magnetic field energy to make antibodies tumoricidal and more therapeutically selective, without the side effects of conventional therapies. Developed and manufactures a novel, biomaterial which utilizes hydrogel nanoparticles which aggregate to form a material of varying strength and elasticity which has medical application including wound management and burn care, tissue regeneration and drug delivery devices. http://www.stanfordmaterials.com/ T E R I Report No. 2006ST21:D2 http://www.qsinano.com/ http://www.ravellc.com/ http://www.rntfoil.com/ http://www.reade.com/ http://www.salvona.com/ http://www.seal-guard.com/ http://www.sesres.com/ http://www.silco-intl.com/ http://www.fullereneproduct.com/ http://www.solarisnano.com/ http://www.swnano.com/ http://www.strem.com/ http://www.synkera.com/ http://www.telomolecular.com/ http://www.fullerenesforsale.com/ http://www.third-order.com/ http://www.adurobiotech.com/ http://www.uluruinc.com/ 77 A review of NT developments as applicable to developing countries Company XetaComp Country USA Xintek USA Zyvex USA Zyvex Performance Materials Chemicon CIMA NanoTech USA USA USA Dais Analytic USA Dendritic Nanotechnologies USA MicroMagnetics USA Seashell Technologies USA American Dye Source Canada Labopharm Canada MCH Nano Solutions Canada Nanoledge Canada NanoNB Nanox Canada Canada Northern Nanotechnologies Canada Raymor Industries - Canada LaSys Mexico Products Focusing on the manufacture and commercialization of physical sunblocks that are broad-spectrum UVA/UVB attenuators. Major products include: carbon nanotube(CNT)based field emission electron source, field emission grade CNT material, field emission x-ray source and CNT AFM probes. Nanotechnology research and development company. Creates technology for atomically precise manufacturing. Provides carbon nanotube powered producucts such as additives and concentrates. Molecular biology research tools. Manufactures nanomaterial-based products for use in electronics applications. These products include conductive inks and pastes for inkjet and conventional printing of electronics. Nanotechnology polymer materials company. A developer and provider of advanced dendritic polymers. Leader in commercial applications of spintronics, a new technology which combines the fields of magnetism, electronics, and nanotechnology. Supplies nanoparticles and nanostructured materials for academic research, development projects and for industrial processes. The unique properties of these materials and devices are utilized for biomedical, photonic, thermal, electronic, metrology, envir Manufacturer of various nanoscale materials such as fillerenes, quantum dots and nanoparticles. Develops novel polymeric, nano-delivery systems for delivery of water-insoluble and poorly bioavailable drugs. Manufactures photocatalytic coatings with nanoTiO2. Design of industrial standard nanotube-based materials for the following markets: aeronautics, automobile, sports, telecom's, plastics processing, renewable energy sources, building and public works and electronics. Supplier of carbon nanotubes and fullerenes. Producing engineered high performance advanced materials, including nanocomposites and nanomaterials, for applications in the environmental and energy industries. Develops and supplies custom nanomaterials to both industry and researchers. Single-walled carbon nanotubes and metallic nanopowders. Develops novel nanocomposite materials with enhanced optical properties. T E R I Report No.2006ST21:D2 URL http://www.xetacomp.com/ http://www.xintek.com/ http://www.zyvex.com/ http://www.zyvexpro.com/ http://www.millipore.com/ http://www.cimananotech.com/ http://www.daisanalytic.com/ http://dnanotech.com/ http://www.micromagnetics.com/ http://www.seashelltech.com/ http://www.adsdyes.com/ http://www.labopharm.com/ http://www.mchnanosolutions.com/ http://www.nanoledge.com/ http://www.nanonb.com/ http://www.nanoxnps.com/ http://www.nntech.com/ http://www.raymor.com/ http://www.lasysinc.com/ 78 A review of NT developments as applicable to developing countries ANNEXURE II: Nanotechnology based consumer items in the food sector Company Country Details La Posta del Aguila NanoSlim Nano Care Technology, Ltd. Shenzhen Become Industry & Trade Co., Ltd. Galaxia Nano Technology Limited Argentina Canada China China China Haier YuHang China Bottled water produced using filtration and nano silver treatment NT based technology for weight loss Tableware & kitchenware with nano silver coating Nanotea Nano Refrigerators Oriental Health Card, Nanotechnology insulation materials and other advanced space technologies, refrigerator. Quan Zhou Hu Zheng Nano Technology Co., Ltd. China Galaxia Nano Technology Limited China Pro-Idee GmbH & Co. KG Melitta Germany Germany Aquanova GmbH Germany Shemen Industries Israel NutraLease Ltd. A-DO Global Daewoo Israel Korea Korea A-DO Global Korea LG Electronics Korea Baby Dream Co., Ltd. Changmin Chemicals Korea Korea Samsung Korea Skybright Natural Health New Zeland SongSing Nano Technology Co., Ltd. Taiwan Nano-Infinity Nanotech Co., Ltd. Taiwan Top Nano Technology Co., Ltd. Taiwan SongSing Nano Technology Co., Ltd. Taiwan GreenPan™ USA NanoFilm® Ltd. OilFresh® Corporation USA USA Saeco USA Inc. USA Nano-silver Storage Box Increase the human immune system and the promotion of metabolism, elimination of subhealth / Nano Oxygen Supply Wateractivater Nanosilver incorporated cutting board Aluminium foil Dietary supplement, functional foods and drinks, as well as the cosmetics industries Canola oil with NSSL (Nano-sized self assembled structured liquids) i.e miscelles as carriers for vitamins, minerals and phytochemicals Nano-sized Self-assembled Structured Liquids (NSSL) technology. Nanosilver incorporated cutting board Refrierator using Nano Silver Poly technology Silver with Nano technology food container for the Antibacterial, Antibiotic effect by Nano Silver Bio silver and Bio shield with nano-size silver particles coat the interior of LG side by side refrigerator (Bio silver) and the gasket (Bio shield) of the refrigerator Silver nano poly system for feeding bottle Nano-silver bowls Nano technology for the interior coating of refrigerators for effective sterilization,deodorization and ant-bacterial effects The Colloidal Silver & Aloe Vera Gel has been formulated specifically for use in healing minor burns, sunburn, cuts, abrasions, insect bites and skin irritations Nanosilver spray for water purification / other applications Glycerin containing nano micelle product for removing pesticide residues on fruits/vegetable and oil/dirt on cutlery Precious metals techniques for reducing spiciness to give more aroma to malt wine Nano Plastic Wrap: which is used for 1. Anti-UV 2. Reflecting IR 3. Sterilizing and anti-mold 4. Having better temperature tolerance 5. Fireproof 6. Bearing grinding PTFE-free hybrid polymer nano-composite non-stick technology (ThermolonTM) 10 nm non-stick coatings for glass bakeware NT based frying oil refining catalytic device Coffee machine with nano silver coating to ensure milk residue buildup within the machine T E R I Report No. 2006ST21:D2 79 A review of NT developments as applicable to developing countries Company Country Details Ceramic non-stick Nano-GlazeTM on the inside and outside of vessels, Ceramcor, LLC USA teaware Nanoceuticals™ Slim Shake Chocolate using cocoa nanoparticles RBC Life Sciences®, Inc. USA ("CocoaClusters") for enhanced flavor without the need for excess sugar Ecosynthetix USA Starch adhesive using NT BlueMoonGoods, LLC USA Silver Nanoparticle Food Storage Containers Sharper Image USA silver nanoparticles food storage container & plastic storage bags Nano-nylon materials that can beat the cost of high-barrier plastics or even Honeywell USA glass. NT based an ultra thin coating applied on a 48 gauge polyester film Constantia Multifilm USA laminated to a CPP or PE sealant web American Biotech Labs USA Engineered Nano Silver Particles Alternative for eliminating Candida, parasites, worms, yeast, fungi, and Nano Health Solutions USA amoebas from the body without harmful side effects Life Enhancement USA Bionic Joint Support Nanotechnological–based supplements specifically targeted for SportMedix, Inc. USA professional and amateur athletes Nano Health Solutions USA Humic and Fulvic Acids Pharmanex USA Nutritional anti-aging program using NT Vitamin C using NT - Deliver tiny amounts of therapeutic substances to LivOn Labs USA specific organs or tissues without being altered and without affecting any other parts of the body MaatShop USA Skin Rejuvenator using nano-ized formula Natural mineral supplement in the form of an iridium colloid consisting of nanometer particles of 0.995 pure iridium / Natural mineral supplement in the form of a copper colloid consisting of nanometer particles of 0.9999 Purest Colloids, Inc. USA pure copper / Natural mineral supplement in the form of a palladium colloid consisting of nanometer particles of 0.9995 / Natural mineral supplement in the form of a platinum colloid consisting of nanometer particles of 0.9999 pure platinum Colloidal gold - has been reported to have a calming effect, increase Colloids for Life LLC USA energy and mental acuity, improve brain functions Nutrition By Nanotech, LLC USA Vitamin B-12 Mag-I-Cal.com USA Nano Calcium/Magnesium Developed a new line of nutritional and skincare supplements using RBC Life Sciences, Inc. USA nanotechnology / lowering the surface tension of drinking water using NT Life Enhancement USA Health supplement using NT Engineered nano-particle silver solution that can be used as an immune Greenwood Consumer Products USA support system NanoNutra Labs USA Nano-engineered medicine for weight loss Nanotechnology that transforms fat-soluble nutrients into water-soluble Solgar USA ones Nano Nutritional Supplement supporting cellular function for balanced Revive Health, LLC USA blood sugar levels and to hydrate cells / NT for the production of specialized supplement health products American Biotech Labs USA Engineered silver nano particle Health Plus International®, Inc. USA NT based Vitamin supplements Mercola Advanced Nutrition USA NT based Vitamin D Spray Utopia Silver Supplements® USA Advanced Colloidal Silver Source: http://www.nanotechproject.org/inventories/consumer/browse/categories/food_beverage/food/ T E R I Report No.2006ST21:D2