Full Issue - Pertanika Journal of Scholarly Research Reviews
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Full Issue - Pertanika Journal of Scholarly Research Reviews
The Per t ani kaJ our nalof Sc hol ar l yRes ear c h Re vi ews Vol .1,Dec ember2015 PJSRR(2015) 1(1): 1-7 © Universiti Putra Malaysia Press Pertanika Journal of Scholarly Research Reviews http://www.pjsrr.edu.my/ Internet and Facebook Use among University Students Susan PHUAa,b,*& Su Luan WONGa a Faculty of Educational Studies, Universiti Putra Malaysia, 43400 UPMSerdang. b UniversitiTunku Abdul Rahman, Jalan Sungai Long, Bandar Sungai Long, Cheras, 43000, Kajang, Selangor. *susanslphua@gmail.com Abstract – The Malaysian government continues to invest heavily in computing and Internet resources in the belief that the Internet can improve the academic performance of students, offer elearning for undergraduates, and provide the flexibility of distance learning for adult students. The use of the Internet and Facebook for educational purposes has been a topic of high interest among researchers in recent years. In Malaysia, Internet access is relatively easy, fast, and affordable. It is also a valuable source of information. Research shows that online consumers in Malaysia, Thailand and the Philippines are the most likely to have engaged on social media sites such as Facebook. For this very reason, students must be well-equipped with the requisite skills to exploit to the full the benefits of the Internet and Facebook by the time they graduate. Such skills would certainly help to enhance their employability in the competitive labour market. This study seeks to examine relevant literature regarding the extent of Internet and Facebook use among university students. The literature review will also explore how the use of the Internet and Facebook has impacted the academic performance of university students. Keywords: Facebook use, internet use, university students Introduction The widely held belief that students' academic achievement is impacted, either positively or negatively, by their use of the Internet as well as Facebook (Irwin, Ball & Desbrow, 2012) has led to much discussion among researchers. In a study by Sapari (2008), it was reported that the majority (64.5%) of Malaysian university students from various science and social science faculties use the Internet mostly for communication and information. This is not surprising as university students are encouraged to use the Internet to broaden their knowledge by accessing vital information and also communicating online with the academic community through Facebook (Boach, 2009). Several studies relating to Malaysian university students’ purpose of Internet usage had been conducted by researchers such as Luan, Fung, Nawawi, and Hong (2005), Sam, Othman, and Nordin (2005), Sapari (2008) and Muniandy (2010), and their findings suggested that Malaysian university students used the Internet for similar reasons as their counterparts in more developed countries. With regard to social networking, it can be a healthy form of communication if the user does not indulge in it excessively. Hamat, Embi, and Abu Hassan (2012) reported from their survey that university students made use of social networking sites for informal learning and exchanging information of mutual interest. Selwyn (2007) also found that students’ use of social networking sites had an impact on informal education. Purpose of the Study Encouragement by lecturers and tutors to exploit Information and Communication Technology (ICT) has led to more time being spent on the Internet by university students. A recent study by Newsweek Japan (as cited in Calderon, 2012) reported high Facebook usage amongst university students in 1 PJSRR(2015) 1(1): 1-7 © Universiti Putra Malaysia Press Malaysia, especially among females. Hence there is a need to investigate the extent to which the use of the Internet and Facebook impacts the academic performance of university students. Method A comprehensive search of the literature (magazines, dissertations, journals, and conference papers) through the early 1990sto 2012 was carried out to collect relevant information and data. The main objective of this article is to carry out a comparative literature review of studies on the use of the Internet and Facebook amongst university students in various parts of the world. Literature Review Malaysia was ranked 30th on the Global Networked Readiness Index (Global Information Technology Report, 2014). The most networked ready country was Finland, followed by Singapore in second position, and Sweden in third position. The last country on the list of 148 listed was Chad. Being one of the top 30 countries with network readiness meant that Malaysians used the Internet and were engaged on Facebook more than many other countries. According to official figures, Internet penetration in Malaysia by mid-2011 was among the highest in Asia, reaching as high as 17.5 million users or 60 percent of the population. The figure was further increased after the implementation of Kuala Lumpur Municipality’s new policy which required food and beverage businesses to provide free or low cost WiFi service at their outlets (Choong, 2012). Malaysia's Communications and Multimedia Commission (MCMC) (2014) also reported that the high Internet penetration in Malaysia in the second Quarter of 2014 was concentrated in Wilayah Persekutuan Putrajaya (98.9%), followed by Wilayah Persekutuan Labuan (86.7%), and Wilayah Persekutuan Kuala Lumpur (81.7%). Malaysia was dubbed the country with the most social network friends in 2010 and Facebook accounted for 77% of social network users (as cited in Calderon, 2012). Malaysia experienced a 26.4% growth in Facebook penetration within 12 months, with male users comprising 53% of Facebook accounts. By early 2012, Facebook was among the top five most visited websites, and Malaysians over the age of 15 spent approximately one-third of their time on social-networking services (ComScore, 2010). Facebook’s popularity will likely continue to soar with more people gaining access to the mobile web through the convenience of their smartphones. Internet users go online for various reasons. The Internet is used for both work and pleasure (Hills & Argyle, 2003). Besides providing entertainment and education materials for young and old (Madell & Muncer, 2004), it is also a platform for buying and selling products (Kraut, Lundmark, Kiesler, Mukhopadhyay, & Scherlis, 1997). As a result, the Internet has quickly become a natural part of everyday life (Bargh& McKenna, 2004). Nielsen, a leading global information and analytics provider, revealed in its survey that 1,321 Malaysian digital consumers who were surveyed spent close to 20 hours online each week ("Surging Internet Usage", 2011). According to the same survey, 53% of those surveyed accessed the Internet daily, 5% accessed it once or twice a month while the rest were less often Internet users. The report by Nielsen concluded that Malaysians were among the top users of the Internet in Southeast Asia. A recent summary of studies on Internet use in various countries was carried out by Wong, Bakar, Ayub, Sapari, Moses, and Khambari (2012). Their findings, which included the purpose of Internet use in various countries, reviewed a total of nine related studies. Table 1 depicts how undergraduate students used the Internet for various academic and non-academic activities. As can be seen in Table 1, Malaysian students generally used the Internet to perform four major and similar activities, namely information gathering, e-mailing, downloading software, and reading online newspaper. Other uses of the Internet included social networking, online banking, online shopping, online games, video watching and downloading music. Wong et al. (2012) concluded that Malaysian students used the Internet no differently from their counterparts in countries where Internet access was more readily available. 2 PJSRR(2015) 1(1): 1-7 © Universiti Putra Malaysia Press Table 1: Summary of Studies for Internet Use in Various Countries Authors Design Sample/Location Age (yrs) Size Purpose of Internet use Study 1: Weiser (2000) Survey University students/Texas, USA Exact age 506 range is not stated Entertainment, e-mail; educational & academic assistance; interpersonal communication; course information; research Study 2: Palesh, Saltzman &Koopman (2004) Survey University students/Moscow, Russia Exact age 198 range is not stated School-related activities; email; entertainment; chat & pornographic materials Study 3: Jones, JohnsonYale, Millermaier& Pérez (2008) Survey College students/USA Age range: 18-24 7421 Information, e-mail, instant messaging, wikis & chat Study 4: Okon (2010) Survey University students/Nigeria Not stated 536 Research; admission registration & tuition fees payment; e-mail; scholarship application; online newspaper Study 5: Tutgun, Deniz, & Moon (2011) Survey University students/Korea & Turkey Age range: 17-37 595 Study 6: Luan, Fung, Nawawi and Hong (2005) Survey University students/Malaysia Mean age: 22.63 310 Friendship; games; chat; develop websites & blogs; shopping, pornographic materials; gambling; games Information; e-mail; download software; online newspaper; games; shopping; e-banking Study 7: Sam, Othman and Nordin (2005) Survey University students/Malaysia Mean age: 23.8 148 Information; e-mail; download software; online newspaper; games; shopping; Study 8: Sapari (2008) Survey University students/Malaysia Age range: 21-26 361 Information; e-mail; download software; online newspaper; games; shopping; e-banking; & pornographic materials Study 9: Muniandy (2010) Survey University students/Malaysia Age range: 20–34 92 Information; e-mail; download software; upload files Adapted from “Malaysian Students’ Internet Use: Some Research Evidence” by S.L. Wong, A. R. Bakar, A. F. M.Ayub, N. A., Sapari, P., Moses, & M. N. M. Khambari, 2012, In Chang, B. et al. (Eds). Workshop proceedings of the 20th International Conference on Computers in Education, p. 102.Copyright 2012 by the Asia Pacific Society of Computers in Education. 3 PJSRR(2015) 1(1): 1-7 © Universiti Putra Malaysia Press Generally, 84% of students who used the Internet for academic purposes believed that the Internet had positively impacted their academic performance (Jones, Johnson-Yale, Millermaire & Perez, 2008).Today, most university libraries offer free access to hundreds of electronic databases and thousands of peer-reviewed journals, books and other online resources. The Internet has enabled education to be borderless and limitless. It is a just a matter of whether students know how to exploit these resources for their educational advancement (Wang & Artero, 2005). The Internet is clearly recognised as a powerful technological tool with various academic benefits, including access to abundant sources of news and information. Universities have begun to use management systems such as Blackboard and portals that connect them to online university resources and services. In fact, 94% of students reportedly used the Internet as a source of information when conducting research for their courses (O’Brien, 2011). Results of a research regarding the use of the Internet for academic communication purposes revealed that 84% of students used the Internet to communicate with their professors; they also agreed that using the email helped them express thoughts that they otherwise would not have shared in a classroom (Jones et al., 2008). The email is also extremely useful for student-instructor communication as queries on assignments, progression checks, feedback, and administrative matters can be conveyed with ease. Group projects are also made easy via email. One considerable advantage of the email is its ease of communication. One can write and receive emails anytime and anywhere if network connections are available. Online voice mail and video conferencing have emerged as technologies that can enhance long distance learning and online courses. Student interactions and student-lecturer interactions are made easy by these emerging technologies which are supported by the Internet (Carr-Chellman & Duchastel, 2000). The Internet allows lecturers and students to exchange thoughts, engage in intellectual discourse, brainstorm ideas, and share knowledge; lecturers can also offer their students emotional support (Baker, 2000). However, not everyone shares the view that the Internet and Facebook positively impact academic performance. Nie, Hillygus, and Erbring (2002) assert that time spent on the Internet displaces time for other activities while Franzen (2000) suggests that the Internet enables its users to increase efficiency and save time. Eberhardt (2007) reiterates that more research is needed to determine whether time spent on social network sites diminishes time spent on schoolwork or studying. It is unsure whether blame should be placed on the Internet and social networking sites as students already had the habit of procrastination long before the Internet and Facebook came into being (Wesley, 1994). A study by Kuh and Hu (2001) showed a positive relationship between the use of the Internet and engagement in effective educational practices. Communale, Sexton, and Voss (2002) found evidence to suggest that higher course grades were related to more frequent website use whilst a study conducted in a university in Sarawak revealed that in general, students had positive attitudes towards learning using the Internet regardless of their scholastic ability. It was found that students from the Faculty of Information Technology, Faculty of Engineering, and Faculty of Resource Sciences and Technology had more positive attitudes compared to students from other faculties. This could be because the students in these faculties were more exposed to the Internet for course related activities. These students had basic skills in using the Internet and were able to supplement their learning with the assistance of the Internet to improve their studies (Hong, Ridzuan & Kuek, 2003). A large majority of undergraduates have benefitted from the use of the Internet to do research and to communicate with their faculty and classmates (Jones et al., 2008). Facebook too, has been incorporated into classroom activities in universities globally. It helps university students better understand their assignments by enhancing their classroom experiences. It offers students a chance to break out of the traditional education norms. Facebook can create a school climate that is beneficial to both learning and growing (Olabanji, 2011). 4 PJSRR(2015) 1(1): 1-7 © Universiti Putra Malaysia Press Boogart (2006) observed that students who were frequent Facebook users reported a closer connectedness to their university than those who accessed it less frequently. It has also been reported that engaging on Facebook also helps build and maintain relationship among students. However, the same study reported a correlation between heavy Facebook engagement and lower GPAs. Another highly publicised report by Kirschner and Karpinski (2010) suggests that a relationship exists between the use of Facebook and low grades. Hamatet al. (2012) observe that the surge of interest to incorporate social media tools into education is due to their characteristics which allow interactivity and collaboration. Learning, according to advocates of socio-cultural theories of learning (Selwyn, 2007), becomes more effective in a social setting.Students and lecturers can communicate with one another because Facebook is an interactive website where messages and chats can be shared instantaneously. It can be used as a tool to enhance the academic integration of students (Madge, Meek, Wellens, & Hooley, 2009). Many students use Facebook to schedule group meetings and exchange information about assignments and deadlines. Lecturers post class announcements and offer reviews and academic support online. Facebook has the potential to be used as a technology that enhances classroom engagement. From the student’s perspective, education becomes more meaningful, and this will help to improve his or her academic performance (Olabanji, 2011). Facebook is considered as an extension of the classroom where different kinds of connection take place (Schwartz, 2009). In contrast, studies on the relationship of Internet use and academic performance by Chou and Hsiao (2000), Kubey, Lavin, and Barrows (2001) and Niemz, Griffins and Banyard (2005) revealed a negative association between Internet use and perceived impact on academic performances. However, a study by Gulek and Demitras (2005) found that after a year in a laptop immersion program, students showed significantly higher achievement in overall grade point average (Gulek & Demitras, 2005). Conclusion Rather than alienating the space between the home and university, educators should understand that the present generation of students is exposed to ICT at a very young age outside the classroom. By implementing the use of the Internet and Facebook engagement in the syllabi, students would benefit from making a meaningful connection between their personal lives and their academic lives. The most effective way to determine whether the Internet and Facebook have been properly integrated into the education of students is to observe the academic progress of the students who have used the technology (Hayes, 2006). Over-dependence on technology can be avoided if students are taught, prior to the integration of technology in the classroom, that they are not to rely solely on the Internet and Facebook but rather to use it as a tool to access and share ideas and information. Lastly, the authors of this paper acknowledge that the review was limited to studies carried out between the early 1990s and 2012. By and large, the Internet and social media technologies available to students during that period of time maybe different from the ones students have today. 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(2011).A comparative study of problematic internet use and loneliness among Turkish and Korean prospective teachers. Turkish Journal of Educational Technology, 10(4), 14-30. Wang, Y.M.& Artero, M. (2005).Caught in the web: University student use of web resources. Educational Media International,42(1), 71-82. Weiser, E. B. (2000). Gender differences in internet usage patterns and internet application preferences: A Two-Sample Comparison. Journal of Cyber Psychology & Behavior, 3(2), 167178. Wesley, J.C. (1994). Effects of ability, high school achievement, and procrastinatory behaviour on college performance. Educational and Psychological Measurement, 54(1), 404-408. Wong S.L., Bakar, A. R., Ayub, A. F. M., Sapari, N. A., Moses, P.,&Khambari, M. N. M. (2012). Malaysian students’ Internet use: Some research evidence. In Chang, B. et al. (Eds).Workshop proceedings of the 20th International Conference on Computers in Education (pp.98104).Singapore: Asia Pacific Society of Computers in Education. 7 PJSRR (2015) 1(1): 8-17 © Universiti Putra Malaysia Press Pertanika Journal of Scholarly Research Reviews http://www.pjsrr.edu.my/ Deep Mixing Columns a Shahram POURAKBARa* Department of Civil Engineering, Faculty of Engineering, Universiti Putra Malaysia, 43400 Serdang, Selangor Darul Ehsan, Malaysia a* Shahram.pourakbar@yahoo.com Abstract - The deep mixing columns (DMCs) is a stabilisation technique that uses cement and lime as stabilisation agents to improve the ultimate bearing capacity of soils. This method has numerous applications, such as foundation engineering, providing supporting wall for excavation, liquefaction mitigation, hydraulic cut-off wall, and environmental remediation. This current paper presents a brief history and a review of this promising technique for the purpose of ground improvement. Moreover, several previous works related to the ultimate bearing capacity of DMCs ground are reviewed which includes analytical analyses, laboratory works (small scale), and full scaled field tests. Finally the paper suggests further study and development topics and proposes steps forward to enhance the potential of alternatives for cement and lime replacement in this promising technique. Keywords: Deep mixing columns, soil stabilisation, ultimate bearing capacity Introduction A variety of soil stabilization techniques have been applied to improve the bearing capacity of soft ground, such as granular and prefabricated vertical drains, vacuum consolidation, granular column reinforcement (sand compaction piles, vibrated stone columns), and stabilising techniques (deep mixing, pre‐mixing and lightweight treated soil) (Kirsch & Bell, 2012; Sabih, Shafique, & Hussain, 2011). Of the soil stabilising techniques, deep mixing columns (DMCs) is becoming well established in an increasing number of countries because it is a cost-effective approach with numerous technical and environmental advantages including speedy implementation, elimination of off-site disposal, high ground strength, and impeding of biodegradation (Fang, Chung, Yu, & Chen, 2001; Saitoh, Suzuki, & Shirai, 1985). In a broad perspective, deep stabilisation of soils is an in situ soil modification technique using a stabilizing agent not only to improve bearing capacity but also to reduce settlement, preventing shear deformation of soils, and treating contaminated soils (Porbaha, 1998; Topolnicki, 2004). According to the literature, this method has several advantages (Kitazume, 2002; Kitazume & Terashi, 2013): (1) speed of construction, (2) strength calibration, (3) reliability, (4) variety of applications, and (5) effective use of resources. This method has numerous applications, such as foundation engineering, providing supporting wall for excavation, liquefaction mitigation, hydraulic cut-off wall, and environmental remediation (Hashizume, Okochi, Dong, Horii, Toyosawa, & Tamate, 1998; Okumura, 1996; Terashi, 2005). For instance, this method was successfully used to develop soft soil areas such as the Rawang-Ipoh Rail Double Tracking Project in Malaysia (Raju, Abdullah, & Arulrajah, 2003), and the Carriageway Trasa Zielona in Poland (Topolnicki, 2004). Several road and rail embankment stabilization projects have been completed in China, France, United Kingdom and Italy using this method (Massarsch & Topolnicki, 2005; Liu, Yi, & Zhu, 2008). Besides, the method has widely been used in the United Kingdom to treat the contaminate soil and encapsulation of contaminated soils, including cut‐off walls 8 PJSRR (2015) 1(1): 8-17 © Universiti Putra Malaysia Press and reactive barriers (Al Tabbaa & Evans, 2003). In addition, Japan extensively uses this promising method for different applications, one of which was the construction of about 15 km long Trans-Tokyo Bay Highway; whereby the soft clayey foundation soil was improved using a cement mixture to safeguard the tunnel (Kitazume, 2002). Elsewhere, this method was used for stabilizing failed levees and flood walls along Orleans Avenue Canal in New Orleans, USA (McGuire, Templeton, & Filz, 2012). In DMCs, the chemical agents, which are either slurry (wet mixing) or powder (dry mixing), are mixed into the soft ground to form columns of soil binders. For this purpose, a rotary mixing auger is drilled to the treatment depth. The drill's rotation direction is then reversed and retrieved whilst binders are pumped through the auger drill bit and the soil and binders are mixed (Bruce, 2001). Due to their robustness, easy adoptability, and economic value, cement and lime are employed as stabilizing agents in DMCs to produce stronger and firmer ground, namely soil–cement/lime columns (Kawasaki, Suzuki, & Suzuki, 1981; Prusinski & Bhattacharja, 1999; Saitoh, 1988). Although these traditional cementitious binders can improve many engineering properties of soils, they have several shortcomings, especially when viewed from an environmental perspective. This current paper presents a brief history and a review of this promising technique for the purpose of ground improvement. Moreover, several previous works related to the bearing capacity of DMCs ground are reviewed which includes analytical analyses, laboratory works (small scale), and full scaled field tests. Finally the paper suggests further study and development topics and proposes steps forward to enhance the potential of alternatives for cement and lime replacement in this promising technique. Deep mixing installation pattern Specially designed machines are used to construct in situ columns of soil-binder in various patterns. Several configurations of this method have been applied in the field, including: group, grid, wall, and block (Kitazume, 2002; Kitazume & Terashi, 2013). In the group column type improvement, treated soil columns or elements are installed in rows with either rectangular or triangular arrangements in a ground. The execution needs a relatively short curing period, and the volume of improvement is quite small (Figure 1 (a)). The group column type has been constructed to support small structures especially on land (Kitazume & Terashi, 2013). In the wall type improvement, as shown in (Figure 1 (b)), the long walls of treated soil with or without short walls oriented perpendicular to the centreline of superstructures are produced by overlapping adjacent columns (Kitazume & Terashi, 2013). The expected function of long wall is to bear the weight of superstructure and other external loads, and transfer them to the deeper stiff layer. The grid type improvement is an intermediate type between the block type improvement and the wall type improvement. The stabilized soils columns are installed by overlapping execution so that grid shaped improved masses are produced in the ground (Figure 1 (c)). This pattern is highly stable next to the block type improvement and its cost ranges between the block type and wall type improvements (Bruce, 2001; Kitazume & Terashi, 2013). In the block type improvement, a huge improved soil mass is formed in a field by overlapping all the stabilized soil columns (Figure 1 (d)). This type of improvement is normally applied to heavy and permanent structures such as breakwater and sea revetment in port, and harbour structures (Kitazume & Terashi, 2013). 9 PJSRR (2015) 1(1): 8-17 © Universiti Putra Malaysia Press Figure 1: Several configurations of deep mixing have been applied in the field including (a) Group column type improvement, (b) Wall type improvement, (c) Grid type improvement, and (d) Block type improvement From economical and construction considerations, the group columns type is desirable due to the small amount of improvement area and ease of installation as the treated columns are constructed without any overlapping (Kitazume & Terashi, 2013; Terashi, 1981). The deep mixing columns (DMCs) technique has some features in common with other ground improvement techniques such as the stone column technique. Both methods are employed to improve bearing resistance and control settlement in soft ground condition (Terashi, 2005). In addition, the design used in both cases depends on the area replacement area ratio. However, important differences are the material and installation technique used. The stone columns require granular material of suitable grading to be available and the vibrations generated during installation can cause problems. Deep mixing design The DMCs are designed to precisely address the needs of any particular situation, either by adjusting one or a combination of the following variables: columns diameter, replacement area ratio, mixing definitions, binder quantity, and binder type (Porbaha, Shibuya, & Kishida, 2000). In DMCs, the diameter of the columns ranges from 0.5 to 1.75 m, the spacing is generally 1.0 to 1.5 m centre to centre and the length usually varies from 10 to 30 m in normal practice for land applications. In some circumstances especially for harbour structures, 60 m long cement columns have been used (Bruce, 2001). The replacement area ratio, α, is the ratio between the total sectional area of the columns to the area of the ground occupied by the columns. According to Bruce (2001), in the common treatments applied in the Scandinavia and the United States, α, varies between 10 to 30%. In some situations, for preventing a sliding failure and lateral deformation due to seismic conditions, an α value of 30 to 50% has been applied (Bergado, Anderson, Miura, & Balasubramaniam, 1996). Those authors suggested that the total width of improved ground should be more than half of the thickness of the soft ground if a low α value is used. In DMCs, the stabiliser agent is injected at a pressure of up to 280 Bar into the hole by using a pumping system and a nozzle to mix the soil with the stabiliser agents either in the form of slurry (wet) or powder (dry) (Druss, 2002; Porbaha, 1998). After mixing process, there is a chemical reaction between the stabilising agent and soil that produces a composite material. This composite material is often compacted to a relatively high density so that its properties become similar to soft rock. The shear strength and modulus of elasticity of this material could be typically 10 to 20% of plain concrete (Jo, Hafez, & Norbaya, 2011) and hence they can be considered as an engineered low strength concrete columns. In such a condition, a substantial improvement in the soil bearing capacity is achieved which in turn reduces the overall foundation cost by allowing the structures to be built on shallow footing rather than pile foundation. It has been documented that the degree of this substantial improvement in the soil bearing capacity can be related to quantity of binder, 10 PJSRR (2015) 1(1): 8-17 © Universiti Putra Malaysia Press binder type, and curing time (Chew, Kamruzzaman, & Lee, 2004; Kawasaki et al., 1981; Kitazume & Terashi, 2013; Terashi, 1981). A number of studies have investigated the maximum effective percentage of binders to be mixed with particular types of soils to gain a considerable increase in the compressive strength and to achieve a desired improvement ratio (Kitazume & Terashi, 2013). Ahnberg, Ljungkrantz, and Holmqvist (1995) reported that between 5 to 40% of binder content with respect to the dry weight is usually required to stabilise soil columns. Meanwhile, 20 to 30% of binder content is typically used in Japan (Okumura, 1996; Yoshizawa, Tanaka, & Shekdar, 2004) and 10 to 50% of binder content is used in the United States (Bruce, 2001; Porbaha et al., 2000). From the literature, the difference in binder amount is due to the binder type and different reaction pathways in order to attain structural integrity (Kawasaki et al., 1981). Binder type Traditional cementitious binders Traditionally, the common binders in soil stabilization are lime, cement, or lime/cement (i.e., a mixture of lime and cement) (Kawasaki, Saitoh, Suzuki, & Babasaki, 1984; Kawasaki et al., 1981). Incorporation of these cementitious binders has gained popularity due to their robustness, easy adaptability, and cost effectiveness (Akpokodje, 1985; Miura, Horpibulsuk, & Nagaraj, 2001; Prusinski & Bhattacharja, 1999). In cemented soil, when the pore water of the soil makes contact with cement, hydration of the cement occurs rapidly and the major hydration (primary cementitious compounds) produces calcium silicate hydrate (C-S-H), calcium silicate hydrate (C-A-H), and hydrated lime Ca(OH)2 (Janz & Johansson, 2002). In lime-stabilized soil, soil particles become closer and the soil is treated through flocculation and pozzolanic reactions (Bell, 1996; Kamon & Nontananandh, 1991). Although the type of reaction in cemented soil is completely different in comparison with lime-stabilized soil, the final products, based on Si and Ca compounds, are very much alike. In terms of mechanical strength, cement-based binders usually deliver substantially better results than lime-based binders (Janz & Johansson, 2002). It should be noticed that the use of cementitious binders (i.e., cement and lime) in soil stabilization and specifically in DMCs is under discussion, not only for their negative environmental effects during manufacture but also for their cost. In the case of cement, this traditional binder generates around 7% of artificial CO2 emissions, because of carbonate decomposition (Gartner, 2004; Matthews, Gillett, Stott, & Zickfeld, 2009). It is estimated that every ton of cement produces around one ton of CO2, a major greenhouse gas implicated in global warming (Kim & Worrell, 2002; Lothenbach, Scrivener, & Hooton, 2011; Taylor, Tam, & Gielen, 2006). In addition to the emission of CO2, another by-product of cement production is NOx. Most of these nitrogen oxides are produced in cement kilns, which can contribute to the greenhouse effect and acid rain (Hendriks, Worrell, De Jager, Blok, & Riemer, 1998). Beyond these problems, the use of cementitious binders in DMCs shows poor tensile and flexural strength and a brittle behaviour (Correia, Oliveira, & Custódio, 2015; Sukontasukkul & Jamsawang, 2012). For instance, when the cemented soil column is subjected to seismic loads, either lateral earth pressures (as for deep-mixed soil walls) or horizontal displacements (as in the case of columns installed under the sides of embankments and in slopes), the stabilized soil tends to fail under tension, due to its brittleness (Correia et al., 2015; Sukontasukkul & Jamsawang, 2012). Another issue concerning about cement is associated with the intrinsic characteristics of the material that allow water and other aggressive elements to enter cemented soil columns, resulting in corrosion and carbonation problems (Fang et al., 2001). In the case of lime, it is essential to note that this soil binder reacts with water rapidly and increases the difficulty during deep mixing projects (Bell, 1996; Cong, Longzhu, & Bing, 2014). 11 PJSRR (2015) 1(1): 8-17 © Universiti Putra Malaysia Press Pozzolanic materials Several studies have focused on finding supplementary materials as partial replacements for traditional cementitious binders. In this respect, the use of pozzolanic materials deserves special attention. These materials are rich in silica (SiO2), alumina (Al2O3), and iron oxide (Fe2O3) with little or no cementitious value. It is a well-documented fact that pozzolanic binders cannot react completely by themselves during stabilization (Basha, Hashim, Mahmud, & Muntohar, 2005; Chen & Lin, 2009). However, when certain pozzolanic materials containing silica and alumina are added during the hydration of cementitious binders, the reaction produces an additional amount of C-S-H and C-A-H gels, the main cementing components (Dwivedi & Jain, 2014). A pozzolanic reaction takes place when high amounts of reactive SiO2, Al2O3, and Fe2O3 are mixed in the presence of water. Usually CaO is added to the mixture as lime or cement in Equation 1, while SiO2, Al2O3, and Fe2O3 can be presented in the pozzolan to develop further cementation gels including C-S-H and C-A-H. In this process, as shown in Equation 2, the hydration of the CaO liberates OHions, which causes the pH value to increase up to approximately 12. Under such circumstances, as shown in Equations 3 and 4, pozzolanic reactions occur: the Si, Al, and Fe combine with the available Ca, resulting in further cementation gels. Depending on the pozzolanic activity, the contribution of this reaction is usually developed at later curing stages (Dermatas & Meng, 2003; Pourakbar, Asadi, Huat, & Fasihnikoutalab, 2015; Seco et al., 2012). Therefore, pozzolanic materials require Ca(OH)2 in order to form strengthening products, while cementitious materials themselves contain quantities of CaO and can exhibit a self-cementitious (hydraulic) activity (Papadakis & Tsimas, 2002). (1) 2(3CaO.SiO2) + 6H2O = 3CaO.2SiO2.3H2O + 3 Ca(OH)2 Hydrolysis: Ca(OH)2 = Ca ++ + 2(OH)- (2) Pozzolanic reactions: Ca ++ + 2(OH)- + SiO2 (pozzolan rich in silica) = C-S-H (3) Ca ++ + 2(OH)- + Al2O3 (pozzolan rich in alumina) = C-A-H (4) The use of pozzolanic materials in DMCs is still at the early stage of development and, hence, need comprehensive research works in order to become technically and economically viable. Researches on deep mixing Analytical analyses Theoretically, a stress concentration on the treated soil columns occurs when the treated columns are much stiffer than the surrounding soil (Broms, 2003). In such condition, the foundation components will carry external loads and deform together. Thus, the internal stability of the columns may become a significant aspect of the design. Consequently the majority of the existing analytical methods for the determination of ultimate bearing capacity (qult) value of treated soil columns were mainly dependent on the strength performance of the columns. In light of the abovementioned explanation, the qult value of the model ground has been determined in several laboratory and full scale experiments based on two analyses including Broms (2000) and weighted method as shown in Equations 5 and 6, respectively. Broms’ method Weighted method qult =0.7 quc.α+ λ (1-α).Cus (5) qult = Cuc.α+ (1-α). Cus (6) 12 PJSRR (2015) 1(1): 8-17 © Universiti Putra Malaysia Press where Cus and quc are undrained shear strength of the soft ground and the unconfined compressive strength (UCS) value of the treated columns, respectively, where λ is a dimensionless coefficient, proposed by Bergado et al. (1996) to equal 5.5. Furthermore, as mentioned earlier, α is the replacement area ratio. Lower bound (qmin) and upper bound (qmax) of the qult of treated soil by means of group columns were established by Boussida and Porbaha (2004), and Bouassida, Jellali, and Porbaha (2009). Those researchers established lower and upper bounds based on the yield design theory. They assumed that the treated soil columns and untreated surrounding columns, which are deemed to have the same unit weight, are purely cohesive materials and that their resistance obeys Tresca’s criterion. According to the above-mentioned studies, the lower and upper bonds of qult can be computed using Equations 7 and 8. In addition, Kc indicates the cohesion ration band on Equation 9. qmin=Cus. [ 4 + 2α (kc-1)] (7) qmax= Cus.(2 √2 .√[1 + 𝛼(𝑘𝑐 − 1)][2 + α(kc − 1)]) (8) Kc= Cuc⁄Cus (9) in which Cus and Cuc are undrained shear strength of native soil and treated soil column, respectively, and α is replacement area ratio. Laboratory research studies A study conducted by Terashi (1981), who performed ten physical modelling tests in a laboratory with a range of improvement of the area ratio from 13 to 32% and the strength ratio that ranged from 11 to 173. That author used cement as a soil binder and the prefabricated soil cement columns were inserted into consolidated model ground for the column installation process. A rigid plate was used to load the model ground and the loading was displacement controlled. They reported a clear peak was observed when a strong column was used (quc = 1040 kPa) which indicates a brittle failure. According to their test results, progressive failures in the columns occurred so that individual column displacements at the overall peak load did not coincide. Other studies were conducted by Kitazume (1996), and Kitazume, Okano, and Miyajima (2000), who carried out physical modelling tests with an improvement area ratio of 79%, subjected to various combinations of vertical loads. The strength of the columns, quc, ranged from 213 to 27200 kPa. Sand was used as a drainage layer at the bottom of the specimen box and the box was then filled with kaolin slurry. Acrylic pipes with 20 mm inside diameter and 250 mm length were used to fabricate the cemented columns and extracted after seven days of curing. Further weeks of curing were conducted under water at room temperature. All the model tests were carried out in an undrained condition. They reported that the magnitude of the stress increased rapidly with the increase in displacement and the peak stress occurred at about 0.05 to 0.10 of normalised vertical displacement. Moreover, they found that the failure mode depends on the column strength (due to presence of cement) and vertical load component. Boussida and Porbaha (2004) carried out the research on the qult of ground improved by means of the group column type. The study focused on an improvement area ratio of 18.8% with varying column strength. Clay was used to construct the soft ground and sand was used for a drainage layer at the bottom of the box. Soil cement columns of diameter 20 mm were constructed and cured outside of the 13 PJSRR (2015) 1(1): 8-17 © Universiti Putra Malaysia Press soil. The column installation technique was similar to that of Terashi (1981). The model was left in fully saturated conditions for two days before loading was carried out. According to their test results, peak load values were observed for all tests at less than 10% of normalised displacement and the failures were classified as brittle failures. A study was performed by Yin and Fang (2010), who conducted a physical modelling test on DMCs with an improvement area ratio, α, of 12.6%. A rigid box with dimensions 900 mm width by 300 mm length was used to study the qult value of the cemented soil column under a 300 mm wide footing. The column preparation and installation technique were similar to that of Terashi (1981). According to this study, a brittle failure was observed from the stress‐normalised displacement curve. Full scale-field tests Bergado, Ruenkrairergsa, Taesiri, and Balasubramaniam (1999) conducted a case study on the Bagna‐ Bangkapong Highway in Thailand improved by the DMCs. The purpose of the study was to investigate the qult and settlement of the DMCs. The column diameter was 0.6 m and the length was either 14 m or 16 m. The spacing centre to centre between the columns was 1.5 m. A wet mixing method with 150 kg/m3 of cement was used in order to achieve 600 kPa column strength in the field. The floating column group was constructed on soft clay having an average shear strength of 12.5 kPa. Those authors found that the qult was larger than the embankment loading and measurements from plate bearing tests. Lin and Wong (1999) conducted a static load test on floating soil cement columns at the Fu‐Xia Expressway, Fujian Province, China. Two columns were loaded, after being mixed in situ and cured for 28 days, by jacking against steel beams loaded with sand bags. The diameter of the columns was 0.5 m and the length was 9.6 m for column three and 8.6 m for column four. By considering that the failure occurred when the settlement reached 25 mm, the qult of columns was 150 kN and 183 kN and the maximum compression strength was 667 kPa and 832 kPa, respectively. Lin and Wong (1999) concluded that the failure of columns three and four could be due to either soil or column material failure. Those authors found that the ultimate unit skin friction was 50% for column three and 70% for column four of the average shear strength of the soft clay, 15 kPa. Disturbance of the surrounding clay during column installation could have reduced the skin friction initially. For the column material failure, they suspected that could have been caused by the heterogeneity of the cement mixing with the soil in the field. As a result, the strength of the column in the field was lower than the strength obtained from a laboratory trial mix. Chai, Liu, and Du (2002) observed the performance of the DMCs at the Lian‐Yun‐Gang section of the Xu‐Lian Expressway in eastern China. The field vane shear strength ranged from 5 kPa to 25 kPa over a 10 m depth. A group of cement columns with a diameter of 0.5 m and 10 m long were installed using the dry mixing method. The columns were arranged in a triangular pattern with 1.1 m to 1.6 m spacing. In most cases, the amount of cement used was 59 kg/m3 to achieve the strength of 0.8 MPa. Field loading tests were conducted on a single column and on a composite foundation which covered either two or three columns. For the single cement column, a square loading plate with an area of 0.25 m2 was used. Chai and his co-workers found that the average compression strength of the column was 0.96 MPa which was close to the value of the laboratory unconfined compression strength (0.8 MPa). As a result, they concluded that the qult of a single fully penetrated cement column was due to the failure of the column itself. For the composite foundation, a study was made with different column spacing (1.1 m, 1.2 m, 1.4 m and 1.6 m) with different areas of loading plate for the three columns group (3.14 m2, 3.84 m2, 5.25 m2 and 6.65 m2). As a result, different improvement area ratios underneath the loading plate were tested (8.9%, 11.2%, 15.3% and 18.8%). They concluded that the qult increased with increasing improvement area ratio, although the conditions in each test were not exactly the same and a precise comparison is not possible to achieve under field conditions. 14 PJSRR (2015) 1(1): 8-17 © Universiti Putra Malaysia Press Summary and conclusions From the review of the literature available to date, it can be seen that the DMCs provides an alternative to more traditional methods of soil stabilization. Several configurations of this method have been applied in the field, including: group, grid, wall, and block. From economical and construction considerations, the group columns type is desirable due to the small amount of improvement area and ease of installation as the treated columns are constructed without any overlapping. The majority of the existing analytical methods for the determination of ultimate bearing capacity value of DMCs were mainly dependent on the strength performance of the columns. In this respect, the ultimate bearing capacity value of the model ground has been determined in several laboratory and full scale experiments based on two analyses including Broms and weighted methods. According to the laboratory results, the failure mode depends on the column strength (due to the presence of cement and other cementitious binders) and vertical load component. Moreover, according to full scale tests, the strength of the column in the field was lower than the strength obtained from a laboratory trial mix. Traditionally, the common binders in DMCs are lime, cement, or lime/cement (i.e., a mixture of lime and cement). Although the type of reaction in cemented soil is completely different in comparison with lime-stabilized soil, the final products, based on Si and Ca compounds, are very much alike. The use of cementitious binders (i.e., cement and lime) in DMCs is under discussion, not only for their negative environmental effects during manufacture but also for their cost. Since the pozzolanic materials are rich in silica, alumina, and iron oxide with little or no cementitious value, the use of these materials in DMCs deserve special attentions. References Ahnberg, H., Ljungkrantz, C., & Holmqvist, L. (1995). Deep stabilization of different types of soft soils. Paper presented at the Proceedings of 11th Conference on Deep Mixing Method, Copenhagen. Akpokodje, E. (1985). The stabilization of some arid zone soils with cement and lime. Quarterly Journal of Engineering Geology and Hydrogeology, 18(2), 173-180. Al Tabbaa, A., & Evans, C. (2003). Deep soil mixing in the UK: geoenvironmental research and recent applications. Land Contamination and Reclamation, 11, 1-14. Basha, E., Hashim, R., Mahmud, H., & Muntohar, A. (2005). 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Study of bearing capacity of lime–cement columns with pulverized fuel ash for soil stabilization using laboratory model. Electronical Journal of Geotechnical Engineering, 16, 1595-1605. Kamon, M., & Nontananandh, S. (1991). Combining industrial wastes with lime for soil stabilization. Journal of Geotechnical Engineering, 117(1), 1-17. Kawasaki, T., Saitoh, S., Suzuki, Y., & Babasaki, R. (1984). Deep mixing method using cement slurry as hardening agent. Paper presented at the Proceeding of Seminar on Soil Improvement and Construction Techniques in Soft Ground, Singapore. Kawasaki, T., Suzuki, Y., & Suzuki, Y. (1981). On the deep mixing chemical mixing method using cement hardening agent (Technical Research Report No. 26, 13-42). Osaka: Takenaka Corporation. Kim, Y., & Worrell, E. (2002). CO2 emission trends in the cement industry: An international comparison. Mitigation and Adaptation Strategies for Global Change, 7(2), 115-133. Kirsch, K., & Bell, A. (2012). Ground improvement. 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Chinese Journal of Rock Mechanics and Engineering, 27(11), 2272-2280. 16 PJSRR (2015) 1(1): 8-17 © Universiti Putra Malaysia Press Lothenbach, B., Scrivener, K., & Hooton, R. (2011). Supplementary cementitious materials. Cement and Concrete Research, 41(12), 1244-1256. Massarsch, K., & Topolnicki, M. (2005). Regional Report: European practice of soil mixing technology. Paper presented at the Proceeding of International Conference on Deep Mixing– Best Practice and Recent Advances, Stockholm. Matthews, H. D., Gillett, N. P., Stott, P. A., & Zickfeld, K. (2009). The proportionality of global warming to cumulative carbon emissions. Nature, 459(7248), 829-832. McGuire, M., Templeton, E., & Filz, G. (2012). Stability analyses of a floodwall with deep-mixed ground improvement at Orleans Avenue Canal, New Orleans. Geotechnical and Geological Engineering, 211(7), 199-209. Miura, N., Horpibulsuk, S., & Nagaraj, T. (2001). Engineering behavior of cement stabilized clay at high water content. Soils and Foundations, 41(5), 33-45. Okumura, T. (1996). Deep mixing method of Japan. Paper presented at the proceeding of the 2nd International Conference on Ground Improvement Geosystem, Tokyo. Papadakis, V., & Tsimas, S. (2002). Supplementary cementing materials in concrete: Part I: efficiency and design. Cement and Concrete Research, 32(10), 1525-1532. Porbaha, A. (1998). State of the art in deep mixing technology. Part I: Basic concepts and overview. Ground Improvement, 2(2), 81-92. Porbaha, A., Shibuya, S., & Kishida, T. (2000). State of the art in deep mixing technology. Part III: geomaterial characterization. Proceedings of the Institution of Civil Engineers - Ground Improvement, 4(3), 91-110. Pourakbar, S., Asadi, A., Huat, B. B., & Fasihnikoutalab, M. H. (2015). Stabilization of clayey soil using ultrafine palm oil fuel ash (POFA) and cement. Transportation Geotechnics, 3, 24-35. Prusinski, J. R., & Bhattacharja, S. (1999). Effectiveness of Portland cement and lime in stabilizing clay soils. Transportation Research Record: Journal of the Transportation Research Board, 1652(1), 215-227. Raju, V., Abdullah, A., & Arulrajah, A. (2003). Ground treatment using dry deep soil mixing for a railway embankment in Malaysia. Paper presented at the Proceedings of the 2nd Conference on Advances in Soft Soil Engineering and Technology, Kuala Lumpur. Sabih, O., Shafique, M. J., & Hussain, R. R. (2011). Methods of Soil Stabilization. Boca Raton: CRC press. Saitoh, S. (1988). Experimental study of engineering properties of cement improved ground by the deep mixing method (Unpublished PhD Thesis). Nihon University, Tokyo. Saitoh, S., Suzuki, Y., & Shirai, K. (1985). Hardening of soil improved by deep mixing method. Paper presented at the Proceedings of 11th International Conference on Soil Mechanics and Foundation Engineering, San Francisco. Seco, A., García, B., Prieto, E., Ramirez, F., Miqueleiz, L., Urmeneta, P., & Oroz, V. (2012). Types of Waste for the Production of Pozzolanic Materials-A Review. Rijeka: Intech Press. Sukontasukkul, P., & Jamsawang, P. (2012). Use of steel and polypropylene fibers to improve flexural performance of deep soil–cement column. Construction and Building Materials, 29, 201-205. Taylor, M., Tam, C., & Gielen, D. (2006). Energy efficiency and CO2 emissions from the global cement industry. International Energy Agency, 5(2), 117-126. Terashi, M. (1981). Ground improved by deep mixing method. Paper presented at the Procceding of 10th International Conference on Soil Mechanics and Foundation Engineering, Stockholm. Terashi, M. (2005). Keynote lecture: design of deep mixing in infrastructure applications. Paper presented at the International Conference on Deep Mixing Best Practice and Recent Advances, Tokyo. Topolnicki, M. (2004). In situ soil mixing. Proceedings of the Institution of Civil Engineers - Ground Improvement, 5(2), 331-428. Yin, J. H., & Fang, Z. (2010). Physical modeling of a footing on soft soil ground with deep cement mixed soil columns under vertical loading. Marine Georesources and Geotechnology, 28(2), 173-188. Yoshizawa, S., Tanaka, M., & Shekdar, A. (2004). Global trends in waste generation. Recycling, Waste Treatment and Clean Technology, 7, 1541-1552. 17 PJSRR (2015) 1(1): 18-26 © Universiti Putra Malaysia Press Pertanika Journal of Scholarly Research Reviews http://www.pjsrr.edu.my/ Olivine for Soil Stabilization Mohammad Hamed FASIHNIKOUTALABa* a Department of Civil Engineering, Faculty of Engineering, Universiti Putra Malaysia, 43400 Serdang, Selangor Darul Ehsan, Malaysia * hfasih@gmail.com Abstract-The aim of this paper is to review the potential capability of olivine as a new binder for soil stabilization. The recent research shows that using environmental friendly materials for soil stabilization is expanding. The increasing amount of greenhouse gasses (GHG) such as CO2 has also instigated research into finding environmentally friendly materials for soil stabilization. For quite some time, cement is one of the well-known binders in soil stabilization, but it releases high amount of CO2, and energy consumption of cement have caused civil engineers to use some other materials or by-products to fully or partially replace cement for soil stabilization. Recently, alkaline activation process in soil stabilization is an interesting option at medium-term to fully eliminate traditional cementitious binders such as cement and lime. Olivine is a well-known material for CO2 sequestration. Furthermore, the high amount of SiO2, Al2O3 and Fe2O3 in olivine could classify this mineral as a pozzolanic material in soil stabilization. Keywords: Carbonation, olivine, soil stabilization, pozzolanic material, dissolution Introduction Using cement in civil engineering comes with several significant disadvantages, the most important of which is the resultant release of carbon dioxide (CO2) into the atmosphere. CO2 is the leading greenhouse gas which is an outcome from fossil fuels and human activities, and it causes climate change and global warming. In the 1950s, CO2 doping grew about 0.7 ppm per year. In the last decade, the CO2 level significantly increased by 2.1 ppm per year (Hanle, Jayaraman, & Smith, 2004; Ke, Mcneil, Price, & Khanna, 2013). Olivine is a sustainable material that has the potential for use in treating soils as it can capture CO2 because of the high amount of MgO. The literature indicates the effect of carbonating reactive magnesia for soil stabilization and the positive role of reactive magnesia against cement treated soil (Yi, Liska, Unluer, & Al-Tabbaa, 2013; Yi, Liska, Akinyugha, Unluer, & Al-Tabbaa, 2013). Soil stabilization Soil stabilization is one of the oldest and most widespread techniques among the ground improvement methods because construction on soft ground is a main problem in civil engineering. If the ground is 18 PJSRR (2015) 1(1): 18-26 © Universiti Putra Malaysia Press untreated, it is not good enough for the construction, and the bearing capacity or slope failure may occur because of insufficient soil strength (Lee & Karunaratne, 2007). Stabilized soil is, in general, a composite material that results from a combination and optimization of properties in individual constituent materials. Well-established techniques of soil stabilization are often used to obtain geotechnical materials improved through the addition into soil of such cementing agents (Basha, Hashim, Mahmud, & Muntohar, 2005). The solution of refining these soils in-situ by stabilization often becomes handy, as this has the insinuation of natural resource conservation, reduction in energy usage and carbon dioxide release and increased cost efficiency (Obuzor, Kinuthia, & Robinson, 2012). Many binder materials possess hardening applications which could potentially be used for the stabilization of soils. Soils with high water content stabilized by traditional mixtures have been commonly used for the construction purpose to enhance bearing capacity, reduce settlement, control shrinking and swelling, and reduce permeability (Miller & Azad, 2000; Åhnberg & Johansson; 2003, Basha, Hashim, Mahmud, & Muntohar, 2005). Although such traditionally chemical stabilizers have been economically attractive, from an environmental point of view, it is more prudent to consider industrial by-products for soil stabilization that are most cost-effective, and not affecting the surrounding soil and groundwater ecology upon treatment. Nevertheless, there are some negative effects of using some of these materials in soil stabilization. Soil stabilization by cement and lime Cement is often used as an additive to improve the strength and stiffness of soft clayey soils, and the increase in strength of soft soil by cement is well recognized. Cement treated soils have been developed in the field of geotechnical engineering (Uddin, Balasubramaniam, & Bergado, 1997; Miura, Horpibulsuk, & Nagaraj, 2001; Chew, Kamruzzaman, & Lee, 2004; Horpibulsuk, Rachan, & Suddeepong, 2011). Cement can be used for both modification and stabilization purposes. The addition of a few percentages by weight of cement has shown its success to better control the workability during compaction, and significant cost savings over the removal and replacement of filled materials in some projects (Sariosseiri & Muhunthan, 2009). The properties of cement-treated soil can be divided into primary and secondary cementitious materials in the soil cement matrix. The primary cementitious materials formed by hydration reaction are composed of hydrated calcium silicates (C2SHx, C3S2Hx), calcium aluminates (C3AHx, C4AHx), and hydrated lime Ca(OH)2. A secondary pozzolanic reaction between the hydrated lime and the silica and alumina from the clay minerals leads to the formation of additional calcium silicate hydrates (CSH) and calcium aluminate hydrates (CAH) (Chew et al., 2004; Kasama, Zen, & Iwataki, 2007). The reduction in plasticity index (PI) caused by an increasing plastic limit (PL) and soil swelling, and outstanding increase in strength, modulus of elasticity, and resistance against the effects of moisture can be significantly achieved by cement stabilization. The addition of cement increased the optimum water content (OWC) but decreased the maximum dry density (MDD) (Muhunthan & Sariosseiri, 2008; Horpibulsuk et al., 2011). Lime, CaO or Ca(OH)2, is the burned byproduct of lime stone (CaCO3), which is one of the oldest developed construction materials that is still popularly used to improve fine-grained soils. Today, lime stabilization is extensively used in numerous structures such as highways, railways, airports, embankments, foundation base, slope protection, canal linings, and others (Muhunthan & Sariosseiri, 2008; Wilkinson, Haque, Kodikara, Adamson, & Christie, 2010; Dash & Hussain, 2011). A considerable amount of literature has been published on soil stabilization by lime. On a major study about the chemical stabilization, the researcher investigated the data on the interaction of the clay from the Mirkovo deposit with lime, and he suggested that under the chosen experimental conditions, the increase in strength during the first six months is entirely caused by the initially formed and hardened gelated products of pozzolanic reactions involving mainly the clay minerals (Ref?). A stabilized soil material is obtained with dry unconfined compressive strength (UCS) of the order of 19 PJSRR (2015) 1(1): 18-26 © Universiti Putra Malaysia Press 5MPa to 6MPa. The processes causing changes in the phase composition of the calcium hydrosilicates occur at long storage times (Ninov, Donchev, Lenchev, & Grancharov, 2007). Lime can change the soil plasticity. First, a decrease in the liquid limit (LL) and an increase in the PL result in an important reduction in PI. Reduction in PI facilitates higher workability of the treated soil. Second, a reduction in water content occurs as a result of chemical reaction between soil and lime (Petry & Little, 2002; Barker, Rogers, & Boardman, 2006). Apart from modifying the plasticity and swelling characteristics, lime can stabilize the soils through cementation, visible increasing soil strength and stiffness (Rajasekaran & Narasimha Rao, 2000; Alavéz-Ramírez, Montes-García, Martínez-Reyes, Altamirano-Juárez, & Gochi-Ponce, 2012). The strength of lime-treated soils is primarily dependent on the dissolved SiO2 and Al2O3 available for pozzolanic reactions, as well as on the existing amounts of Ca2+ and OH-. Once the ions Ca2+ and OH- are fully consumed, the pH drops, and the pozzolanic reactions cease, unless the amounts of Ca2+ and OH- are restored to the soil limewater system (Barker et al., 2006; Consoli, Lopes, Prietto, Festugato, & Cruz, 2011). However, the lime-treated soil shows a complex behavior that is affected by several factors such as the physicochemical properties of the soil, porosity, and the lime content at the time of compaction (Pedarla, Chittoori, Puppala, Hoyos, & Saride, Sireesh, 2010). Cement and lime production involves CO2 emission. The cement industry produces 5% of global man-made CO2 emissions, of which 40% and 50% are from burning fuel and chemical process, respectively. The rests are divided between transport and electricity uses (The Cement Sustainability Initiative, 2002). This emission is a contributing factor to the significant global warming expected in future decades. For example in 2010, the China cement output was 1.9 gigatonnes, which accounted for 56% of the world cement production. The Total CO2 emissions from the Chinese cement production can therefore exceed 1.2 gigatonnes (Ke et al., 2013). CO2 is emitted from the calcination process of limestone, from combustion of fuels in the kiln, and from power generation. In addition, CO2 is formed by calcination, which can be expressed by Equation 2.1. According to the equation, 1 kg of CaCO3 can release 0.44 kg of CO2 (Worrell, Price, Martin, Hendriks, & Meida, 2001). CaCO3 + Heat → CaO + CO2 1kg (1) 0.56 kg + 0.44 kg Using magnesium oxide in soil stabilization Soil stabilization may be a technique introduced several years ago with the main purpose to render the soils capable of meeting the necessities of the particular engineering projects (Kolias, KasselouriRigopoulou, & Karahalios, 2005). Stabilized soil is a composite material that results from the combination and optimization of properties in individual constituent materials. Well-established techniques of soil stabilization are typically used to obtain geotechnical materials that are improved by adding into soil of such cementing agents as Portland cement, lime, and asphalt. The replacement of natural soils, aggregates, and cement with solid industrial by-product are extremely captivating (Basha et al., 2005). Previous studies show the effects of using Mg oxide for soil stabilization, for example, the use of Mg hydroxide to stabilize the swelling clay. The results concluded that the Mghydroxide is absorbed by swelling clays both on their external and internal surfaces, whereas it is adsorbed on the external surface by non-swelling clays. The internally adsorbed phase of Mghydroxide forms an ill-defined interlayer of brucite to retard swelling, whereas the external phase covers the particles drastically to modify their surface properties (Xeidakis, 1996). The study indicated that the principal forces concerned in the process are believed to be physical adsorption on the external surface, and a few chemical bonding, largely in the inner surface. Furthermore, cementation occurs because of crystallization and, in the long term, some pozzolanic reactions occur. Internal adsorption of the Mg-hydroxide is postulated to be in the shape of completely charged mono- and/or small polymers, and it is chiefly diffusion controlled. Given that 20 PJSRR (2015) 1(1): 18-26 © Universiti Putra Malaysia Press Mg-hydroxide is internally adsorbed by swelling clays whereas Ca-hydroxide (lime) is not, and also the Mg Ca-clay aggregates are more stable than the Ca-clay or the Mg-one, the mixture of the two hydroxides might provide higher results in soil stabilization than hydroxide alone (Xeidakis, 1996). Another study showed the effect of a low grade MgO on the stability of contaminated soil. The investigation showed that the contaminated soil is stabilized with a low grade MgO, independent of the amount of stabilizer used, and a pH close to 9.2, that is controlled by the solubility of the Mg(OH)2 (García et al., 2004). In 2010, the investigation about the sustainable material for soil stabilization indicated that the industrial by-products, specifically GGBS, PFA, and cement kiln dust (CKD), and innovative materials such as reactive magnesia and zeolite, clearly have various sustainability benefits over PC in terms of reduced environmental impacts and enhanced technical and durability performances. The stabilization of gravelly sand and clayey silt with a range of PC-blended binders using the above materials showed that all these materials can act as partial replacement for PC in ground improvement applications, which rely on the dosage applied and/or curing time that provided higher strengths (Jegandan, Al-Tabbaa, Liska, & Osman, 2010). Another study has looked at the properties of the two kinds of soil with different blends and contents of GGBS, lime, MgO, and PC. The investigation has focused on the effect of mixed MgO and GGBS and compared the result by using PC and GGBS-lime mixture on soil stability. The final outcome of this research concluded that the UCS results showed that GGBS-MgO was more extreme than GGBSlime for soil stabilization with an optimum MgO content in the range of 5% to 20%; also the 28 days UCS value of MgO-GGBS are up to four times higher than mixed PC (Y. Yi, Liska, & Al-Tabbaa, 2014). The recent study in 2013 mentioned the effect of carbonating magnesia for soil stability. The study concluded the effect of carbonated reactive magnesia on the soil stability compared with PC blended in soil. Results showed the treated soil by reactive carbonated magnesia after a few hours has the same stability of 28 days of soil stabilized by PC. The main products of reactive magnesia carbonated are nesquehointe and hydromagnesite-dypingite that are responsible in soil stability (Yaolin, Martin, Cise, & Abir, 2013; Yi, Liska, Unluer, & Al-Tabbaa, 2013). Olivine characterization Olivine with the formula (Mg,Fe)2SiO4 is a magnesium iron silicate. It is a prevalent mineral within the Earth's subsurface and is usually found in mafic to ultramafic igneous rocks. It is found less commonly in marbles and some alternative metamorphic rock types (Jesa, 2011). The ratio of magnesium to iron can vary in any proportion from pure Mg2SiO4 (fosterite) through to pure Fe2SiO4 (fayalite). Olivine can exist with colours ranging from yellowish green, olive green, greenish black and reddish brown with densities from 3.27 to 3.37 and averaging 3.32 g/cm3 (Barthelmy, 2010). Table 1 shows the nominal chemistry and physical properties of olivine, which, according to chemical composition, consists of approximately 45% to 49% of MgO. Table 1: Physical properties of olivine MgO 48.28% SiO2 40.32% Fe2O3 8.9% Al2O3 1.37% LOI 1.13% Olivine worldwide distribution Olivine is found all over the world: India, Myanmar, Egypt, Pakistan, South Africa, Russia, Norway, Sweden, Germany, France, Brazil, Mexico, Ethiopia, China, Australia, and the USA. As early as 1500 BC Egyptian pharaohs mined olivine on Zabargad Island in the Red Sea. Olivine can be detected in the green beaches in Hawaii as well as in meteorites on Mars and Moon(“What is Olivine,” 2013). In Malaysia, according to its geology, there is a possibility of olivine being mined. According to a study 21 PJSRR (2015) 1(1): 18-26 © Universiti Putra Malaysia Press of the Tawau geological heritage area located in the eastern part of Semporna Peninsula in Sabah, West Malaysia, volcanic rocks of the andesite-dacite association form the major mountainous backbone in this area. The rocks contain plagioclase, olivine, hornblende phenocrysts, clinopyroxene, and magnetite microcrystals (Tahir, Musta, & Rahim, 2010). There is every possibility of surface mining the substantial amount of olivine that exists here. Alternatively in tropical areas, the great advantage of this is the fast weathering in tropical areas (Schuiling & Praagman, 2011). Olivine dissolution Dissolution and hydrolysis are the results of reactions with acids. Hydrolysis occurs as the transformation of silicate and carbonate minerals into new minerals. In this process, there is total dissolution of the original rock leaving no solid residue(Kayar, 2011). It can be generally explained that olivine dissolution happens when-carbonate-saturation-is-attained in the fluid stage, resulting in the precipitation of magnesite, and summarized as follows (Dufaud, Martinez, & Shilobreeva, 2009): Mg2SiO4 + 3H2O + 2CO2 → Mg2+ + Mg3Si2O5(OH)4 + 2HCO−(2) Earlier research findings on the description of the dissolution rate of olivine at low-temperature-canbe-extended-to-higher temperature, which could contain its behaviour as a function-of-pH, in the presence of CO2, and at pH ≤ 5 (at 120 °C).Dissolution rates have been found to be two times greater than-those-without-CO2-at the same pH. Citric acid, another ligand previously studied in the literature, also shows a dissolution improvement effect (Hänchen, Prigiobbe, & Storti, 2006). As a result, certain scholars have pointed out that-sorption-of-inorganic carbon type to surfaces can affect dissolution performance for Fe oxides and Ca or Mg silicates. Even at alkaline conditions; silicate dissolution rates demonstrate only an-insignificant-or-at-best-weak condition on PCO2 when pH is held constant. For example, the liberation of Ca and Mg from diopside during dissolution decreased slightly or not at all for PCO2> atmospheric (Brantley, 2008). Many factors affect the dissolution rate of olivine, and some of the most important factors are: the grain size, temperature, solution chemistry (pH, concentration of carbonate, magnesium, silica, organic acids, ionic strength), and the formation of the coating on the grains (Veld, Roskam, & Enk, 2008). Mineral carbonation, that includes the reaction of Mg-rich minerals with CO2 to produce geologically stable mineral carbonates, has been proposed as a promising CO2capturing technology. Potential of using olivine for soil stabilization Regarding the chemical properties of olivine as shown in Table 1, olivine is the major source of magnesium oxide (MgO) which makes up to between 45% to 49% by weight. Prior research has demonstrated that magnesium oxide can be successfully utilized for soil stabilization, for example, the use of Magnesium hydroxide to stabilize swelling clay (Xeidakis, 1996). Another investigation studied how a low grade MgO affected the stability of contaminated soil, and the results showed that the contaminated soil was successfully stabilized with the low grade MgO (García et al., 2004). A significant study conducted in 2010 addressed the use of sustainable materials for soil stabilization. The study investigated the effect of mixing industrial by-products with innovative materials such as reactive magnesia and zeolite. These were demonstrated to clearly show a variety of sustainability benefits over PC in terms of reduced environmental impacts and enhanced technical and durability performance (Jegandan et al., 2010). A recent study in 2013 investigated the effects of carbonating magnesia on soil stabilization by comparing it with PC blended in soil. The results showed that soil treated with reactive carbonated magnesia after a few hours had the same stability of soil stabilized by PC after 28 days. The main reaction products of carbonated magnesia responsible for the increased stability were nesquehointe and hydromagnesite-dypingite (Yi, Liska, Unluer, & Al-Tabbaa, 2013). The formulations below show the main products of reactive carbonated magnesium: MgO + H2O → Mg(OH)2Brucite (3) 22 PJSRR (2015) 1(1): 18-26 © Universiti Putra Malaysia Press Mg(OH)2 + CO2 +2H2O → MgCO3 . 3H2O Nesquehonite (4) 5Mg(OH)2 + 4CO2 + H2O → (Mg)5(CO3)4(OH)2 . 5H2O 5Mg(OH)2 + 4CO2 → (Mg)5(CO3)4(OH)2 . 4H2O Dypingite (5) Hydromagnesite (6) Conclusion The aim of this paper is to review the olivine potentials as a new binder for soil stabilization. Olivine is a sustainable martial to not only can capture CO2 from atmosphere through the high amount of MgO, but also the chemical composition of olivine will put this mineral as a pozzalanic material for soil stabilization because of the high amount of SiO2, Al2O3 and Fe2O3. The use of olivine as a new martial for soil stabilization will be a great opportunity for environmental friendly soil stabilization. Acknowledgment This review study is for a related research project entitled “Sustainable soil stabilization by olivine and its mechanisms” supported by the Fundamental Research Grant Scheme (FRGS) funded by Ministry of Higher Education in Malaysia (Project ID 93474-135837). Sincere thanks are also due to Prof. Bujang B.K. Huat, Dr. Afshin Asadi and Dr. Haslinda Nahazanan, Prof. Emeritus Dr. R.D. Schuiling from the Netherlands, and Ir. Parminder Singh from Malaysia who have contributed ideas to the research. References Åhnberg, H., & Johansson, S. (2003). Stabilising effects of different binders in some Swedish soils. Proceedings of the ICE - Ground Improvement, 7(1), 9–23. Alavéz-Ramírez, R., Montes-García, P., Martínez-Reyes, J., Altamirano-Juárez, D. C., & GochiPonce, Y. (2012). The use of sugarcane bagasse ash and lime to improve the durability and mechanical properties of compacted soil blocks. Construction and Building Materials, 34, 296– 305. Barker, J. E., Rogers, C. 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Canadian Geotechnical Journal, 50(8), 899–905. 26 PJSRR (2015) 1(1): 27-32 © Universiti Putra Malaysia Press Pertanika Journal of Scholarly Research Reviews http://www.pjsrr.upm.edu.my/ Data Envelopment Analysis Models and Software Packages for Academic Purposes a Abdullahi ILIYASU, *a Zainal Abidin MOHAMED,a & Rika TERANO Department of Agribusiness and Information System, Faculty of Agriculture, Universiti Putra Malaysia, Selangor Malaysia. * manawaci@yahoo.co.uk Abstract – Data envelopment analysis (DEA) is a popular technique used in measuring the performance of an industry. DEA has wide applications in agriculture, manufacturing, health care, transportation, education, energy and environment, as well as banking and finance. However, many students and academicians are in dilemma in finding the appropriate software to execute a particular DEA model. In recent years, different DEA software packages have been developed by some universities and companies for both academic and commercial purposes. The software packages offered wide varieties of most recent DEA models that could be used in science and technology. Some of these software packages are free for academic users while others are commercialised. In this study, nine different DEA software packages were reviewed. Among them, only three are free for academic purposes while four have been commercialized. One of the former is still in the development stage, but expected to be available soon. Keywords: Academic, commercial, data envelopment analysis, review models, software packages Introduction Data envelopment analysis (DEA) involves the application of linear programming technique to estimate the performance of an industry such as agriculture, health care, transportation, education, manufacturing, power, energy and environment, communication, banking, and finance (Liu et al., 2013). Table 1 shows the number of articles published in various industries that employed DEA models in their data analysis. In addition, many empirical research studies that employed DEA models as tools of analysis have been published in ISI or Scopus journals (see Table 2). Since the novel works by Charnes et al. (1978), many software packages have been developed to applied DEA models in various industries. Barr (2004), Hollingsworth (2002), and Herrero and Pascoe (1997) did a good review of these software packages. However, some of these software packages are no longer available for empirical analyses while new ones have emerged. Furthermore, many models that are previously undiscovered are now available. The recent DEA models include dynamic DEA with network such as a slack-based measure approach (Tone & Tsutsui, 2014), an alternative approach of a slack-based measure of super-efficiency in DEA, (Fang et al., 2013), a modified super-efficiency measure based on simultaneous input–output projection in data envelopment analysis (Chen et al., 2011), super-efficiency in DEA by effectiveness of each unit in society (Nuara et al., 2011), a slack-based measure of super-efficiency in DEA (Du et al., 2010), an epsilon-based measure of efficiency in DEA (Tone & Tsutsui, 2010), and variations on the theme of slacks-based measure of efficiency in DEA (Tone, 2010). Other models include network DEA such as a slacks-based measure approach (Tone & Tsutsui 2009), models for performance benchmarking (Cook et al., 2004), Undesirable Measure (Seiford & Zhu, 2002), a slack-based measure of superefficiency in DEA (Tone, 2002), a slack-based measure of efficiency in DEA (Tone, 2001), Network DEA (Färe & Grosskopf, 2000), and bootstrapping DEA (Simar & Wilson 1998). 27 PJSRR (2015) 1(1): 27-32 © Universiti Putra Malaysia Press Consequently, a need arises to review existing packages to help students and academicians to select the one that best fits the DEA model of interest. Information on the DEA software packages such as license price, developers, models, and website are, therefore, of paramount importance. It is against this backdrop that this review study is conducted. Table 1: DEA applications in industries Industries Total no. of papers Banking 323 Health care 271 Agriculture 258 Transportation 249 Education 184 Power 156 Manufacturing 146 Energy 109 Communication 70 Finance 51 (%) 17.8 14.9 14.2 13.7 10.1 8.6 8 6 3.9 2.8 2005–2009 147 107 140 131 75 87 75 75 28 33 Source: Liu et al. (2013) Commercial DEA software packages In this study, five commercialized DEA software packages are discussed in details. Three out of these five packages (DEA Solver, Frontier analyst, and MaxDEA) were developed by commercial companies. The other two (PIM-DEA and DEA Frontier) were developed by universities/polytechnics (see Table 3). Table 2: Commercial and academic DEA software Software Developer DEA-Solver Frontier Analyst PIM-DEA DEAFrontier MaxDEA FEAR DEAP EMS SAITECH, Inc, USA Bonxia Software Ltd, Uk Emrouznejad A. and Thanassoulis E. Joe Zhu Beijing Res. & Con. Com. Ltd China Paul W. Wilson Tim Coelli Holger Scheel License price (single CPU) Academic Commercial $800 $1,600 £395-£3995 £395-£3995 £245-£966 £490-£1932 $699 $2,889 $890 &2000 Free $180 Free Free Free Free DEA Solver Pro version The DEA Solver Pro version is developed by SAITECH Inc., New Jersey, USA and runs within Microsoft Excel. The latest release is Version 10.0, which has additional features not available in the previous versions. The lists of comprehensive models in this package are shown in Appendix A. The license price for single central processing unit (CPU) is $800 (academic purposes) and $1600 (commercial purposes) as illustrated in Table 3. However, a temporary license is also available at a price of $200, $250 and $350 for classes comprising up to 20, 30, and 40 students, respectively. The software package can be purchased from the developer’s website (http://www.saitech-inc.com). Alternatively, a potential user may buy a textbook (Cooper et al., 2006) to use the student trial version packaged with the book. The student trial version is, however, limited to only 50 Decision Making Units (DMUs). 28 PJSRR (2015) 1(1): 27-32 © Universiti Putra Malaysia Press Frontier Analyst Frontier Analyst is developed by Bonxia Software Limited, UK. The strongest feature of this software is its ability to display a variety of results. These include graphs of technical efficiency scores, distribution of efficiency tables, frontier plots, pie charts, reference set frequency, X-Y plots, and efficiency plots. Appendix A displays different DEA models available in this software package. However, unlike most of the DEA software packages reviewed, there is no difference between the license prices for academic or commercial users for Frontier Analyst. The license price escalates as the number of DMUs increases from £395 (75 DMUs only) to about £3995 (20000 plus). Furthermore, the cost for a single CPU and a three-month trial version with a maximum of 500 DMUs is £295. The annual maintenance and upgrading of the software costs about £289 per CPU but it is optional. Therefore, Frontier Analysis is the most expensive among all the commercial DEA software packages based on this review. This software package can be bought online through the developer’s website (www.bonxia.com). Performance Improvement Management Software (PIM-DEA) PIM-DEA Version 3 is developed by A. Emrouznejad and E. Thanassoulis at Aston Business School, Aston University Birmingham, England. This software can handle large data sets, which can be directly imported from Microsoft Excel. Similarly, outputs can be easily exported to Microsoft Excel including different types of graphs for presenting results. Additionally, it allows computation of different DEA models as showed in Appendix A. PIM-DEA, same as Frontier Analyst, has a variety of prices depending on the license type (academic or commercial), validity type (permanent or temporally), number of DMUs, additional packages, maintenance duration and postal methods. For instance, the permanent license price for academic purposes is £245 (100 DMUs) to £966 (5000 DMUs) whereas £490 (100 DMUs) to £1932 (5000 DMUs) for commercial users. PIM-DEA is the second most expensive DEA software package based on this review. For further information on PIM-DEA, visit the developer’s website (www.deasoftware.co.uk). DEA Frontier DEA Frontier is written by Joe Zhu of Operations and Industrial Engineering, School of Business, Worcester Polytechnic Institute, USA. The software solves different DEA models (Appendix A) using Microsoft Excel solver and with no limitation in the number of DMUs, inputs or outputs. However, unlike most DEA software, well-illustrated tutorials are available online on how to use the software to solve various DEA models. Although the software is commercialized, it has a free download trial version, but the trial version can only handle 20 DMUs and has very limited DEA models. The developer advised potential users to try the trial version before purchasing the licensed version. The license prices for single CPUs are $699 and $2889 for academic and commercial purposes, respectively. This license includes one month free technical support for using the software package only. The pricing and order information is available on the developer’s website (www.deafronier.net). MaxDEA MaxDEA is developed by Beijing Real World Research and Consultation Company Limited. This software is easy to use because it comes in a folder and as such requires no installation. Multiple DEA models can be run at the same time and results can be displayed in Microsoft Excel. The software is of two types, basic and professional. The former allows free download, but it also has a limited number of DEA models that can be executed. On the other hand, the latter is strictly commercialized but deals with comprehensive DEA models as shown in Appendix A. The license price varies depending on the validity type (permanent or temporal) and usage purpose (commercial or academic). The one year license price per single CPU is $360 and $800 for academic and commercial purposes, respectively. On the other hand, the perpetual license price for a single user is $890 and $2000 for academic and commercial users. However, the prices of the license escalate as the number of DMUs increases. Further information on the software can be obtained from the developer’s website (www.maxdea.cn). 29 PJSRR (2015) 1(1): 27-32 © Universiti Putra Malaysia Press Free DEA software packages (academic purposes only) Unlike commercial DEA software, the free downloadable packages are developed by universities. Although Frontier Efficiency Analysis in R (FEAR) is free for academic purposes, a license fee needs to be paid for commercial usages. Frontier Efficiency Analysis in R (FEAR) FEAR is developed by Paul W. Wilson of Department of Economics and School of Computing, Clemson University, USA. Unlike most DEA software, FEAR works in General Purpose Statistical Package called R, which can be freely downloaded from the website. However, in order to use FEAR, R needs to be downloaded first in the CPU. The FEAR library is then linked to R for various DEA computations. The FEAR package is free for academic purposes, but users must cite Wilson (2008) in all reports, papers, and publications. On the other hand, the FEAR package is not free for commercial users, but costs only $180 (single CPU license). The user guide and FEAR packages are available at the following website: www.clemson.edu/economics/faculty/Wilson/software/FEAR. Data Envelopment Analysis Program (DEAP) DEAP is a DOS programme developed by Tim Coelli of Centre for Efficiency and Productivity Analysis (CEPA), School of Economics, University of Queensland, Australia. This software can be downloaded freely from the website (www.uq.au/economics/cepa/deap.php) in zip form, which contains user guide (Coelli, 1996), read me, and many short examples. Three text files are normally used when conducting an analysis using DEAP. These include data file, instruction file and output file, and all can be edited according to the user analysis. Three analysis options are available in DEAP, standard CRS and VRS DEA models, cost and allocative efficiencies, and Malmquist DEA approach (Appendix A). DEAP is the most popular DEA software package especially among students and academicians perhaps because it is user friendly. Efficiency Measurement System (EMS) EMS Version 1.3 is developed by Holger Scheel at University of Dortmund, Germany. The software is free for download for academic purposes. EMS accepts data files from Microsoft Excel or text format, and it operates in Window 9x/NT. There is no limitation in the number of inputs, outputs, and DMUs in using the software. The EMS is distributed in zip file together with the user guide from the website (www.holger-scheel.de/ems/). Data Envelopment Analysis using Stata (DEAS) DEAS is not yet available for academic and commercial purposes because it is still in the developing stage. According to the developers, the package was registered with Source Forge.net on January 3, 2013. However, the main aim of developing DEAS is to replace the existing DEASTATA that was proposed for management performance analysis. According to the developers, DEAS models will include CCR, BCC, slack-based measure of efficiency, super-efficiency, allocative efficiency, revenue efficiency, profit efficiency, cost efficiency, free disposal efficiency, additive model, virtual price model, and Malmquist productivity index among others. Conclusion The study reviewed nine different DEA software packages for executing various analysis models. Three of these software packages are free for academic purposes while the remaining five need to be purchased accordingly. The other one is still in the developing stage, and expected to be available soon. The major shortcoming of all these software packages reviewed is that none of them performs all the DEA analysis. In addition, the free software packages have limited number of DEA models when compared with the commercial versions. The licensed software is very expensive and hence not affordable by many students and academicians especially in developing countries. Effort should be geared towards producing a single software that computes all the DEA models and at a cheaper price or free of charge to enable wider applications. 30 PJSRR (2015) 1(1): 27-32 © Universiti Putra Malaysia Press References Barr, R. S. (2004). DEA software tools and technology. Handbook on Data Envelopment Analysis, Boston: Kluwer Academic Publishers. Charnes, A., Cooper, W. W., & Rhodes, E. (1978). Measuring the efficiency of decision making units. European Journal of Operational Research, 2(6), 429-444. Chen, J.-X., Deng, M., & Gingras, S. (2011). A modified super-efficiency measure based on simultaneous input–output projection in data envelopment analysis. Computers & Operations Research, 38(2), 496-504. Coelli, T. J. (1996). A guide to FRONTIER version 4.1: A computer program for stochastic frontier production and cost function estimation: CEPA Working papers. Cook, W. D., Seiford, L. M., & Zhu, J. (2004). Models for performance benchmarking: measuring the effect of e-business activities on banking performance. Omega, 32(4), 313-322. Cooper, W. W., Lawrence M. S., & Kaoru Tone (2006). Data Envelopment Analysis: A comprehensive text with models, applications, references and DEA-Solver Software. Second Edition. New York: Springer. Du, J., Liang, L., & Zhu, J. (2010). A slacks-based measure of super-efficiency in data envelopment analysis: a comment. European Journal of Operational Research, 204(3), 694-697. Fang, H.-H., Lee, H.-S., Hwang, S.-N., & Chung, C.-C. (2012). A slacks-based measure of superefficiency in data envelopment analysis: An alternative approach. Omega - The International Journal of Management Science, 41(4): 731–734.Färe, R., & Grosskopf, S. (2000). Network dea. Socio-economic planning sciences, 34(1), 35-49. Herrero, I., & Pascoe, S. (2002). Estimation of technical efficiency: a review of some of the stochastic frontier and DEA software. Computers in Higher Education Economics Review, 15(1), 38-43. Hollingsworth, B. (1997). A review of data envelopment analysis software. Economic Journal, 107(443): 1268-1270. Liu, J. S., Lu, L. Y., Lu, W.-M., & Lin, B. J. (2013). A survey of DEA applications. Omega, 41(5), 893-902. Kaoru Tone, M. T. (2014). Dynamic DEA with network structure: A slacks-based measure approach. Omega, 42(1), 124-131. Noura, A., Hosseinzadeh Lotfi, F., Jahanshahloo, G. R., & Fanati Rashidi, S. (2011). Super-efficiency in DEA by effectiveness of each unit in society. Applied Mathematics Letters, 24(5), 623-626. Seiford, L. M., & Zhu, J. (2002). Modeling undesirable factors in efficiency evaluation. European Journal of Operational Research, 142(1), 16-20. Simar, L., & Wilson, P. W. (1998). Sensitivity analysis of efficiency scores: How to bootstrap in nonparametric frontier models. Management science, 44(1), 49-61. Tone, K. (2001). A slacks-based measure of efficiency in data envelopment analysis. European Journal of Operational Research, 130(3), 498-509. Tone, K. (2002). A slacks-based measure of super-efficiency in data envelpoment analysis. European Journal of Operational Research, 143, 32-41. Tone, K. (2010). Variations on the theme of slacks-based measure of efficiency in DEA. European Journal of Operational Research, 200(3), 901-907. Tone, K., & Tsutsui, M. (2009). Network DEA: a slacks-based measure approach. European Journal of Operational Research, 197(1), 243-252. Tone, K., & Tsutsui, M. (2010). An epsilon-based measure of efficiency in DEA–a third pole of technical efficiency. European Journal of Operational Research, 207(3), 1554-1563. Wilson, P. W. (2008). FEAR: A software package for frontier efficiency analysis with R. SocioEconomic Planning Sciences, 42(4), 247-254. 31 PJSRR (2015) 1(1): 27-32 © Universiti Putra Malaysia Press Appendix A: DEA Software Models Models DEASolver CCR/CRS y BCC/VRS y NIRS,NDRS,GRS y Additive/Slack-Based Method y Malmquist y Non-convex y Non-radial y Preference-structure n Undesirable-measure n Context-dependent n Free-disposal hull (FDH) y Order m efficiency n Allocative efficiency n Cost efficiency y Revenue efficiency y Profit, revenue/cost efficiency y Variable-benchmark n Fixed-benchmark n Minimum-efficiency n Weak disposability n Congestion y Super Efficiency n Scale elasticity y Slack-Based Super Efficiency n Bootstrapping n Network n Dynamic n Cross Efficiency n Epsilon-Based Measure (EBM) n Restricted multiplier n y = available; n = not available Frontier Analyst DEA MaxDEA Frontier Pro PIMDEA FEAR DEAP EMS Y Y N y y y y y y y y y y y y y y n y y y N y n n n n n n n n n n y y y y y y y y n n y y y y n y y y y y n n y y n y n n n n n n n y y n n y n n n n n y y n y y n y n n n n n n n n y n y y y n n n n y n n n n n n n n n n n n y y y y y y y n y y y y y n y n n n n n n n n y y n n n n n n n n n n n n n n y n n n n n n n n n n n n n y y n n y n y y y y n y n n n n y n n n n n n n n n n n n n n n n y y y n n n n n n n n 32 PJSRR (2015) 1(1): 33-39 © Universiti Putra Malaysia Press Pertanika Journal of Scholarly Research Reviews http://www.pjsrr.edu.my/ Renewable Energy Policy Status and Challenges of POME-Biogas Industry in Malaysia Wong, SIEW YIEN,aAmir, HAMZAH SHARAAI,b*Faradiella, MOHD KUSIN,a & Mohd, MANSOR ISMAIL,c a Department of Environmental Sciences, Faculty of Environmental Studies, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia b Department of Environmental Management, Faculty of Environmental Studies, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia c Institute of Agricultural and Food Policy Studies, Unirversiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia * amirsharaai@upm.edu.my Abstract – Palm oil can be considered as a mainstay in the regional development and economic growth of Malaysia. It is an important raw material for local industries and as an export product. Most recently, palm oil has been referred to as a promising feedstock for the production of biofuel which could lead Malaysia towards a low carbon society. With the growing concern towards the increase of energy demand and global warming, the conversion of palm biomass to biogas for power generation has then been recognized as a feasible option in response to the mentioned problems. Nevertheless, various constraints have come in the way to slow down the biofuel production. Therefore, this paper presents an overview on the existing renewable energy (RE) policy and its current programme status, as well as to identify the challenges facing the Malaysian palm oil mill effluent (POME) and biogas industry in order to propose appropriate measures for further improvement of the programme. Keywords: Biogas, energy demand, energy policy, palm biomass, renewable energy Introduction Global warming has become one of the prominent global issues and its impacts towards human health and environment have always captured the attention of people around the world. Global warming can be ascribed by a substantial emission of greenhouse gas (GHG) into the atmosphere through fossil fuel combustion. In addition to the rapid growth of population and urbanization in the country, the GHG emission rate has become higher as this significant development in the country would require a greater amount of energy consumption for power generation. This condition is more obvious in the United States and China, as both countries have been identified to be the world’s largest and second largest energy user, respectively (IEA, 2010). In comparison, Malaysia is reported to be the third largest energy consumer in ASEAN countries and it is anticipated that the per capita power consumption will further escalate as the country becomes more developed (IEA, 2013). Since 1990, every nation has started to do some negotiations regarding the carbon emission issue and has promised to reduce more carbon content into the atmosphere by maximizing the RE utilization. However, this is merely a blatter rather than a promise as the global carbon emissions at the moment have increased to 65% compared to that in 1990 (Global Carbon Project, 2014). In the current trend of 370 hundred million tons of carbon emissions, it is predicted that the global carbon emissions will hit 432 hundred million tons by 2019, of which 127 hundred million tons of the carbon emissions will be mostly contributed by China (Global Carbon Project, 2014). The rapid increment rate of carbon 33 PJSRR (2015) 1(1): 33-39 © Universiti Putra Malaysia Press emissions should has struck the nations’ senses back to reality and it should have served as a vital reminder for all parties to play their parts in response to the concerned global problem. In fact, many countries have implemented various regulations or incentives in favour of RE particularly bioenergy derived from biomass resources such as POME biogas. The intention is obvious, which is to alleviate the carbon emission rate and the dependency on the main fossil energy resources such as natural gas, coal and oil in electricity generation, as well as to achieve the goals of environmental protection and economic advancement. Nevertheless, the result is not very promising as many challenges have been found in the RE industry. Therefore, this review on the existing RE policy and current programme status could be feasible in identifying challenges and loopholes confronted by the industry so that appropriate alternatives could be developed to ensure a sustainable RE development. This paper focuses on the POME-biogas aspect of bioenergy and challenges for the POME-biogas development in Malaysia. Government policies related to RE and POME-biogas production Overview of Malaysian RE Plans Energy policies and relevant programmes have been adopted in Malaysia since 1949, but virtually, they were executed actively only after and up to 2000. Within the period of 2001 to 2010, the Third Outline Perspective Plan (OPP3) under Vision 2020 emphasised on managing both non-renewable and RE resources to accommodate the demands for a rapid economic growth and minimizing pollution and waste generation on the environment was established. Along the same line, the Eighth Malaysian Plan (8-MP) (2001-2005) focused on the initial phase of OPP3 by introducing RE especially biomass as the fifth fuel into the existing energy sources so that 5.5% of the country’s electricity derived from RE can be achieved by 2020 (EPU, 2010). Then, the Ninth Malaysian Plan (9-MP) (2006-2010) continued the efforts built up during 8-MP in strengthening the initiatives for energy efficiency (EE) and RE with a variety of fiscal and monetary incentives (Jalal & Bodger, 2009). Subsequently, the Tenth Malaysian Plan (10-MP) (2011-2015) and National Green Technology Policy (2009) emphasised the creation of new opportunities and stronger incentives for investments in RE projects to boost the growth of green economy and sustainable energy supply (EPU, 2010). As for the recently announced Eleventh Malaysian Plan (11-MP) (2016-2020), the country will emphasize “green growth” in society, which aims to ensure that the environment is facing the least impact whilst conserving natural resources through the aspects of energy-efficient lifestyle and stressing more on 3Rs (i.e. Reduce, Reuse and Recycle) in households and the industrial sector, and improving the current educational systems (EPU, 2015). Undeniably, these implemented Malaysian Plans would have opened up many opportunities to the industry to further explore the RE development notably on palm biomass and POME biogas-derived energy where the biomass resources are generally recognized to be highly abundant in the country. Furthermore, it is projected that the country’s policies and regulation in terms of environmental governance will get improved in line with the execution of the mentioned Plans. However, these Plans do not seem to go far enough and there is no specific explanation or declaration on how the environmental legal framework and principles (in RE context) can be further reinforced which commonly found in most of the relevant environmental policies and regulations. The Plans are more likely to be a little over generalisation and this has led to a poor and unclear comprehension among the nations and RE players towards the country’s current and future environmental governance issues which the Plans do not portend well as a foundation for action. Nevertheless, relevant authorities should not remain overly passive but they need to take initiatives while conserving the environment. Meantime, the policy makers should really be urged to develop more concrete and specific strategies that could attain the environmental objectives targeted in the Plans. POME-biogas development and National Key Economic Area Since the Malaysian palm oil industry is considered as one of the biggest contributors to the national economy because it has reportedly contributed RM53 billion in the country’s Gross National Income (GNI) (NKEA, 2013), its activities are then being further advocated to a certain extent. Up to 2015, 34 PJSRR (2015) 1(1): 33-39 © Universiti Putra Malaysia Press 443 palm oil mills are in operation at present compared to 439 palm oil mills in 2014 (MPOB, 2015). As the development of palm oil mills are in line with the increase of economic growth, eight core Entry Point Projects (EPPs) have been implemented by the Palm Oil National Key Economic Area (NKEA) programme to boost a higher economic status in the country by 2020. As stated in the EPP 5 under the eight core EPPs, the government aimed to achieve the biogas facility installation in all palm oil mills in Malaysia by 2020 (MPOB, 2012). However, based on the data documented by MPOB in 2014, only 67 out of 439 palm oil mills were recorded to have involved in biogas activities in Malaysia (Loh et al., 2014). With less than 20% of the palm oil biogas plants installed in Malaysia, a question on the practicality of EPP 5 is asked. However, it is optimistic that the number of biogas plants will increase in the near future as the generation of palm biomass is anticipated to increase from 80 million dry tonnes in 2010 to 110 million dry tonnes by 2020, and this will definitely initiate more new wealth creations in the industry, if the National Biomass Strategy 2020 is comprehensively executed. Therefore, the implementation of biogas plants should be imposed but under a strict and comprehensive control of environmental management strategy as this implementation could bring a win-win situation to both the country and environment such as 1) reduce cost of production by using in-house energy production, 2) mitigate GHG emissions (carbon credits), and 3) extension of biofuel market by upgrading biogas to a practical transport fuel on roads. POME-biogas development, Clean Development Mechanism and Small Renewable Energy Program Apart from NKEA, a scheme namely Clean Development Mechanism (CDM) under Kyoto Protocol has also been established which aims to facilitate developing countries to achieve sustainable development through the sales of certified emission reductions (CERs). In 2002, Malaysian government has ratified Kyoto Protocol, and biogas projects are eligible for this CDM programme. With the establishment of CDM, more investment opportunities for the public are created to involve in the GHG emission reduction projects. It is also beneficial to palm oil industry by capturing biogas to earn CER revenue as well as to prepare the industry to meet an increasingly stringent sustainability requirement in future. In order to ensure the sustainability of environmental and energy supply in Malaysia, the government also launched a programme known as Small Renewable Energy Power (SREP) on 11th May 2001 to encourage a wider use of RE resources in power generation where the generated electricity is suggested to be connected to a power grid whenever possible (Anuar et al., 2005). In 2002, another project namely BIOGEN Project funded by the Malaysian government, United Nation Development Program (UNDP), Global Environment Facility (GEF) and private sectors was introduced as a compliment to SREP programmes (PTM, 2001). This project plays a role primarily in reducing the GHG emissions from fossil fuel combustion, and it exploits biomass as a highly potential source for energy generation. Under the SREP, it is suggested that all the small power plants are encouraged to sell the electricity produced to Utility through the Distributed Grid System where the biomass and biogas plant operators can enjoy the RM 0.3184/kWh through the Feed-in Tariff (FiT) system (SEDA, 2014). However, the achievement is rather disappointing because less than 4% of the electricity generated from RE resources is being captured. This limit of grid connection of biogas plants can be ascribed by a limit set by the FiT system under the Renewable Energy Act 2011, of which the FiT system is only applicable in Sabah and Peninsular Malaysia but not in Sarawak due to the presence of the state’s own legislation and regulations governing exclusively on their electricity supply (RE Act 2011). Moreover as in the palm oil industry, palm oil mills which have enough power generated from the combustion of their own biomass resources especially fibre and shell, the millers found that this would not be a big deal to the mills even if the electricity produced from the biogas plants is not connected to grid. Challenges for POME-biogas plant development Although the development of POME-biogas plants in Malaysia has come a long way through the years, a few significant challenges have been found to have hampered its development, for example, high costs of investment including plant construction, and lack of required knowledge and technical expertise. 35 PJSRR (2015) 1(1): 33-39 © Universiti Putra Malaysia Press Financial constraint The financial barrier can be considered the main stumbling block in implementing a biomass power plant and POME-biogas plant in Malaysia. At present, majority of the biomass industry players are still facing difficulty in getting feedstock from biomass producers who are mostly private plantations. Thus, when they try to apply for a commercial loan, they have to present the field supply agreement on a long term basis and this is apparently not possible for them to secure. Compared to the biomass industry players, POME-biogas industry players are more concerned with the investment cost of the POME treatment system in the mill, and the construction cost of closed anaerobic digestion tank is found to be comparatively higher than the conventional way of POME treatment in the mill known as anaerobic ponding system. From this point of view, both cases have shown that these biomass and biogas industry players are indeed struggling on solving the financial problems. The POME-biogas systems currently in use in Peninsular Malaysia are found to be more developed compared to those located in East Malaysia (especially in Sarawak) in terms of infrastructure developments, legal implications and tariff deliberations. The lack of infrastructures for feed-in capability into power grids, gridlines availability issue and the long distance between the location of palm oil mills and power grids in the State are the significant factors that resulted in a low possibility of biogas implementation. In other words, the biogas industry players in East Malaysia would require greater efforts and funding to invest the biogas facilities in their mills. Besides, the lack of support from the government and the relevant authorities on the related RE technology adoption at the current market has resulted in a slower growth of biogas plant development in Malaysia. The relevant stakeholders believe that these projects could have high risk when the new RE technology of POME-biogas is adopted. Moreover, a long payback period has also bothered the stakeholders to finance the projects, and it gradually makes the RE technology not commercially viable in Malaysia. In addition, when a high capital is needed, smallholders will definitely find it unattractive to make such an investment. This is where the government should come in with more viable financing schemes. Therefore, the cooperation among the government, private sectors and institutions is important in developing such projects because the financial assistance from each authority can support a high initial cost and enough capital to adopt appropriate RE technology in plants. With respect to this economic issue, the understanding and trust among the financiers and investors are vital because any misunderstanding and lack of communication related to RE among the groups will lead to a low participation of national financiers. Availability of technical expertise Advanced technologies are required to ensure the biogas digesters and maintenance activities going all well and to reduce extra expenses on repairing the machines as time passes. Hence, personnel with good skills are most needed to monitor the related technologies under a careful supervision. However, what makes it difficult is that Malaysia is facing a shortage of professional technicians in the country. Therefore, maintenance activities to address technological monitoring are difficult. Furthermore, some of the local conversion technologies available in local universities are still at the lab level, and this situation has indirectly affected the development of the biogas power plant as many entrepreneurs are not fully confident to use local technologies. Unlike Malaysia, many western countries have technologies that are always developed and commercialized up to industrial practice. Their technologies can even developed to the extent of proposing policy implementations of certain related models. When the Malaysian government is taking the initiative to implement and rely on the western technology in Malaysia, it might not be reliable due to differences found in management and required knowledge which demanded highly skilled personnel and careful maintenance. Furthermore, the capital-intensive initiative requiring huge costs to cover such imported technologies to the country is unsustainable. Thus, an overview on the existing biogas systems in Malaysia will enhance the wastes management measure as well as to be served as a reference in providing basic guiding principles for policy makers and researchers. Nevertheless, the information on biogas production system in Malaysia is rather limited due to the lack of systematic analysis and outdated periodic documentation, and this again has slowed down the research progress. 36 PJSRR (2015) 1(1): 33-39 © Universiti Putra Malaysia Press Termination of CDM and inefficient environmental tool application As aforementioned, the CDM programme could further facilitate the biogas development through the sales of CERs where the profits could actually be used to recover part of the operating cost. However, after the announcement of its termination at the end of 2012, only those CDM developers whose projects were accepted before 31st December 2012, were allowed to sell their CERs to the Europe’s Emissions Trading Scheme until the mid of 2015 (CDM, 2014). This also means that CDM projects that were accepted after 2012 have a difficulty in financial support to run the biogas system in the mills as they cannot sell their CERs. Correspondingly, the termination of the programme would also denote that the improvement of the present anaerobic digestion technology is prompted to stop moving forward as there will be no enforcement on the current increasingly stringent sustainability requirement which is supposed to be adopted in the plants to manage the wastes. Moreover, there are no rigorous restrictions and/or standard technology in treating POME in the country and this situation has resulted in an establishment of an unclear biogas development schedule among the majority of palm oil companies. This trend is believed to be the main driving force of an uncontrollable of GHG emissions in the atmosphere. Therefore, it is suggested that the continuity of the CDM programme should be taken into consideration by the government so that the POME-biogas players are incentivized and thus attracting them to invest in the initiative. However, under certain circumstances where no subsidy is provided by the government, biogas industry players might confront a bigger financial issue. Therefore, the efficient use of environmental tools in the companies could be a feasible solution to them. Environmental tools such as Life Cycle Assessment (LCA) and Environmental Life Cycle Costing (ELCC) could be employed in the relevant palm oil mills to evaluate the performance of their mills and plants from the environment and economic aspects, in terms of their life cycle perspective (raw materials extraction to end-of-life process). With the employment of these tools, palm/biogas industry players can determine the possible environmental impacts that could arise throughout the entire life cycle of biogas production system (by using LCA) while evaluating the efficiency of their financial management of which each unit process of the biogas production system should be allocated with appropriate amount of capital (by using ELCC). Consequently, palm/biogas industry players could avoid unnecessary expenses on environmental remediation by referring to the results computed from the assessments. This selfgovernance system could possibly reduce their high operating and environmental costs while attaining a sustainable environment in their mills and plants. Nonetheless, the majority of the palm companies are not familiar and have no experience on using the mentioned approaches in their mills and plants. Therefore, the relevant authorities should train their employees on the related course which will definitely be a credit to the companies and environment in the near future. Debate on loss of biodiversity and climate change The rapid emerging of palm biomass industry in the country for economic advancement has caused an active clearance of land for oil palm plantations to boost a higher yield of productions. This has gained attention from environmental groups such as Greenpeace and Friends of the Earth who strongly criticized that the related projects have triggered a severe threat on biodiversity loss especially those involved endangered species including the orangutans, Sumatran tigers and elephants (Buckland, 2005). Moreover, many other environmentalists also claimed that the deforestation for palm oil cultivations has caused a significant production of CO2 emission (Karousakis, 2007; Stern, 2006). Nevertheless, a study reported by Tan et al. (2009) stated that an oil palm plantation can actually assimilated a number of 64.5 t ha-1y-1 of CO2 whereas only 42.2 tha-1y-1 of CO2 is assimilated by a rainforest. Hence, if the oil palm plantation could qualify as planted forests, this agri-industrybased activity can actually contribute towards biodiversity conservation efforts as well as facilitating carbon sequestration (carbon sink) and GHG reduction. This is because most of the oil palms planted in the country are on forest peripheries, of which majority of the palm oil developers have starting to commit or have already committed themselves in implementing good agricultural practices in the fields. 37 PJSRR (2015) 1(1): 33-39 © Universiti Putra Malaysia Press Conclusion Most policies would give a general picture on the status of RE management in Malaysia and the necessity to provide detailed information, realistic and conducive regulatory frameworks on RE management and energy recovery is commonly been treated carelessly. Hence, despite a huge number of current RE policies and frameworks that have been strongly promoted to attract developers and investors to get involved in the field, the current biogas development in Malaysia is still considered very discouraging compared to other countries such as Germany, Denmark and China as many of the palm oil mills in the country are having difficulty in financial acquisition. The limiting factors such as high investment cost, new technology, skilled personnel and termination of CDM programme are forcing oil palm companies to adjust their RE strategy. Consequently, this has led to an increment of reluctance level among the millers to venture into higher efficiency technologies in the mills. However, it is believed that a comprehensive RE Policy, effectively application of relevant environmental tools and a long term commitment associated with an effective cooperation from the government and related stakeholders can lead to a rapid growth of RE development and to create a sustainable biogas market in the country. References Anuar, A. R., Norasikin, A. L., & Zulkifli, A. R. (2005). Current scenario and future challenges of the oil palm biomass energy. Sixth National Seminar on the Utilisation of Oil Palm Tree. Organized by OPTUC, 15-17 December 2003, Kuala Lumpur, Malaysia. Buckland, H. (2005). The oil for ape scandal: how palm oil is threatening orangutan survival (pp. 150). Retrieved from https://www.foe.co.uk/sites/default/files/downloads/oil_for_ape_full. pdf Clean Development Mechanism (CDM). (2014, November 20). United Nations framework convention on climate change. Retrieved from http://cdm.unfccc.int/ Economic planning unit (EPU). (2010). Tenth Malaysia Plan 2011–2015 (pp. 1-429). Retrieved from https://www.pmo.gov.my/dokumen attached/RMK/RMK10_Eds.pdf Economic Planning Unit (EPU). (2015). Eleventh Malaysia Plan 2016-2020 (pp. 159-190). Retrieved from http://rmk11.epu.gov.my/book/eng/Elevent-Malaysia-Plan/RMKe-11%20Book.pdf Global Carbon Project. (2014, December 15). The Global Carbon Project. Retrieved from http://www.globalcarbonproject.org/ International Energy Agency (IEA). (2013, December 10). Energy statistics. Retrieved from: http://www.iea.org/statist/index.htmS International Energy Agency (IEA). (2013). (2014, December 10). IEA: Malaysia's energy consumption to record moderate growth in 2014. Retrieved from http://www.nst.com.my/business/todayspaper/iea-malaysia-s-energy-consumption-to-recordmoderate-growth-in-2014-1.447079 Jalal, T. S., & Bodger, P. (2009). National energy policies and the electricity sector in Malaysia. Proceedings of ICEE 2009 3rd international conference on energy and environment, 7-8 December 2009, Malacca, Malaysia. Karousakis, K. (2007). Incentives to reduce GHG emissions from deforestaton: lessons learned from Costa Rica and Mexico (pp.1-50). Retrieved from http://www.oecd.org/env/cc/38523758.pdf Loh, S. K., Nasrin, A. B., Nurul Adela, B., Mohamad Azri, S., Muzzammil, N., Daryl Jay, T., Stasha, E. R. A., Mohd Faris, M. R., Lim, W. S. & Choo, Y. M. (2014). Biogas capture and utilisation from palm oil mill effluent [Brochure]. Bangi, Malaysia: Perpustakaan Negara Malaysia Cataloguing-in-Publication Data. Malaysia Palm Oil Board (MPOB). (2009). (2015, August 10). Economics & Industry Development Division: Sectoral status. Retrieved from http://www.mpob.gov.my/en/palminfo/environment/520-achievements Malaysia Palm Oil Board (MPOB). (2014, November 12). Malaysia Palm Oil Board, NKEA: National biogas implementation (EPP5). Retrieved from: http://www.mpob.gov.my/en/component/content/article/153-demo-content/992-nkea-nationalbiogas-implementation-epp5 National Key Economic Areas (NKEA). (2013). National biogas implementation (epp5): biogas capture and CDM project implementation for palm oil mills (pp. 1-19). Retrieved from http://www.e-kilangmpob.com.my/NATIONAL_KEY_ECONOMIC_AREAS.pdf 38 PJSRR (2015) 1(1): 33-39 © Universiti Putra Malaysia Press Pusat Tenaga Malaysia (PTM). (2013, September 17). Biogen. Retrieved from http://www.ptm.org.my/biogen/index_new.htm Renewable Energy Act 2011. (2014, November 28). Retrieved from http://seda.gov.my/ Stern, N. (2006). Stern Review: The Economics of Climate Change. Cambridge, UK. Cambridge University Press. Sustainable Energy Development Authority Malaysia (SEDA). (2014, December 12). Feed-inTariff (FiT) rates for biogas. Retrieved from http:// seda.gov.my/ Tan, K. T., Lee, K. T., Mohamed, A. R., & Bhatia, S. (2009). Palm oil: addressing issues and towards sustainable development. Renewable and Sustainable Energy Reviews, 13(2), 420-427. doi:10.1016/j.rser.2007.10.001. 39 PJSRR(2015) 1(1): 40-49 © Universiti Putra Malaysia Press Pertanika Journal of Scholarly Research Reviews http://www.pjsrr.upm.edu.my/ Comparing Asynchronous and Synchronous Interaction Using Online Technology Yolanda Lee Lee HIEW* & Bee Hoon TAN Department of English, Faculty of Modern Languages and Communication, Universiti Putra Malaysia * yolanda.hiew3@gmail.com Abstract – The move from traditional face-to-face classroom learning to the use of information and communication technology (ICT) has been implemented by universities in Malaysia and abroad vigorously with computer-mediated communication (CMC) systems. These technologies promote interaction among tertiary level students in collaboration where they can have discussions with peers for collaborative tasks by means of posting messages (asynchronous) and instant messaging (synchronous). This review paper focused on comparative studies of asynchronous and synchronous interaction among university students using online tools. The quantitative and qualitative research studies were reviewed preliminarily based on the types of CMC used, looking at the theories, methods, respondents, and findings. This paper also discusses the online tools used for interaction such as Wiki and Skype, and concludes with an understanding of students’ experience of different online systems and tools in their communication that may affect their learning. Keywords: Asynchronous, computer-mediated communication, interaction, Skype, synchronous, Wiki Introduction A number of universities in Malaysia and other countries are actively implementing online learning, through learning management system (LMS) and virtual learning environment (VLE) at undergraduate and postgraduate levels (Embi, 2011; Goi & Ng, 2009; Hussain, 2004; Kirkwood, 2009). Computer-mediated communication (CMC) systems facilitate asynchronous or synchronous interaction among individuals in an online environment. In addition, educational technologies such as WebCT, Moodle or Blackboard are widely used in collaborative learning (Alavi, Yoo & Vogel, 1997; Williams, Duray & Reddy, 2006). Thus, asynchronous and synchronous interaction using online tools, and Wiki and Skype are reviewed in this paper. Asynchronous Learning Network (ALN) is defined as environments where students use computers to communicate and work with their peers and instructors (Mayadas, 1999). One of the benefits of asynchronous interaction is that the participants have more time to think and reflect on the course content and contribute (Biesenbach-Lucas, 2003). Asynchronous interaction takes place through a discussion forum in a private webpage where students discuss their task collaboratively. Synchronous interaction using a CMC tool involves real-time participation among students, such as live chat using text, audio and video-conferencing (Martin, Parker, & Deale, 2012). Providing synchronous elements to online courses can enhance meaningful interactions (Repman, Zinskie & Carlson, 2005). 40 PJSRR(2015) 1(1): 40-49 © Universiti Putra Malaysia Press Computer-mediated communication Computer-mediated communication (CMC) has started since the late 1960s. Murray Turoff was the first to introduce computer conferencing in 1970 to offer a setting for scholarly community for exchanging information and effective problem-solving (Hiltz & Turoff, 1978). Some studies on asynchronous discussion also indicate that using writing to communicate with peers online is easier to control or take charge. This is because there is no need for immediate feedback in the writing process, so students have sufficient time to think and validate so as to convey meaning clearly (Koschmann et al., 1996). However, in a face-to-face team, members may interact through facial expressions, such as smiling, body language and gestures, and such interaction does not occur in online teams (Macdonald, 2003). Moreover, the process of collaboration becomes more visible when students in an online team use text messages to communicate, thus, postings among students on discussion boards can be used to verify both their joint effort and contribution in the procedure. Consequently, the result of the teamwork can reflect students’ collaboration by means of a written essay or report. According to Chou (2002), asynchronous interaction is more suitable and sufficient for a course that needs memorising factual knowledge. However, the author suggests that synchronous interaction is more appropriate when the course objective is to improve online interaction skills. Thus, synchronous interaction is as important as asynchronous interaction depending on the context and nature of task, though some online interaction and collaboration studies have merely used asynchronous system (e.g. Biesenbach-Lucas, 2003; Elgort, Smith & Toland, 2008). Some universities use the LMS platform and other social media software that consist of features of live chat and discussion board to facilitate students’ collaborative learning and writing. There are a handful of comparative studies of asynchronous and synchronous communication and most of these compared text-conversations and real-time chat among undergraduates and graduates. Their framework is based on collaborative and social constructivist theories. These studies have used, inter alia, content analysis, interviews, observation and survey as the main methods of analysis (e.g. Bonk et al., 1998; Chou, 2002; Davidson-Shivers et al., 2001; Hrastinski, 2007; Schullo et al., 2005). A few major studies have indicated considerable differences between asynchronous and synchronous interaction that were mainly found in qualitative content analysis in smaller groups. Table 1 presents a summary of the comparative studies. The findings in these studies indicate that asynchronous discussions promote more complex ideas (Bonk et al., 1998), more attention on the task (Chou, 2002), more reflective statements (DavidsonShivers et al., 2001), and effective for collaborative writing (Mabrito, 2006). Synchronous discussions allow students to interact more frequently (Bonk et al., 1998), exchange socio-emotional interactions (Chou, 2002), teacher-student as well as student-student can communicate effectively (Haythornthwaite, 2001; Schullo et al., 2005), and the chat sessions are satisfying (Spencer & Spencer, 2002). However, Ng and Detenber (2005) found that synchronous discussions were viewed as more useful and influential but this form of discussion has no considerable impact on student’s participation. Moreover, Schwier and Balbar (2002) found that synchronous interaction was less efficient in dealing with content, and students spent lesser amount of time on course task in the chat discussions (Mabrito, 2006). Thus, the studies suggested that asynchronous interaction was more appropriate for thinking and discussing complicated views (Hrastinski, 2008), while learners favoured synchronous communication as there were more social communications. Despite the utilisation of CMC among business corporations and educational communities, the effectiveness of these tools should be realised, where asynchronous and synchronous systems should also facilitate knowledge sharing in group interaction and collaboration. 41 PJSRR(2015) 1(1): 40-49 © Universiti Putra Malaysia Press Table 1: Comparative Studies of Asynchronous and Synchronous Interaction Source Type of CMC Purpose of Study Methods Respondents Findings Bonk et al. (1998) Text-discussion board and chat Content analysis 65 pre-service teachers Chou (2002) Text-discussion board and chat To explore how to use the Web to foster collaboration and interaction To examine the patterns of learner-learner interaction Content analysis Number of undergraduates not indicated DavidsonShivers et al. (2001) Text-discussion board and chat To investigate how graduates participated in online discussion Content analysis, survey 14 graduates Haythornthwaite (2001) Text-discussion board, chat, e-mail, and audio Interviews, survey 14 graduates Hrastinski (2007) Text-discussion board and chat Content analysis, interviews, surveys 8 graduates Mabrito (2006) Text-discussion board and chat Content analysis, survey 16 undergraduates Ng & Detenber (2005) Text-discussion board and chat Survey 153 Schullo et al. (2005) ElluminateLive (synchronous) and WebCT (mainly asynchronous) Schwier & Balbar (2002) Text-discussion board and chat Spencer & Spencer (2002) Text-discussion board and chat To explore how group members exchange information online To examine how synchronous chat complementing asynchronous discussion affect participation To examine students’ collaborative writing in synchronous and asynchronous interaction To investigate the effects of two features of CMC and students’ perceptions of online discussion To investigate the use of synchronous system as a supplement to existing courses To experiment synchronous and asynchronous interaction in a theory course To investigate the effects of synchronous chat in supplementing asynchronous online courses Students conveyed more complicated views in asynchronous interactions and engaged frequently in synchronous discussions Students concentrated on the subject in asynchronous discussions, and exchanged socio-emotional relations in synchronous discussions Students stated more reflective comments in the asynchronous discussions, and put some remarks in the synchronous discussions Class used discussion board and chat for communication, and e-mail for intra-team communication undergraduates Content 70 graduates, analysis, 5 instructors interviews, surveys, observations Not specified 7 Graduates Content analysis, interviews, survey 133 students 42 Not easy to acquire asynchronous discussions initiated with a few students. Combining asynchronous and synchronous interaction enhance participation Asynchronous interaction were effective for collaborative writing. Students spent less time focusing on tasks in synchronous sessions Synchronous discussions were observed as more informative and persuasive but did not have significant impacts on students’ intention to participate Synchronous interaction allowed instructors to build connections with and among students more effectively Synchronous interaction contributed to stability and sense of community but was less effective in dealing with content Students found synchronous sessions satisfying, various hypotheses were examined but few were statistically significant. PJSRR(2015) 1(1): 40-49 © Universiti Putra Malaysia Press Interaction through online tools Distance educators have classified interactions in distance learning in several ways. Although there are many classifications available, the classification suggested by Moore (1989) has been largely recognised. According to Moore, there are three types of interaction: (1) interaction between studentstudent, (2) interaction between student-instructor, and (3) interaction between student-content. This classification has been influential to researchers even in recent studies. For instance, some researchers agreed that most communications have reflected student-instructor, student-content and studentstudent interactions, thus receiving considerable attention as they believe that such form of interaction can promote collaboration (e.g. Balaji & Chakrabarti, 2010; Howarth, 2006). However, Hillman et al. (1994) identified that the interaction between student and interface also plays an important role in the distance learning environment. Hence, Moore and Kearsley (1996) suggested that the learning interaction can be categorised into four types: student-content, student-instructor, student-student, and student-interface. The first three are most frequently used to assess interactions, thus, this review focused on student-student interaction for collaboration. Student-student interaction occurs in several modes within the course environment. These interactions among students take place through email, discussion boards, video- and audio-conferencing, or chatting, and interaction with peers helps the student to understand the course content (Dewey, 1996). Garrison (1990) stated that students who interacted on a regular basis with other students were more motivated and participated actively in their learning. Nonetheless, Freed (2004) reported that interaction between instructor-student and student-student remained as the major barrier in the online distance learning environment. It is vital for online distance learning instructors to design and develop a learning environment to promote student-content, student-instructor, and student-student interactions (Anderson & Garrison, 1997; Garrison & Cleveland-Innes, 2005). Besides, Olson and Wisher (2002) observed the difficulties of many students, who lacked high-speed computers and Internet connections to respond promptly during interaction. In addition, Ko and Rossen (2001) proposed that if the size of the class was too small, engaging students in interaction became rather difficult. McGreal and Elliott (2008) proposed some of the most stimulating technologies and features used in online instruction, and these multimedia applications offer various opportunities for educators. For instance, audio chat and web-conferencing on Skype are commonly used for teaching and learning while mobile technologies are also explored along with wikis, blogs, and other instant messaging in a virtual world. However, the availability of technology to students and their skill levels in using the medium can support or hinder collaborative dynamics as the technology can be the cause of either frustration or motivation (Brindley, Blaschke & Walti, 2009). Asynchronous system hinders the discussion of complicated problems and conversations that require immediate response, and breaks in between communication can delay initial postings and responses. Brindley et al. (2009) state that tools which are more suitable for collaborative learning such as Wiki and Skype are readily obtainable on the Internet. However, these tools are not necessarily introduced to students or incorporated into traditional and virtual classroom efficiently. Table 2 illustrates various online interaction tools. Two categories are relevant to this review: Wiki and Skype. Wiki is an asynchronous system with free open-sources that permits multiple writers to create and write on a page in the website. Skype is a synchronous system that consists of voice call, video call and instant chat that comes free or with very low rates. Apart from personal computers, Skype can be run steadily on smart phones and tablets across multiple platforms. Besides, both Wiki and Skype can be used for online interaction among students to carry out their group projects. The former offers discussion forum with delays in time to response, while the latter provides real-time chat with instant responses. The use of the Internet in educational settings provides opportunities for interaction and collaboration between students living at a distance. The similarities between asynchronous and synchronous systems are that both types of interactions are user-friendly and requiring basic ICT skills, and they are both time efficient and not costly. This could be the reason why online learning is gradually becoming popular. 43 PJSRR(2015) 1(1): 40-49 © Universiti Putra Malaysia Press Name Blackboard, WebCT Elluminate GoToMeeting, Zoho Table 2: Online Interaction Tools (Adapted from Kask, 2009) Type of Categories Comments Communication Learning Management System Message Board Synchronous and (LMS) provides a learning Forum, Chat, Email asynchronous environment to students though it is costly. Application allows voice and video Whiteboarding, Synchronous and communication and costly. Good for Chat, VoIP, Video asynchronous presentation of material. Web conferencing allows people to Whiteboarding, Synchronous and meet and do presentation and it is Chat, VoIP, Video asynchronous low cost. Suitable for short term use or long term assignments. Facebook, Myspace, Nexopia SNS, Chat Synchronous and asynchronous MediaWiki, Wiki Wiki discussion forum Asynchronous Moodle CMS, Forum, Chat Synchronous and asynchronous Messenger Chat Synchronous Google Wave Email, Chat Synchronous and asynchronous Skype VoIP, Video, Chat Synchronous Web 2.0 technology supports social participation and it is free to users. Free open-source allows for multiple writers and suitable for collaborative writing tasks. Free open-source but requires an existing web server to run on, and accessible to a SQL database. Instant messaging with no costs, and can be functioned as an email. Application allows groups to share documents for free, and email is available to facilitate group tasks. Accessible in multiple platforms (Windows, MacOS, Linux, etc.), and can be run on few mobile devices. Free for basic features, but at a cost for other features. Wiki as a tool for asynchronous interaction Students working in a group have been a challenge for both instructors and students as they are frequently dissatisfied with its content and process. While content can be the goal of a course instruction, the process of learning becomes the roots to understanding of content as part of the goal. Thus, content exists within the process of acquiring that content, not outside of it (Tobin & Tippins, 1993). The establishment of new technology such as Wiki could possibly offer a solution for asynchronous interaction (Karasavvidis, 2010). Wiki discussion forum Wiki is known as server software that permits users to produce and edit content of a piece of writing, and it can be used to coordinate a group using any Web browser (Cunningham, 2002). Wiki is an integrated Web environment that also allows users to simply produce and uphold a Web presence for their subjects in collaboration with others. There are lists of Wiki software platforms available such as MediaWiki, WikiMatrix, XWiki, Tiki Wiki, WikiFoundry, and so on. WikiFoundry (previously known as Wetpaint) is a free website hosting service where anyone can create their own Wiki site. The system consists of features where students can access from any place at any time through an Internet connection. Further key features of the system are areas for the group members to post messages and respond to others postings, create forums or topics for discussion. Members have the opportunity to reply the messages in a manner that is not time and place dependent, as long as a 44 PJSRR(2015) 1(1): 40-49 © Universiti Putra Malaysia Press computer connected to the Internet is accessible. Each member can create new threads to the discussion topics or respond to the comments of other members in the forum. Moreover, all members have access to the above features and able to view, download, or print out the information. A Wiki consists of features exist in traditional content management systems (CMS) such as blogs and discussion forums. A CMS is a computer application that permits creating, deleting, editing, publishing, modifying content, and also maintenance from a central interface (Boag, 2009). It can also upload files to share information and download files sent by group members. The opening view of a forum shows the subject heading for the postings. The group member has the choice of either reading just the threads of a discussion forum or expanding the thread list to expose all threads or the responses to these threads. Individual messages can be viewed by clicking on the subject heading and then proceed through the thread and read each message. Černá, Poulová and Draessler (2011) conducted a survey via an online questionnaire on social software applications at a university and the respondents’ satisfaction towards the software. The data were collected from more than three hundred students at the University of Hradec Králové. The results show that wikis can be served as platforms for knowledge incorporation and collaboration in developing common knowledge. In relation to knowledge incorporation, wikis websites are wholly editable as any user can read, write or add content to a Wiki site. In a study, Augar, Raitman and Zhou (2004) used Wiki for an icebreaking activity at Deakin University, Australia, to facilitate online interactions among group members. The findings reveal that Wiki is indeed a useful tool for facilitating online education and can enhance the process of teaching and learning online. The features in a Wiki Webpage show that it is an exceptional tool for collaboration in an online environment which is also a valuable system for teaching and learning. In another study, Chu and Kennedy (2011) reported the use of Google Docs and MediaWiki as collaboration tools for co-constructing knowledge in an online group project. Twenty two undergraduates from the Information Management program at The University of Hong Kong participated in the study. All students have used MediaWiki for the major project and Google Docs for their final year project. Questionnaires and telephone interviews were conducted after completion of the final projects. They found that some of the students had positive experiences from using the tools where MediaWiki was effective in knowledge management, while Google Docs features were more user-friendly. However, Judd, Kennedy and Cropper (2010) investigated a learning activity which involved a large group of 177 undergraduates studying psychology at The University of Melbourne. There were 30 groups that consisted of 20-30 students and Wiki was used in the investigation. The authors found that although the features in Wiki are designed to facilitate collaboration, it does not constantly promote collaborative learning. This is due to little use of Wiki commenting feature and thus many students’ contribution were superficial. In another study, Witney and Smallbone (2011) have utilised Wiki to support group assessment for full-time undergraduate students. They observed the main constraint to the use of online tool was that student preferred traditional face-to-face teamwork. Elgort, Smith and Toland (2008) examined the perceptions of students and lecturers using wikis as a platform for group project in two postgraduate Master’s level courses. The authors highlighted that students’ attitude to group work are mixed and utilising Wiki is insufficient to improve these attitudes, though on the positive side the students considered Wiki as useful for sharing knowledge and organising information. Skype as a tool for synchronous interaction The synchronous, real-time interactions with free software such as Skype can actually enhance conventional classroom teaching and learning, and engage students to communicate, share and write on various projects. Skype is a software program using Voice over Internet Protocol (VoIP) technology (Fryer, 2014). The software is free for download and users can also make audio calls and 45 PJSRR(2015) 1(1): 40-49 © Universiti Putra Malaysia Press video conferences over the Internet everywhere in the world without any costs (Tsukamoto, Nuspliger & Senzaki, 2009). Skype instant messaging A Skype network can be used as a real-time interactive chat among group members. Skype provides services that enable users to communicate with their peers either by voice with a microphone or by video with a webcam and instant messaging by text over the Internet. The name ‘Skype’ was derived from ‘sky’ and ‘peer’ where originally it was a hybrid peer-to-peer and client-server system (Bryant, 2006). Its free version is often used among teachers and students to fulfill their educational goals. For instance, Skype is being used for communication among scholars in completing projects from different parts of the world as well as locally by real-time chat. Skype is also used in the classroom implemented by the teacher to facilitate sharing of ideas synchronously among students which makes the classroom more interactive (Sivula, 2011). It also enables teachers to collaborate with other teachers around the world for resources and getting to know the experts in the same field (Eaton, 2010). All synchronous dialogues that emerged in Skype Chat were automatically archived by date. In the survey of Černá et al. (2011), the authors found Skype an exclusive social communication application. Indeed, Skype is an example of a twenty-first century educational tool as it can basically support the teaching and learning environment, changing from traditional classroom learning to successful online collaborative learning. For instance, online technologies promise massive transformation in language learning (Mullen, Appel & Shanklin, 2009), and students are allowed to talk with an author via Skype (Foote, 2008). However, Sivula (2011) utilises Skype for courses involved a team in a collaborative project, claiming that problems do occur within the team interaction while completing the assignment, whether applied traditionally or online. Team members can share resources and information within their team through real-time meeting at a chosen time in Skype. Kearsley and Schneiderman (1999) suggested that learning activities should: (1) take place in a group setting (e.g. collaborative teams); (2) be task-based, and (3) have an external focus (authentic). Skype facilitates interaction by allowing students to form groups and they can also use their smartphones, iPads, iPods, tabs and a range of personal computers to interact with team members using Skype software. Conclusion The review suggests that online interaction systems have encouraged collaboration, thus CMC has become a topic of interest. Indeed, online collaboration offers new opportunities in learning with the arrival of technological innovations. In tertiary education, students need to generate in-depth understanding in their learning through managing interaction effectively and utilise online technology for collaborative tasks. Such management entails students’ interaction with resources, teachers, and peers. This type of interaction focuses online collaboration and this explains how a course should be designed to promote student participation and satisfaction. From this review, it is suggested that asynchronous interaction is good for students to practise and to improve writing skills, while synchronous is good for developing students’ social interaction or communication skills. In terms of pedagogical aspect, online collaboration involves learning resources and supports active learning which enables students to construct knowledge and attain their learning goals. For instance, students can perform collaborative writing through CMC interaction. In terms of social aspect, constant social interaction may also encourage students’ readiness to participate in online collaboration. Thus, it is significant to study further in order to understand more thoroughly concerning the usefulness of CMC for interaction and collaboration either asynchronous or synchronously in completing collaborative tasks. 46 PJSRR(2015) 1(1): 40-49 © Universiti Putra Malaysia Press References Alavi, M., Yoo, Y., & Vogel, D. R. (1997). 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TANGb & Mashohor Syamsiahc a b Department of Mechanical and Manufacturing Engineering, cDepartment of Computer and Communication Systems Engineering, Faculty of Engineering, Universiti Putra Malaysia * gs44638@student.upm.edu.my Abstract – Legged robot locomotion is a challenging field. Problems can occur during locomotion such as morphology, controller, and ambience factor, to name a few. However, there are always tradeoffs in designing legged robots, for example, speed against stability, number of limbs against complexity of controller, and mass of the robot against energy consumption of the actuators. Therefore, the problems can be minimized when the hardware and software complement each other. Active compliance mechanism describes a closed-loop system which actively sense-and-act according to the surroundings. Passive compliance mechanism, as its name suggests, is a regulatory mechanism in which it does not rely on the controller to actively respond in order to achieve adaptability. The composition materials of a legged robot provide the advantages during locomotion. In this review, we are going to investigate the differences of the mechanisms and how they can be complemented to diminish problems during locomotion. Keywords: Active compliance mechanism, legged robot, locomotion, passive compliance mechanism Introduction Legged robots belong to the family of mobile robots. Mobile robots are capable of moving around an environment by means of discrete foothold, continuous foothold, or hybrid foothold. A legged robot possesses a number of feet, which provide the maximum number of supporting points. As opposed to a legged robot, a wheeled robot locomotes around the environment with a continuous foothold. A hybrid mode combines the advantages of both legged and wheeled robots by producing continuous support on flat terrain and discrete support on uneven terrain. Mobile robots can be manually controlled or operate autonomously. Walking is a sequential mass shifting procedure which comprises a series of actuation of joints in a systematic manner. Several popular methods to generate a walking motion are zero-moment point (ZMP) (Vukobratović & Borovac, 2004), inverted pendulum (Kajita et al., 2002), inverse dynamics (Fujimoto & Atsuo, 1998), central pattern generator (Ijspeert, 2008), tri-pod gait (Cham, Karpick, & Cutkosky, 2004), to name a few. Therefore, it is a strenuous effort to perform the walking task. The interaction between a legged robot and the arbitrary surroundings is challenging because of high uncertainties ahead. Therefore, designing an intelligent controller is the ultimate goal of a legged robot locomotion. Floating-base inverse dynamics on LittleDog exhibits superior walking performance on uneven terrain by a precise foothold selection and a variable step length (Buchli, Kalakrishnan, Mistry, Pastor, & Schaal, 2009). However, a frequent controller activity results in high energy consumption and relatively low walking speed. Moreover, crashing with the surroundings and excessive foot impact forces are less desirable. 50 PJSRR (2015) 1(1): 50-57 © Universiti Putra Malaysia Press In this study, we are going to review two main streams of solving legged robot locomotion problems, namely, active compliance and passive compliance mechanisms. Active compliance mechanism is a closed-loop system, which the robot responds to the environment according to the sensory information. In contrast, passive compliance is an open-loop system, which the robot responds to the environment based on the body regulatory mechanisms, such as spring-damper mechanism, adjustable joint, and link stiffness. In the next section, active compliance and passive compliance mechanisms are equally investigated. The investigation includes fundamental principles of both mechanisms. Then, the importance of fusion of active and passive compliance mechanisms is discussed. In the conclusion section, problems of designing legged robots are summarised. Active compliance mechanisms As its name suggested, active compliance mechanisms require sensory information to aid decision making. The behaviour of the robot is solely reflected from sensory information. Therefore, an intelligent control paradigm is required in order to produce a walking behaviour. A legged robot possesses sensors, which are attached around its body to perceive the world. Robot cognition is a house of storing and retrieving information to aid a decision-making process. Kaplan (2000) implemented a learning mechanism in which the robot is able to interact with its user in order to acquire knowledge (object recognition). A cognition process is important because it allows the robot to understand the world, and acts accordingly. Figure 1 exemplifies three different layers of constructing a controller for a legged robot locomotion. The highest level is the main command to the robot, i.e. wandering aimlessly or target-oriented locomotion. Then, based on the start-point and the end-point, the path is planned. Lastly, according to the prearranged path, the trajectories of the joints are mapped. Explore the world Robot’s path planning Robot’s joints trajectories Figure 1: Hierarchical classification of active compliance mechanism controller The controller can be designed to act reactively or deliberatively. A reactive controller is defined as an action that is caused directly by the controller. A remarkable example is from Kimura, Fukuaka, and Cohen (2007) in which the robot is programmed with CPG to produce walking behaviour; reflexes and responses are designed to provide immediate response in order to cope with uncertainties (Kimura, Fukuoka, & Cohen, 2007). On the other hand, a deliberative controller is meant for prudent jobs. Tasks such as mine removal cannot afford a single failure, even for a minor case (Kato & Hirose, 2001). Brooks asserted that the traditional AI is weak to problem solving, because it requires internal representation of the world to make every decision. Comparatively, he proposed Subsumption Architecture (SA) of which a hierarchical set of layers is used to represent the behaviours (Brooks, 1991). Next, the robot behaviour is elicited by the mutual inhibition of signals from different layers. Details of traditional AI and SA are illustrated in Figure 2. 51 PJSRR (2015) 1(1): 50-57 © Universiti Putra Malaysia Press Figure 2: The principle of traditional AI is explained. The sensory information is required to penetrate into every single layer before a decision can be made. Therefore, it is time consuming and not applicable to highly dynamic world. Conversely, SA as shown in the lower figure decomposes the behaviour into layers with various priorities (Brooks, 1991) Passive compliance mechanisms A passive compliance mechanism, on the other hand, is a regulatory mechanism that does not rely on the controller to actively respond in order to achieve adaptability. The composition materials of a legged robot provide the advantages during locomotion. As observed in nature, we experience the flexibility and durability of bone structure, which allows us to perform prominently in sports, recover from stumbling, and protect the viscera against forces. Several studies have been conducted on tensile characteristics of human rib cortical bone, adaptability of bone properties to individual’s physical activities, and biomechanical properties of bone (Natali & Meroi, 1989; Rittweger et al., 2000; Subit, de Dios, Valazquez-Ameijide, Arreigui-Dalmases, & Crandall, 2011). There are a number of researches based on improving the material characteristics of the robot. For example, spring-damper mechanism (Poulakakis, Smith, & Buehler, 2005), variable link stiffness (Brown & Zeglin, 1998; Bailey, Cham, Cutkosky, & Full, 2000; Takuma, Ikeda, & Masuda, 2010; Galloway, Clark, Yim, & Koditschek, 2011), and adjustable joint stiffness (Pratt, Williamson, 1995; Poulakakis, Smith, & Buehler, 2005; Ham, Sugai, Vanderborght, Hollander, & Lefeber, 2009; Scarfogliero, Stefanini, & Dario, 2009). An experiment done on Scout II (Poulakakis, Smith, & Buehler, 2005) demonstrated the flexibility of the hip joints facilitate the running gait of the robot with only one actuator in a leg. The elasticity and flexibility of the materials bestow the capabilities of the legged robot to confront with various kinds of danger. Nonetheless, passive compliance mechanisms are still lack of flexibility, because the material properties are not changeable. Unlike living organisms, robots cannot adapt to the environment psychologically and physiologically. Energy storage in links and joints are useful to eliminate transient effects of external perturbation on the robot (Kim, Clark, & Cutkosky, 2006). Because the limbs and torso are interacting in unison, the chain reaction of the extrinsic disturbances are not negligible. The effect is more distinguishable when a higher locomotion speed and bouncing gait are required (Poulakakis et al., 2005). The former indicates the continuous impact between the limbs and terrain results in instability of robot; the latter illustrates the importance of releasing and storing energies to realize the bouncy movement. Thus, passive compliance mechanisms deliver the supplementary function to combat against disturbance from surroundings and to enhance the mobility of the robot. 52 PJSRR (2015) 1(1): 50-57 © Universiti Putra Malaysia Press Discussion In the previous section, we have revealed the functions of active compliance and passive compliance mechanisms. Next, we are going to make a comparative study on robot locomotion and animal locomotion, especially human. The study is divided into three facets, namely, pure active compliance mechanism, pure passive compliance mechanism, and combination of active compliance and passive compliance mechanisms. Pure active compliance mechanism Deliberative actions such as path planning, footstep placement on unstructured terrain require massive amount of signal processing. It emphasizes continuous perception-action cycle to generate the right behaviour to deal with current situations. The array of sensory information is utilized to determine the action which is more rewarding. There is a number of researches to show that emotion affects decision-making in human beings. (Carver, Sutton, Scheier, 2000; Wood, Quinn, & Kashy, 2002; Baumeister, DeWall, Vohs, & Alquist, 2010) The effect is twofold: emotion causes behaviour (Baumeister, Vohs, DeWall, & Zhang, 2007), and behaviour pursues emotion (Baumeister, Stillwell, & Heatherton, 1994). The former explains that an action of an individual is caused by the inner state (such as joy, grief, angry, and thirst), e.g. he is giving up because the weather is bad. By contrast, the latter denotes an action taken to acquire or refrain from the inner state, e.g. he is striving to reach the destination because he triumphs for achievement. It is still difficult to implement an emotional decision-making algorithm on a mobile robot because of our limited understanding of the brain. The concept of adaptive control is to control the movements of the joints in order to provide adequate joint stiffness and proper posture. Gait adaptation can be done by visual input, proprioceptive responses, force feedback at the feet, to name a few (Weingarten, Lopes, Buehler, Groff, & Koditschek, 2004; Manjanna & Dudek, 2015). A muscle-like property in the actuator can be realized by adjusting the parameters of the controller, and the joint position and stiffness can be varied according to various situations. A PD-controller is used to model a virtual spring-damper mechanism with the aim of increasing stability (Kimura et al., 2007). Xiong, Worgotter, and Manoonpong (2015) have created a modular neural network (MNN) controller to automatically tune the leg stiffness, thereby gaining adaptability on different surfaces. Pure passive compliance mechanism When the controller is inactive, a passive compliance mechanism demonstrates the practicality in a legged robot. A passive walker exemplifies the utilization of gravitational force to walk on slightly down slope without actuation (McGeer, 1990). The potential energy to kinetic energy conversion eliminates the power consumption from actuation. Besides, there is a 20% failure rate for a twolegged robot to walk steadily, mostly due to inappropriate initial conditions (Collins, Wisse, & Ruina, 2001). A morphological design of the robot is an important factor for maximum locomotion efficiency. Centre of gravity, number of limbs, type of limbs, type of actuators, material, and size are important components to robot building. For example, the bow leg design by Brown (1998) shows the possibility of using a string to control the elastic leg for robot locomotion. The leg compressed and extended during landing and lifting. As a result, it eliminates the knee and ankle actuators to produce locomotion. Another example of a single rotary actuator to produce forward locomotion is EduBot by Galloway (2011). In order to increase the passive compliance of the robot on various terrain conditions, the stiffness of the leg is tuneable. The study also discusses the effect of leg stiffness on walking speed and terrain conditions. In Takuma’s (2010) work, a wire is holding a series of elastic discs and a rigid block, and is attached to a winch. The winch is used to control the flexibility of the spine. As a result, this structure produces 53 PJSRR (2015) 1(1): 50-57 © Universiti Putra Malaysia Press a unique oscillation according to the degree of viscoelasticity. A simulation study is conducted to illustrate the effect of rigid spine, unidirectional flexibility spine, and bidirectional flexibility spine on passive running down on a slope (Kani, Derafshian, Bidgoly, & Ahmadabadi, 2011). The result shows that the bidirectional flexibility spine is the best in terms of stability and velocity. It is also worth mentioning that the joints are not controlled by actuators. Thus, the motion is generated by gravitational force. There are also many studies working on passive walkers. Thus, an energy efficient walker can be created using the concept of passive walkers with little power actuators to walk on slopes and flat terrains. In the next section, the combination of active and passive walking mechanisms is discussed in detail. Combination of active compliance and passive compliance Active compliance and passive compliance mechanisms are equally important for legged robot locomotion. It is recognizable in a complex situation, for instance, walking over uneven terrain, deformable surface, dynamic obstacles, and high speed locomotion. Because energy storage in the links and joints depress the external forces and disturbance, it indirectly regulates the behaviour of the robot. For example, a robot walks on a flat terrain with a fixed behaviour, and it stumbles over the uneven platform. The passive compliance mechanism is activated to buffer the ground perturbation. Another example illustrating the importance of combination of active and passive compliance mechanisms is leg configuration in Figure 3. Usually, a robot with an insect leg configuration has its legs widely spread and has lower centre of gravity. On the other hand, a mammal leg configuration has a smaller support polygon and a taller centre of gravity. In this example, it shows that different leg configurations attribute to different stabilities, walking speeds, energy expenditures, etc. It would be a long explanation for detailed elaboration for leg configuration alone. Böttcher (2006) explains the energy expenditure, stability, leg configuration and number of legs in order to get the right combination in legged robot design. On the other hand, Jones and Hurst (2012) analyse the effect of leg configuration on running and walking legged robots. In the study of De Santos, Estremera, and Garcia (2005), the energy requirement of the actuators is reduced by strategically placing the legs around the robot’s body. Figure 3: The left figure is a model of an insect-type leg configuration. The right figure is a model of mammal leg configuration. In another study, Zhao, Sumioka, and Pfeifer (2011) used two motors to actively control the spine motion. The spine is constructed using deformable and rigid blocks. By removing deformable blocks at different positions, it creates a virtual joint. In addition, the flexibility and length of the spine can be adjusted according to the specification of the robot. A flexible spine is also used in biped robot to increase the degree of freedom of the torso, and the advantage of flexibility and variability (Mizuuchi, Inaba, & Inoue, 2001). The flexibility of the torso allows the robot to have various postures and better impact absorption when the robot falls. A simulation study also shows that a flexible spine increases travel distance and walking performance (Moore, McGowan, & McKinley, 2015). 54 PJSRR (2015) 1(1): 50-57 © Universiti Putra Malaysia Press A semi passive walking study is done by Omer, Ghorbani, Lim, and Atsuo Takanishi (2011). A passive compliance mechanism is added to ankle joint. The ankle has springs built-in to store and release energy during walking. By adjusting the stiffness of the ankle joint, semi-passive motion can be realized. When a robot is walking, there are impact and friction losses. In order to continuously walking on flat surface, actuators can be added to compensate the energy losses during walking. Passive walker Veronica uses series elastic actuator to control swing phase and stand phase of the passive walker (Van Ham, Vanderborght, Verrelst, Van Damme, & Lefeber, 2006). A study also shows that serial elastic actuators have several benefits such as shock tolerance, lower reflected inertia, more accurate and stable force control, less damage to the environment and energy storage (Hutter, Remy, Hoepflinger, & Siegwart, 2011; Pratt, 1995). The difference between living organisms and robots is recoverability. Nevertheless, a true intelligent robot design emerges from the hardware and software designs. The hardware design fortifies the manoeuverability with resilient properties; the software design enhances the efficiency of actuation during locomotion. 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In Proceedings of the International Conference on Morphological Computation (pp. 130-132). 57 PJSRR (2015) 1(1): 58-66 © Universiti Putra Malaysia Press Pertanika Journal of Scholarly Research Reviews http://www.pjsrr.upm.edu.my/ Antioxidant Vitamins, Oxidant Injuries and Diseases Yusuf ABBAa, Hasliza Abu HASSIMb, Hazilawati HAMZAHa & Mohamed Mustapha NOORDINa* a Department of Veterinary Pathology and Microbiology, bDepartment of Veterinary Preclinical Sciences, Faculty of Veterinary Medicine, Universiti Putra Malaysia, 43400 Serdang, Selangor *noordinmm@upm.edu.my Abstract – Over the past few decades antioxidant vitamins have been shown to aid in disease prophylaxis as well as treatment. Deficiencies of these vitamins in diets have resulted in associated deficiency syndromes in both humans and animals. Since a handful of disease conditions is associated with imbalances of antioxidant enzymes such as catalase, superoxide dismutase, glutathione as well as increases in reactive oxygen species (ROS), nitrogen oxide species (NOS) and lipid per-oxidation markers such as malondialdehyde, supplementation with antioxidant vitamins has resulted in amelioration of oxidative damage and ultimately disease recession. Vitamins A, C and E together with compounds such as carotenoids have been extensively studied for their roles in disease modulation or exacerbation. However, while Vitamins C and E have been shown to have immense potentials in the alleviation of several conditions, Vitamin A and especially carotenoids had shown little or no use in conditions such as cardiovascular disease and cancer prevention. This review highlights the documented roles of these vitamins in disease prevention over the past few decades and the potentials that need to be explored further. Keywords: Antioxidant vitamins, disease, oxidative stress, antioxidant enzymes Introduction An antioxidant is any substance that significantly reduces or impairs the oxidation of a substrate once present in small amounts. The term oxidizable substrate includes every type of molecule found in vivo (Halliwell, 2001; Niki, 2014). Antioxidant vitamins are readily available in food items; however, most of them are not available in sufficient quantities to meet the daily recommended amount for humans or animals. Thus, in order to avert problems associated with chronic deficiencies, supplemental doses have to be taken to meet up the shortages. Most of the classical deficiency syndromes associated with these vitamins are not seen in the western countries. However, chronic deficiencies are common and associated with a lot of complex health problems especially in the elderly (Iqbal et al., 2004; Rao & Rao, 2007). Oxidant injuries to cells result from production of reactive oxygen species (ROS) and nitrogen oxides (NO). Reactive oxygen species such as superoxide (O2- ) and hydrogen peroxide (H2O2) cause respiratory burst and damage to cells. On the other hand, cellular enzymes such as catalase, glutathione and superoxide dismutase (SOD) modulate various chemical reactions that prevent oxidant injury to the cell. For example, while catalase activates the breakdown of hydrogen peroxide into water and oxygen, SOD catalyzes the dismutation of superoxide radicals to O2- and H2O2 and glutathione plays a major role in the reduction of oxygen species formed during respiratory burst and cellular metabolism (Halliwell & Whiteman, 2004). Since various disease processes have been shown to induce oxidant injury in cells, the use of antioxidant vitamins have been equally shown to modulate such oxidant injuries and ameliorate its deleterious effects in the body (Blokhina et al., 2003; S. Zaidi & Banu, 2004; S. M. Zaidi et al., 2005). Thus, this review discusses the various antioxidant vitamins and their mechanisms of preventing certain illnesses or conditions. 58 PJSRR (2015) 1(1): 58-66 © Universiti Putra Malaysia Press Antioxidant vitamins There are three main documented antioxidant vitamins, namely Vitamin A, Vitamin C and Vitamin E (α-tocopherol). Carotenoids (β-carotene) and selenium are also considered important since they have been shown to function synergistically with Vitamins A and E, respectively. Carotenoids are converted to Pro-Vitamin A and thus posses similar antioxidant roles in the physiological system to Vitamin A. This write-up also discusses the major antioxidant Vitamins A, C and E, as well as carotenoids and their mechanisms of action. (a) Trans-retinol (b) Ascorbic acid (C) α-tocopherol (d) β-carotene Figure 1: Chemical structures of (a) trans-retinol, (b) Ascorbic acid, (c) alpha-tocopherol and (d) βcarotene. Mechanisms of antioxidant vitamin action Aerobic microorganisms are shielded from ROS and NOS produced from oxidative stress by a diverse mechanism involving multiple antioxidants which have different functions and roles (Niki, 2014). While all antioxidants are either micro or macro molecules such as proteins and enzymes, they all proffer several defensive strategies against damage caused by oxidant damage (Halliwell & Whiteman, 2004). The first defensive action involves the prevention of ROS/NOS production by catalyzing the breakdown of hydroperoxidase and hydrogen peroxides to hydroperoxides and water. In the second defensive action, the antioxidants neutralize ROS/NOS before they induce cellular injury to the cells. Thirdly, damage caused to membranes and tissues are repaired by these antioxidant compounds or enzymes. Hence, antioxidants act cooperatively and synergistically in a dynamic defensive network to 59 PJSRR (2015) 1(1): 58-66 © Universiti Putra Malaysia Press cope with oxidative stress (Niki, 2014). Antioxidant defense against oxidative stress involves both enzymatic and non-enzymatic activities. While enzymatic defenses require enzymes such as glutathione peroxidase, catalase and superoxide dismutase, non-enzymatic defenses involve the presence of antioxidants such as carotenoids, lipoic acid, Vitamin C and Vitamin E. In order to minimize the effects of ROS, cells produce superoxide dismutase, glutathione peroxidase and catalase. Superoxide dismutase catalyzes superoxide anions to oxygen and hydrogen peroxide, catalase then reduces the hydrogen peroxide formed to water. Ascorbate peroxidase and dehydroascobate peroxidase formed by ascorbic acid in the cell also catalyzes the breakdown of hydrogen peroxide to water (Blokhina et al., 2003). This is a very important step in the neutralization of the peroxide and in alleviating oxidative stress in the cell. Vitamin A and β-carotene in disease prevention Vitamin A is one of the most essential vitamins of the biological system. It is required for maintaining the injury of the epithelium, immune function and cellular differentiation. Retinol is the active compound that is responsible for its numerous functions in the body system. The primary storage of Vitamin A in the kidneys, liver and adipose tissues is in the form of long chain fatty esters and provitamins (carotenoids). Its antioxidant action is exhibited through its excellent radical quenching ability, thus making it more effective in hypoxic state (Harabawy & Mosleh, 2014; Palace et al., 1999). Vitamin A has not been as efficient as Vitamins C and E in regulating the levels of oxidative stress enzymes such as glutathione, catalase and superoxide dismutase in stressed cells. In a study of chickens exposed to carbon tetrachloride, Vitamin A supplementation reduced glutathione levels in the plasma of chickens. However, while concurrent administration of Vitamin E was found to reduce plasma levels of SOD and glutathione, Vitamin A was found to attenuate this effect (Mahmoud & Hijazi, 2007). Similarly, it was earlier observed that retinol administration resulted in increased levels of SOD, catalase and glutathione peroxidase in rat sertoli cells thereby modulating oxidative enzyme activities (Dal-Pizzol et al., 2001). Vitamin A supplementation has been shown to lower the risk of coronary heart disease and ischemic heart disease. In another study, Vitamin A was observed to reduce injury and scarring following pyelonephritis (Dalirani et al., 2011). Β-carotene, which is a precursor for retinol and a carotenoid has been shown to have no protective effects against various conditions. For example in a randomized trial study in 18,314 smokers and asbestos workers given 30 mg of beta-carotene and 25,000IU of Vitamin A per day, it was observed that there was no reduction in the incidence of lung cancer, and adverse effects were seen in cancer development and cardiovascular disease (Omenn et al., 1996). In another randomized trial, administration of 20mg/day of beta-carotene was reported to be associated with a slight increase in the incidence of angina pectoris in 29,133 male smokers (Rapola et al., 1996). In a related study, a metanalysis study on the effect of beta-carotene administration and lung cancer development found an association between high dose of beta-carotene and risk of cancer (Tanvetyanon & Bepler, 2008). However, in a 9.4-year randomized trial study testing the effects of supplementation of 50mg of betacarotene given every other day to women, there was no overall effect of the supplementation on the outcomes of myocardial infarction, stroke, coronary revascularization or cardiovascular disease death (Cook et al., 2007). Thus, it can be seen from these numerous studies that the vitamin has very little or no beneficial effect on the prevention of conditions such as cancer and cardiovascular disease. Earlier studies with carotenoids reported beneficial and protective effects of carotenoids against ischemic heart disease, stroke, cancer, aging, immunomodulation, macular degeneration, cataract and photo-protection (Mayne, 1996; Rao & Rao, 2007). However, the manner at which most of these studies were conducted such as source of carotenoids, dose and duration of exposure were variable, and in most cases the studies were irreproducible. Nevertheless, these studies have contributed to the literature of the compound (Mayne, 1996; Rao & Rao, 2007). Vitamin C and its prophylactic role in disease Vitamin C (ascorbic acid) is a commonly available compound that acts effectively as an antioxidant and reducing agent at physiological pH, thus neutralizing the effect of reactive oxygen species (ROS) 60 PJSRR (2015) 1(1): 58-66 © Universiti Putra Malaysia Press in the body. This vitamin is required in many other processes such as collagen synthesis, synthesis of L-carnitine and conversion of dopamine to nor-epinephrine. Most animals can synthesize ascorbic acid physiologically, but humans, primates and hamsters cannot synthesize this vitamin because of the deficiency of gulonolactone oxidase. Hence, Vitamin C is unable to meet their daily requirements and they need daily supplementation in order to avert deficiency syndromes such as scurvy, spontaneous bleeding and joint and muscle pains (Iqbal et al., 2004; Y. Li & Schellhorn, 2007). As a nonenzymatic antioxidant defense system, ascorbic acid plays a crucial role in the regulation of hydrogen peroxide levels in oxidative stress. It has been shown to work concurrently with glutathione and glutathione transferase, thus its presence may boost cellular glutathione levels. Since it does not have a direct role in lipid peroxidation, it may not significantly alter the level of malondialdehyde in oxidative stress (Padayatty et al., 2003). In addition, Vitamin C was found to regulate the levels of SOD, catalase, GST, GSH and MDA in immobilized stressed rats (S. M. Zaidi et al., 2005). This shows the potential of regulating increased level of MDA and decreased levels of SOD, catalase, GST and GSH by this vitamin. However, since different factors such as infection, injury and toxicity inflict oxidative stress via different mechanisms/paths, the amelioration of elevated enzyme levels reported has been conflicting (Padayatty et al., 2003). Moreover, Vitamin C via its antioxidant properties have been shown to prevent or alleviate a lot of conditions including viral diseases. It has been found to alleviate hypoxia-reperfusion induced apoptosis via the release of Cytochrome C and the activation of Caspases 9 and 3 in human endothelial cells (Montecinos et al., 2007). In cancer cells and normal endothelial cells, it was found to alleviate oxidative stress by the uptake of cysteine (Park, 2013). Decreased lung pathology in mice and prevention/suppression of flu symptoms in man were also observed following ascorbic acid administration (Gorton & Jarvis, 1999; W. Li et al., 2006). Vitamin C has also been shown to arrest cancer cell development via both its antioxidant and pro oxidant effects (Y. Li & Schellhorn, 2007). The supplementation of Vitamin C in exercise-stressed rats was shown to cause reduction in the levels of previously elevated enzymes such as Copper SOD, magnesium SOD and glutathione (Ryan et al., 2010). The in vitro and in vivo anti-viral effects of Vitamin C have been studied in a number of viral infections. In general, Vitamin C exhibits either a direct effect on the virus by inhibiting its replication or an indirect one by modulating ROs and NOS production by decreasing bioavailability of superoxide dismutase (SOD), inhibition of SOD mediated NO activation and by preserving the normal enzymatic activity of NOS (Brinkevich et al., 2012). In vitro viral inactivation from Vitamin C administration has been reported in the rabies virus (Madhusudana et al., 2004), cytomegalo virus (Cinatl et al., 1995), influenza virus (Cheng et al., 2012), herpes virus and paramyxo virus (White et al., 1986), and herpes simplex virus (Betanzos-Cabrera et al., 2004), just to mention a few. The in vivo actions of Viatamin C have been reported in HIV, where ROS contributing to viral replication via the activation of NFK-B was attributed to changes in ascorbic acid, Vitamin E, carotenoids, selenium, SOD and glutathione. Overall concentrations were observed to decline in plasma despite an unchanged redox status during the infection course (Baker & Wood, 1992). Ascorbic acid has also been shown to increase levels of IL2, CD4+, CD8+, IgM+ cells and anti IgG antibodies in vaccinated chickens challenged with infectious bursal disease virus (Wu et al., 2000). Decreased lung pathology in mice and prevention/suppression of flu symptoms in man were also observed following ascorbic acid administration (Gorton & Jarvis, 1999; W. Li et al., 2006). Vitamin E (α-tocopherol) and disease prevention There are eight isomers in the Vitamin E family namely α-, β-, γ-, and δ-tocopherols and tocotrienols (4 Tocopherols and 4 Tocotrienols). Several studies have been conducted on the pharmacological uses of these isomers since almost a century ago (1922), when the vitamin was first discovered. Vitamin E is a scavenger for active free radicals through the transportation of hydrogen atom to produce Vitamin E and radical free product. In some situations, Vitamin E may scavenge free radicals through a mechanism of electron transfer to yield a Vitamin E cation radical, which subsequently undergoes fast de-protonation to produce a Vitamin E radical. In other scenarios, Vitamin E scavenges lipid peroxyl 61 PJSRR (2015) 1(1): 58-66 © Universiti Putra Malaysia Press radicals and lipid hydroperoxide resulting in the formation of Vitamin E radicals (Niki, 2014). Although there are conflicting reports on its mode of action as an anti-oxidant, some believe that its major function is that of peroxyl radical scavenger, which is important for maintaining the integrity of membranes of cells (Traber & Atkinson, 2007). However, others believe its action are due to its antioxidant properties (Brigelius-Flohé & Davies, 2007). Since it has been shown that the most abundant and readily available form of Vitamin E is α-tocopherol, most of the studies were conducted using this isomer (Paul et al., 2012; Traber & Atkinson, 2007). Interestingly, other researchers argued that tocotrienols and other tocopherol isomers (δ and λ) are better than α-tocopherol especially in preventing cancer (Yang et al., 2012). As a potent lipid peroxyl radical, tocopherol has been reported to reduce the level of lipid peroxidation associated with oxidative stress in highly lipogenic tissues like the brain. Thus it was found to reduce the level of MDA in the tissues and alleviate tissue damage. Additionally, it was found to reduce the level of SOD, GST, catalase and glutathione (S. Zaidi & Banu, 2004). Vitamin E was also found to restore decreased SOD, catalase, GST, GSH and increased MDA, ALT and AST in rats after immobilization (S. M. Zaidi et al., 2005). In a related study, the vitamin was found to decrease SOD and GPx activities that were increased following restraintinduced stress (S. M. Zaidi et al., 2005). Moreover, Vitamin E has been reported to reduce the incidence of cancer, aging, restoration of blood flow following ischemia and reperfusion injury, arthritis, cataract and platelet hyper-aggregability (Packer, 1991). Several human and animal trial studies have shown the beneficial roles of Vitamin E in the prevention of a number of diseases and conditions. However, some findings are contradictory in the sense that different research groups propose different findings. An example is in the case of prostate cancer; while some found it to have a preventive role (Klein et al., 2011; Virtamo et al., 2014), others found it to predispose more to the development of cancer (Albanes et al., 2014; Lippman et al., 2009). However, Yang et al. (2014) explained that the vitamin can have a double role in cancer prevention or potentiation due to the absence of other isomers in current therapeutic forms. In other studies, Vitamin E administration was found to reduce cardiovascular conditions and related deaths in women by 7% and 24%, respectively (Lee et al., 2005). However in a recent study, the administration of vitamin E did not show any beneficial effect in the prevention of cardiovascular disease in human participants (Myung et al., 2013). Other reported uses of the vitamin include the prevention of pro inflammatory state in calves and the enhancement of passive maternal antibody transfer (Krueger et al., 2014); prevention of vascular degeneration through reduction in homocysteine and cholesterol levels in rats (Kirac et al., 2013); reduction in inflammatory stressor; IL2, C-reactive protein and vascular endothelial growth factor which lead to atherosclerosis due to heavy and chronic alcohol consumption (Shirpoor et al., 2013); protection against contrast induced acute kidney injury in chronic kidney disease patients (Tasanarong et al., 2013); the reduction in renal scarring secondary to pyelonephritis in children (Sobouti et al., 2013); the reduction in the incidence of angina pectoris in male smokers (Rapola et al., 1996), and the prevention of mono sodium glutamate induced renal toxicity in rats, among many other preventive functions (Paul et al., 2012). Synergistic actions of antioxidant vitamins in prophylaxis Several antioxidant vitamins have been shown to have synergistic effects when combined together. For instance, Vitamins A, C and E prevented the gastro-esophageal disease, Barret’s esophagus and esophageal carcinoma (Lukic et al., 2012), while other observed a low incidence of in heavy metal toxicity following the administration of a combination of Vitamins A, C, E and selenium in fish, as compared to administration of a single vitamin (Harabawy & Mosleh, 2014). In a 9.4-year randomized trial study testing the effects of a combination of 600IU of Vitamin E and 500mg of Vitamin C on women, there were fewer incidences of stroke in participants taking a combination of the two vitamins as compared to those taking either of the two (Cook et al., 2007). These few examples show the compatibility these vitamins have in the biological system and they may act better together than alone, in some instances. Conclusion Antioxidant vitamins play important roles in the biological system as they counteract the oxidative stress and imbalances in the system produced by excess ROS and NOS production. Vitamins E and C 62 PJSRR (2015) 1(1): 58-66 © Universiti Putra Malaysia Press are most effective in ameliorating decreased levels of SOD, GSH, GPx and catalase, while they were also found to modulate increased levels of MDA. Vitamin A has so far been shown to be poor in modulating these enzyme alterations. Therefore, the safety of prolonged usage of this vitamin in humans and other animals still needs to be evaluated as several reports have shown them to be either inefficient or even increase mortalities in certain trail cases (Bjelakovic et al., 2012). Acknowledgements The authors are grateful for the funding from Universiti Putra Malaysia (Grant No: 9438740) and Ministry of Higher Education Malaysia (Fundamental Research Grant: 5524641). 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Drugs in R & D, 6(3), 157-165. doi:634 [pii] 66 PJSRR (2015) 1(1): 67-81 © Universiti Putra Malaysia Press Pertanika Journal of Scholarly Research Reviews http://www.pjsrr.edu.my/ Quantum Dot-sensitized Solar Cell Based on nano-TiO2 Electrodes Wardatun Nadrah, MOHD AMIN1, a Zulkarnain, ZAINAL1,2, b * Zainal Abidin, TALIB3, c Hong Ngee, LIM1, 4, d and Sook Keng, CHANG2,e 1 Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia 2 Material Synthesis and Characterization Laboratory, Institute of Advanced Technology, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia 3 Department of Physic, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia 4 Functional Device Laboratory, Institute of Advanced Technology, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia a wardatunnadrah@gmail.com, bzulkar@upm.edu.my, czainalat@upm.edu.my, d hongngee@upm.edu.my Abstract - Quantum dots-sensitized solar cell (QDSSC) is one of the third generation solar cell that is the most promising low cost, easy to manufacture and highly efficient solar cell. Compared to Dyesensitized solar cell (DSSC), quantum dots (QDs) of QDSSC has a narrow bandgap and possess excellent properties such as tunable band gaps, strong light absorption and high multiple electron generation. Titanium dioxide or titania (TiO2) is an oxides semiconductor material that is frequently used as a photoanode in this photovoltaic system due to high stability under visible light illumination. TiO2 is also known as a good photocatalyst and an excellent choice in environmental purification. The efficiencies of electron injection and light harvesting in QDSSC are affected by the nature, size morphology, and quantity of this nanomaterial. In this review, the concept and principles of the QDSSCs are reviewed. The preparation and fabrication method ofTiO2 electrode in QDSSC are also discussed. It is worthwhile to know the architecture of TiO2 in order to enhance the efficiency of QDSSC. Keywords: Quantum dots-sensitized solar cell, titanium dioxide, quantum dots Introduction Sunlight continued to be harvested by technologies up to the early years of the industrial revolution. Since then, the temperature has risen by 0.6oC because of the global activities which cause the greenhouse effect whereby the quantity of carbon dioxide increases and eventually causing global warming (Du, Li, Brown, Peng, & Shuai, 2014; El Chaar, Lamont, & El Zein, 2011; Gong, Liang, & Sumathy, 2012). In recent years, renewable energy has attracted high interest due to these factors. As an alternative source of energy, the sun sends high quantities of light energy to the surface of the earth (Selinsky, Ding, Faber, Wright, & Jin, 2013). It is also completely renewable and definitely an abundant resource with rapidly declining conversion cost (Jun, Careem, & Arof, 2014). The energy provided by the sun for our planet is 10,000 times more than world demand whereby 10 % of the efficiency of the solar cell would fulfil global needs (Kouhnavard et al., 2014). A broad range of solar cell research is currently underway and they include dye-sensitized solar cell (Abdullah & Rusop, 2014), organic solar cell (Halim, 2012), silicon solar cell (Halim, 2012) and heterojunction solar cell (Church, Muthuswamy, Zhai, Kauzlarich, & Carter, 2013; Guo, Shen, Wu, & Ma, 2012). The photovoltaic technology (PV) is a highly potential candidate for an alternative or renewable source of energy in the current market. PV can be classified into first, second and third generation solar cell. Solar cells based on silicon wafer, so-called first generation technology solar cell, make up 67 PJSRR (2015) 1(1): 67-81 © Universiti Putra Malaysia Press the most number of solar cells present in the market and can reach as high a 27% solar cell efficiency (Green, 2002).Meanwhile solar cell utilized with inorganic film is the second generation solar cell which is cheaper to produce but has less than 14% solar cell efficiency (Jun, Careem, & Arof, 2013). Chronologically, the invention of the third-generation solar cell is to decrease cost by significantly increasing efficiencies as high as above 30% and at the same time maintain the economic and environmental cost advantage (Conibeer, 2007). Figure 1 shows the PV production per square meter against the efficiency of solar cell and the cost unit power. Figure 1: Efficiency and cost projection for first (I), second (II) and third generation (III) (waferbased, thin films, and advanced thin film, respectively) Dye-sensitized solar cell (DSSCs) is the first third generation which has attracted much attention due to low fabrication cost and high efficiency, flexibility in colour, shape and transparency (Golobostanfard & Abdizadeh, 2014). However QDSSCs is the further improvement of dye-sensitized solar cell (DSSCs) in boosting the overall efficiency by coupling synthesized inorganic quantum dots (QDs) semiconducting materials as sensitizers (Prabakar, Minkyu, Inyoung, & Heeje, 2010).QDSSC based on semiconductor nanocrystal has attracted attention as an alternative to DSSCs owing to their great stability, good absorption over wider wavelength range and multiple exciton generation leading to the production of power efficiencies (Z) that are much higher than DSSC (Xu, Zou, Yu, & Zhi, 2013; Yang, Chen, Roy, & Chang, 2011). All these unique characteristics of the QDSSC have raised high interest among researchers in renewable energy research field. Despite all of these good characteristics of QDSSCs, the power conversion efficiency is still not as impressive as DSSCs mainly due to several reasons such as bad charges separation, less efficient photo excited electrons and unsuitable sensitizers (Li, Yu, Liu, & Sun, 2015). The electrode also plays a critically important role in contributing to the high efficiency of the QDSSC performance. Photo anode with high strong light scattering, efficient electron transport, high QD loading and quick electrolyte is of great importance to the QDSSC system (Zhou et al., 2014). The unique textural and structural characteristic of nanostructured material such as TiO2, SnO2 and ZnO has attracted much interest in the past decade(Malekshahi Byranvanda, 2013). The unique textural and structural characteristics are particle size distribution, specific surface area, morphology, crystallinity and crystal structure (Hu et al., 2014). This review paper is focused on TiO2 as an electrode in QDSSC. During the past decade, TiO2 has become one of the most popular electrode materials and different methods apply to photovoltaic application and QDSSC specifically. In addition TiO2 is an ecofriendly commercial product and has been known to be effective and is of great value(Liao et al., 68 PJSRR (2015) 1(1): 67-81 © Universiti Putra Malaysia Press 2012). TiO2 is a semiconductor with wide band gap known to be n-type. It has three crystalline phases which are anatase (tetragonal), rutile (tetragonal) and brookite (orthorhombic).The most stable phase is rutile TiO2 whereby anatase and brookite TiO2 are metastable and they can be converted into rutile phase at high temperature that is, around 750oC (Wang, He, Lai, & Fan, 2014). Single crystal anatase is reported to be more effective than rutile phase in photovoltaic application (Bet-moushoul, Mansourpanah, Farhadi, & Tabatabaei, 2016). Basic principle of QDSSC QDSSCs have similar configuration with DSSCs and the only difference is that QDSSCs uses inorganic semiconductor quantum dots (QDs) as light absorbing material instead of molecular dyes, onto the surface of a thin film of nano-TiO2 electrode that acts as a working electrode (Song et al., 2014). Similar to DSSCs, in QDSSCs, excitons are formed in quantum dots whereby the charge separation occurs in the QD molecule layer upon the photoexcitation as electrons are injected from the QD excited state into the conduction band of the nano-TiO2 and that eventually produces a photovoltaic effect as shown in figure 2. Figure 2: Operating principle of QDSSC QDs is restored through electron donation from the frequently used polysulfide electrolyte, which consist of (S2-/Sx2-) the redox system. The oxidized QD is then restored (hole is filled with electron) when it is reduced by S2- from the electrolyte and in turn it is oxidized into Sx2- that diffuses to the counter electrode. 𝑆 2− + 2ℎ+ → 𝑆 (1) 2− 𝑆 + 𝑆𝑥−1 → 𝑆𝑥2− (𝑥 = 2 − 5) (2) The oxidized group 𝑆𝑥2− are reduced to 𝑆 2− occur on the counter electrode. 2− 𝑆𝑥2− + 2𝑒 − → 𝑆𝑥−1 + 𝑆 2− (3) In the electrolytes, voltage is generated in the Fermi levels between the electron in the photo electrode and the redox potential of 𝐼 − /𝐼3− .𝐼 − ion reduced to 𝐼3− at the counter electrode whereby platinum and carbon based materials coated on the substrate (Guo, Shen, Wu, Wang, et al., 2012; Lee & Chang, 69 PJSRR (2015) 1(1): 67-81 © Universiti Putra Malaysia Press 2008; Yu, Lia, Qiu, Kuang, & Su, 2011). The efficiency of the solar cell can be determined by the equation below: 𝜂= (𝐽𝑆𝐶 ×𝑉𝑂𝐶 ×𝐹𝐹) , 𝑃𝑖𝑛 (4) where 𝐽𝑆𝐶 is the short circuit photocurrent density, 𝑉𝑂𝐶 is the open circuit voltage, 𝐹𝐹 is the fill factor and 𝑃𝑖𝑛 is the power intensity of the incident light. The 𝐽𝑆𝐶 ,𝑉𝑂𝐶 and 𝐹𝐹 values can be calculated from the direct current density-voltage (J-V) curves. TiO2 as an electrode The excellent properties of TiO2such as good chemical stability, low cost production, high corrosion resistance, non-toxicity, high photocatalytic activities and good charge transport properties play an important role in the performance of QDSSC (Barbe et al., 1997; Kong, Chang, & Jang, 2014; Ou & Lo, 2007). TiO2 nanostructure such as nanoparticles(Balis, Dracopoulos, Bourikas, & Lianos, 2013; Chen, Chappel, Diamant, & Zaban, 2001; Ito et al., 2007; Jung, Kim, Kim, Choi, & Ahn, 2012; Kongkan, Tvrdy, Takechi, Kuno, & Kamat, 2008; Zaban, Mic´ic, Gregg, & Nozik, 1998; Zhang et al., 2009), nanotubes (Chen et al., 2009), nanorods (Gonfa et al., 2014), nanowires (Nikhil, Thomas, Amulya, Mohan Raj, & Kumaresan, 2014; Sun et al., 2012) and nanoflower (Yu, Li, Liu, Cheng, & Sun, 2014b) have been widely recognised as excellent photo anodes in QDSSC. The size of the TiO2 building units, apparently in nanometer scale, highly influences the performance of QDSSC (Kavitha, Gopinathan, & Pandi, 2013). Table 1 shows the example of QDSSC and the solar cell efficiency performance based on nano- TiO2 as an electrode. Table 1: Example of QDSSC and the solar cell efficiency performance based on nano-TiO2 as an electrode. TiO2 TiO2 nanoparticle Sensitizer CuInS2 Counter electrode Cu2S Efficiency 1.05% Reference (Gong et al., 2012) TiO2 sol CdSe Cu2S/CNT 1.05% TiO2 nanoparticle CdSe Pt 3.65% TiO2 nanotube TiO2 beads TiO2 nanoparticle TiO2 nanoparticle CdSexTe1-x CdS/CdSe CdSe CdS Pt Cu2S Pt Pt 0.588% 4.33% 2.23% 1.15% Mesoporous spherical TiO2 powder TiO2 sol gel CdS/CdSe Pt 0.29%/0.34 % (Golobostanfard & Abdizadeh, 2014) (Prabakar et al., 2010) (Xu et al., 2013) (Zhou et al., 2014) (Song et al., 2014) (Lee & Chang, 2008) (Kong et al., 2014) InP Pt - TiO2 nanoparticle TNT/TNP ZnS, CdS, CdSe CdSe Pt, CoS, CuS 2.7% - TNP TiO2 nanoparticle TiO2 nanoparticle TiO2 nanoparticle CdS CISe CdS/CdSe/ZnS CdS Pt Cu2S NiS Cu2S 4.3% 2.97% 2.15% 70 (Zaba, Mic´ic´, Gregg, & Nozik, 1998) (Balis et al., 2013) (Kongkanand, Tvrdy, Takechi, Kuno, & Kamat, 2007) (Jung et al., 2012) (Yang et al., 2013) (Kim et al., 2014) (Zhou et al., 2013) PJSRR (2015) 1(1): 67-81 © Universiti Putra Malaysia Press Table 1: Example of QDSSC and the solar cell efficiency performance based on nano-TiO2 as an electrode (continued). TiO2 TiO2 nanoparticle Sensitizer CdS/CdSe Efficiency 1.2% Reference (Jun, Careem, & Arof, 2014) SnSe2 SnS CdS Ag2Se Counter electrode Pt/Cu2S/Graphite/ Carbon soot/ Reduced Graphene Oxide (RGO) Pt Pt/CuS Pt TiO2 nanoparticle TiO2 nanoparticle TiO2 nanosheet TiO2 nanoparticle 0.12% <0.1% 1.95% 3.6% TiO2 nanoparticle CdS NiS 3.6% TiO2 nanorod CdS/PbS Pt 2.0% TiO2 nanoparticle CuInS2 Cu2S 1.85% TiO2 nanodendrite array TiO2 nanoparticle TiO2 hollow sphere TiO2 nanowire CuInS2 Cu2S 1.26% CdS/CdSe CdS/N719 PbSe Brass plate Pt - 0.45% 4.66% - TiO2 nanoparticle CdS CoS2/Pt 2.27% TiO2 nanotube CdS0.54Se0.46 Pt - TiO2 nanoparticle Cu1.8/CuS 3.26% TiO2 nanoparticle CdSxSe1-x/ Mn-CdS CdS/CdSe/ZnS (Yu et al., 2012) (Miyauchi, 2011) (Li et al., 2014) (Tubtimtae, Lee, & Wang, 2011) (Li, Yang, Zhang, Zhang, & Li, 2014) (Jiao, Zhou, Zhou, & Wu, 2013) (Peng, Liu, Shu, Chen, & Chen, 2013) (Peng, Liu, Zhao, et al., 2013) (Shen et al., 2015) (Cui et al., 2015) (Győri, Kónya, & Kukovecz, 2015) (Punnoose, Kim, Srinivasa Rao, & Pavan Kumar, 2015) (Gakhar, Smith, Misra, & Chidambaram, 2015) (Li et al., 2015) NiS 3.03% TiO2 nanorods arrays CdSe/Mn-CdS Cu1.8S/CuS 2.40% (Gopi, Srinivasa Rao, Kim, Punnoose, & Kim, 2015) (Yu, Li, Liu, Cheng, & Sun, 2014a) Preparation of TiO2 as an electrode in QDSSC In QDSSC, TiO2 nanoparticles (example like commercial P25 nanoparticles) have been extensively studied as a photoanode due to their special characteristics as mentioned before (Zhou et al., 2014).Anatase, rutile and brookite are the three crystalline form of TiO2 whereby anatase is the most preferable in solar energy conversion. This is due to the ability to avoid charge recombination and 71 PJSRR (2015) 1(1): 67-81 © Universiti Putra Malaysia Press efficient electron transport in photoanode (Byranvana, Bazarganb, & Kharat, 2012). In recent years, a lot of research have gone into preparing TiO2among them are in achieving low cost production and making them easily reproducible by using a simple method which is eventually imperative for the industrial manufacture of QDSSC (Zhang et al., 2009).The methods in preparing TiO2 such as the hydrothermal method (Gopinathan, & Pandi, 2008; Vijayalakshmi & Rajendran, 2012; Wu et al., 2013), the sol gel method (Behnajady & Eskandarloo, 2013; Guo, Liu, Hong, & Jiang, 2005; Sabataitytė, Oja, Lenzmann, Volobujeva, & Krunks, 2006) and anodization (Tang et al., 2008) have been studied extensively in order to produce excellent characteristics of TiO2 as a photoelectrode. Sol-gel method The sol-gel method for TiO2 synthesis is a very useful tool for photo-induced molecular reaction due to the special variables such as particle size, incident light, phase composition and convenient preparation method (Karami, 2010). Titanium (IV) isopropoxide (TIPP) is usually used as a starting material in this method(Manoharan & Venkatachalam, 2015; Zeng, Chen, Su, Li, & Feng, 2014). The mixture will undergo an aging period and it is kept in the oven to obtain the colloidal solution (Zeng et al., 2014). Next the solution is dried and calcined to get TiO2 nanocrystal powder (Hu, Tang, He, Lin, & Chen, 2014; Laranjo et al., 2014; Zhu, Zhang, Gao, & Cao, 2000). Figure 3 shows TiO2 nanoparticles prepared by the sol gel method at different levels of concentration. Figure 3: SEM surface images of three different kinds of TiO2 concentrations of (a) 17 wt.%, (b) 20 wt.%, and (c) 24 wt.% films on the SnO2:F glass after sintering process(Lee et al., 2009). Hydrothermal method Hydrothermal method is one of the most popular methods to prepare TiO2 nanostructure. Other than TiO2 nanoparticle, other nanostructures such as nanotube and nanorod can also be synthesized via the hyrothermal method (Lee, Lee, Rhee, & Park, 2014). One of the suggested methods is TIPP where it is mixed and stirred with nitric acid, ethanol and distilled water through the sol-gel method. The product produced from the sol-gel method will undergo hydrothermal treatment in the teflon-lined autoclave to produce TiO2 powder and the powder will receive further treatment for calcination to achieve the desired size and crystallinity (Manoharan & Venkatachalam, 2015). Figure 4 shows SEM images of TiO2 nanorod arrays formed by the hydrothermal method by optimization of the seed layer. 72 PJSRR (2015) 1(1): 67-81 © Universiti Putra Malaysia Press Figure 4: SEM images of TiO2nanorod arrays grown by hydrothermal method on (a) bare FTO, (b) FTO immersed in 0.05 M TiCl4 solution, (c) FTO immersed in 0.1 M TiCl4 solution, (d) FTO immersed in0.15 M TiCl4 solution, (e) FTO immersed in 0.2 M TiCl4 solution, respectively (Wang et al., 2013) Electrochemical method The Electrochemical method is an impressive technology to develop the nanotube or nanoporous layer as an electrode especially in QDSSC. TiO2 nanotube can be formed by an anodization of the titanium whose capability is strongly influenced by the variation of parameters. The quality and ability of TiO2 nanotubes also depends on their very own properties such as crystallite size, morphology and the lattice strain. Yulian Zhang et al.,(2015)reported the frequent used of ammonium fluoride (NH4F) as an electrolyte and indicated that high NH4F concentration is beneficial to the growth of ribs around the nanotubes. Figure 5 shows the FESEM images of surface morphologies and cross-section of TNTs obtained in electrolytes with different NH4F concentrations. Meanwhile, Munirathinam, Pydimukkala, Ramaswamy, & Neelakantan (2015) reported on the development of TiO2 nanotubes by the anodization process using the two electrode system whereby titanium was used as anode and a stainless steel plate as a cathode at a specific distance. In this research, two different electrolytes which are hydrofluoric acid, HF (acidic medium) and sodium sulfate, Na2SO4 (neutral) were used and then followed by annealing at 450oC for 2h. The result clearly indicated nanotubes formed from the neutral bath are four times longer than the ones synthesized from the acidic bath. 73 PJSRR (2015) 1(1): 67-81 © Universiti Putra Malaysia Press Figure 5: FESEM images of surface morphologies and cross-section of TNTs obtained in electrolytes with NH4F concentrations of (a) (d) 0.2 wt%, (b) (e) 0.4 wt%, (c) (f) 0.6 wt%, respectively (Zhang et al., 2015) Approach in improving TiO2photoanode in QDSSCs Although QDSSC raised tremendously high attention among researchers in order to improve solar cell performance, energy conversion efficiency remains under 10% as reported in figure 1. A lot of work has been done in the approach to improve QDSSC. One of the important approaches to increase the energy conversion efficiency yield is the architecture of the photoanodes. This is because photoanode material like TiO2 has wide band gap (3.20 eV for anatase and 3.02 eV for rutile TiO2) that limit its usage at UV light region(Maheswari & Venkatachalam, 2015). Other than that, optimal nanoparticle interconnection and pores size can control the charge carrier transport to ensure an efficient electrolyte penetration (Yacoubi, Samet, Bennaceur, Lamouchi, & Chtourou, 2015). Among studies that have been done recently are doping TiO2 electrode with Ni (Maheswari & Venkatachalam, 2015), Au (Liu et al., 2014), Co (Brigham, Achey, & Meyer, 2014; C. Wang et al., 2014), Fe (Wang et al., 2014) and Mn (Wang et al., 2014). Doping TiO2 with impurities dopants will broaden the use of the PV to the visible region and at the same time provide a good surface for the deposition of QDs (Maheswari & Venkatachalam, 2015; Yacoubi et al., 2015). The dopants also act as a light harvesting material which means the light will be scattered and trapped in order to increase the effective path length of incident light of the absorption of the semiconductor (Liu et al., 2014). Some dopant like Fe have been reported as having the ability to increase charge carrier density of TiO2 leading to good carrier transportation and separation and relatively long electron lifetime(Wang et al., 2014). Beside dopants, surface modification also play an important role in order to avoid or reduce recombination of excited electron whereby it is a major problem in QDSSC(Kim et al., 2012). TiCl4is usually applied on the substrate at multiple times of immersion, followed by annealing at 450oC for 30 min before depositing TiO2 paste (Kim et al., 2012). Nevertheless, TiCl4 treatment decreases average 74 PJSRR (2015) 1(1): 67-81 © Universiti Putra Malaysia Press pore size whereby it can lower the recombination and increase the current (Guo et al., 2014). Recently, a study focused on the treatment of TiO2 hydrolysed by hydrochloric acid (HCl) in preparation of TiCl4 stock solution has been reported for the synthesis of nanosized crystalline TiO2 (Lee & Yang, 2005). The result from this study showed that the brookite phase was transformed to the rutile phase with increase reaction time, while through a heat treatment, it was transformed to rutile via anatase phase (Lee & Yang, 2005). Previously, there were so many efforts made to optimize TiO2 structures to enhance QDSSC performance. The first effort made was by creating large pore size distribution of TiO2 to make the loading process of quantum dots much easier due to the small size of quantum dots (Salant et al., 2012). Secondly, the surface area of TiO2 was increased in order to increase quantum dots loading. Moreover, high surface area of photoanaode may improve the quantum dots coverage and retard unnecessary interface recombination (Song et al., 2012). Thirdly, an additional layer of coating was also added to improve the electron transport path in order to enhance the QDSSC performance. However, previous researches reported that an additional layer of TiO2 can hardly balance the required qualities of TiO2 (Wu et al., 2015). Therefore, further studies on optimization of TiO2 should be done to meet the demand in QDSSC. For example, Wu et al. (2015) designed a multi-dimension titanium dioxide made up of mesoporous nanoribbons consisting of oriented aligned nanocrystal. This impressive development resulted in increased surface area of TiO2 that led to a high photocurrent efficiency of 4.15%. Meanwhile, in another study an attempt has been done by doping TiO2 nanocrystal with two dimensional graphene in order to improve the photovoltaic performance owing to the graphene unique characteristics such as good thermal conductivity, good mobility charge carriers and specific surface area (Chen, Tuo, Rao, & Zhou, 2014). The incorporation of graphene with TiO2 increase the photocurrent efficiency by 37% compared to the pure TiO2 and eventually increased the QDSSC performance. Conclusions and future directions The review on TiO2 as a working electrode in QDSSC demonstrated high potential inorder to increase energy conversion efficiency in a novel QDSSC system. The study of photoanode configuration is critically important because the significance can be of high impact particularly in providing high QD loading, strong light scattering, quick electrolyte diffusion and efficient electron transport (Zhou et al., 2014). Different nanocrystal structure such as nanotubes, nanorods and nanowire have been developed whereby particular control is given to recombination and this eventually improves PV performance. Currently, a lot of studies are focused on developing low cost high ability nanocrystal material for PV application and this will no doubt raise its potential when developed and applied in the academia and industry. The low cost nanocrystal material used make the current price of QDSSC cheaper than DSSC ($3/Wp–$4/Wp) and silicon solar cell ($3/Wp) (Kalowekamo & Baker, 2009). Future work should be focused on improving the solar cell efficiency as mentioned in this review paper. Many modifications on QDSSC have been developed however, they are still in their early stages and many other new developments can be done in order to improve the efficiency, robustness and potential of the thin-film-type material. No doubt, as the understanding of the topic continues, more possible ideas can be conceived to improve QDSSC potential. 75 PJSRR (2015) 1(1): 67-81 © Universiti Putra Malaysia Press References Abdullah, M. H., & Rusop, M. (2014). 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The Journal of Physical Chemistry C, 117(51), 26948-26956. doi: 10.1021/jp410615b Zhou, R., Zhang, Q., Uchaker, E., Yang, L., Yin, N., Chen, Y., & Cao, G. (2014). Photoanodes with mesoporous TiO2 beads and nanoparticles for enhanced performance of CdS/CdSe quantum dot co-sensitized solar cells. Electrochimica Acta, 135, 284-292. doi: 10.1016/j.electacta.2014.05.021 Zhu, Y., Zhang, L., Gao, C., & Cao, L. (2000). The synthesis of nanosized TiO2 powder using a solgel method with TiCl4 as a precursor. Journal of Materials Science, 35, 4049-4054. 81 PJSRR (2015) 1(1): 82-90 © Universiti Putra Malaysia Press Pertanika Journal of Scholarly Research Reviews http://www.pjsrr.edu.my/ Nitric oxide and Its Important Role in Plant Defence Nurul Najihah, MOHD NASIR,a & Noor Baity, SAIDI,b* a Department of Cell and Molecular Biology, Faculty of Biotechnology and Biomolecular Sciences, Universiti Putra Malaysia, 43400 Serdang, Selangor Darul Ehsan, Malaysia. E-mail address: n.najihah79@gmail.com b Department of Cell and Molecular Biology, Faculty of Biotechnology and Biomolecular Sciences, Universiti Putra Malaysia, 43400 Serdang, Selangor Darul Ehsan, Malaysia. E-mail address: norbaity@upm.edu.my * norbaity@upm.edu.my Abstract – Nitric oxide (NO) is a signaling molecule involved in numerous physiological processes in both animals and plants. The bioactivity of NO is mainly transduced via post-translational modification of cysteine residues of proteins termed S-nitrosylation. Interestingly, a number of key regulatory components in plant defense responses have been found to be regulated by S-nitrosylation making this type of protein modification an important modulator of plant immunity. As a signaling molecule, NO intimately interact with other important molecules such as reactive oxygen species. Since the identification of NO in plants, increasing number of papers isbeing published in the area of NO biology each year. Here, a collection of papers describing the role of NO in plant immunity has been brought together to provide a bird's-eye view on the focus area. Keywords: Nitric oxide, plant immunity, S-nitrosylation __________________________________________________________________________________ Nitric Oxide: General Properties Nitric oxide (NO) acts as a signaling molecule within species from every biological kingdom. Because of its unique chemistry, which permits permeability, stability and reactivity, NO and its derivatives are ideally suited to its cellular signaling function. At room temperature and at atmospheric pressure, NO is a free radical colourless diatomic gas with lipophilic property. Its small Stoke’s radius and neutral charge allow rapid membrane diffusion (Kiger et al., 1993) and can play a part in cell-to-cell signaling over a brief period of time. Due to the presence of unpaired electron and the free radical nature of NO, it readily reacts with oxygen (O2), superoxide (O2-), transition metals and thiols, which largely shape its cellular function within the cell (Mur et al., 2006; Neill et al., 2008; Hong et al, 2008). The reaction of NO with O2 results in the generation of NOx compounds (including NO2, N2O3, and N2O4), which can either react with cellular amines and thiols, or simply hydrolyze to form end metabolites of nitrite (NO2-) and nitrate (NO3) (Wendehenne et al., 2001). Nitric Oxide Production in Animals and Plants NO is a multifunctional effector involved in numerous mammalian physiological processes, including neurotransmission, immunological and inflammatory responses, and relaxation of vascular smooth muscle (Schmidt and Walter, 1994). However, the use of NO is not confined to the animal kingdom alone. NO is also involved in diverse physiological processes in plants, such as defense response, metabolism, cellular detoxification, transport, iron homeostasis, signaling, flowering, and lignin 82 PJSRR (2015) 1(1): 82-90 © Universiti Putra Malaysia Press biosynthesis (He et al., 2004; Bason-Bard et al., 2008; Wendehenne et al., 2014; Yu et al., 2014). Despite the importance to elucidate the biosynthesis of NO in plants, there is still much uncertainty after years of research. In animals, NO is synthesized primarily by the enzyme nitric oxide synthase (NOS), which catalyzes the NADPH-dependent oxidation of L-arginine to L-citrulline and NO (Stuehr et al., 2004). Three NOS isoforms have been identified (Nathan and Xie, 1994); neuronal NOS (nNOS), endothelial NOS (eNOS) and inducible NOS in macrophages (iNOS). nNOS and eNOS are considered as constitutive and both show fast and transient activation. iNOS is induced in macrophages and many other cell types in response to inflammatory agents and cytokines (Mayer and Hemmens, 1997; Beck et al., 1999). Compared to constitutive NOSs, iNOS activityis able to be sustainedlonger, ismore stable and generates more NO, thus exerting cytotoxic and antimicrobial effects on the immune systems (Beck et al., 1999). NO synthesis in plants involves both arginine and nitrite-dependent pathways. It is well documented that potential enzymatic sources of NO in plant cells include nitrate reductase (NR) and NOS-like activity (Neill et al., 2003; Romero-Puertas et al., 2004; Wang et al., 2006; Medina-Andres et al., 2015). NR catalyzes the in vitro production of NO through a one-electron reduction of nitrite via the use of NAD(P)H as an electron donor (Yamasaki and Sakihama, 2000). Despite a few contradictory evidences that collectively suggest that NR is not likely to be the major generator of the NO synthesized during pathogen-triggered nitrosative burst (Hong et al., 2008; Yamasaki, 2000), it has been viewed as a candidate for NO production during plant-pathogen interaction (Neill et al., 2003). Moreover, recent genetic based approaches using NR-deficient mutants denoted that NO is mainly produced from NR that probably operates downstream of the L-arginine-dependent pathway (Corpas et al., 2009; Vitor et al., 2013) Although there is no obvious homolog of animal NOS in the Arabidopsis genome, several NOS-like activities have been reported (Cueto et al., 1996; Barroso et al., 1999; Corpas et al., 2006). In addition, mammalian NOS inhibitors have been shown to effectively abrogate the pathogen-triggered NO production in plants (Delledone et al., 1998; Neill et al., 2003). Corpas et al. (2009) had elaborately compared animal and plant NOS and concluded that plants also possess L-arginine-dependent NOS activity which is different from canonical animal NOS. A search for the enzyme(s) that catalyze(s) the pathogen-triggered NO production in Arabidopsis led to the cloning of the Arabidopsis NOS 1 (AtNOS1) gene, which exhibited significant sequence similarity to a snail gene that encoded a NOS-like activity, but with no homology to mammalian NOS (Guo et al., 2003). However, it has been difficult to demonstrate reproducibility of typical NOS activity through recombinant AtNOS1 (Crawford et al., 2006). Instead, AtNOS1 was found to serve as a chloroplast-targeted GTPase essential for proper ribosome assembly (Flores-Perez et al., 2008) and therefore renamed Arabidopsis nitric oxide associated 1 (AtNOA1). Several other mutants with altered NO levels had been found to show increased NO accumulation correlated with concentrations of putative substrates for NO biosynthesis but none of them was exclusively involved in NO production (Leitner et al., 2009). The closest evidence to the existence of a plant NOS-like enzyme is the identification of a functional NOS with 40% similarity to human NOSs in the green alga, Ostreococcustauri (Foresi et al., 2010). On the other hand, researchers have reported that NO can also be formed non-enzymatically in a reaction between nitrogen dioxide and plant metabolites, in nitrous oxide decomposition or as a result of chemical reduction of NO2- at acidic pH (Wendehenne et al., 2001). This area of research remains controversial and clearly, it is imperative to determine the key NO generator in plants to improve our understanding of NO metabolism. 83 PJSRR (2015) 1(1): 82-90 © Universiti Putra Malaysia Press S-nitrosylation as a Redox-Based Signalling Factor in Plants NO-related signaling can be attributed to various NO derivatives, collectively referred to as reactive nitrogen species (RNS), which comprise of not only the NO radical (NO·) and its nitroxyl (NO -) and nitrosonium (NO+) ions, but also peroxynitrite (ONOO-), S-nitrosothiols (SNO), higher oxides of nitrogen and dinitrosyl-iron complexes (Leitner et al., 2009). NO and RNS exert their biological actions through the chemical modification of targets by reacting with different amino acids or prosthetic groups. They mostly act through the binding oftransition metals of metalloproteins (metal nitrosylation), the covalent modifications of cysteine (S-nitrosylation) and tyrosine (tyrosine 3nitration). These processes emerge as specific post-translational protein modifications and the best characterized among these is S-nirosylation which involves the covalent attachment of an NO moiety to the thiol side chain of cysteine to form SNO. S-nitrosylated proteins have been identified through a proteome-wide scale analysis in several plants including Arabidopsis, potato, pea and citrus L. (Lindermayr et al., 2005, Kato et al., 2013, Camejo et al., 2013, Tanou et al, 2009). In this framework, S-nitrosylation regulates a wide array of proteins involved in all major cellular activities and the formation of SNO may serve to stabilize and diversify NO-related signals. As a regulatory mechanism in plants and animals, S-nitrosylation is a reversible process. Indeed, Snitrosylated proteins can be easily de-nitrosylated as the S-NO bond is labile in a cytoplasm’s reducing environment, allowing cells to flexibly and precisely modulate protein function in response to environmental signals. S-nitrosylated proteins are in dynamic equilibrium with de-nitrosylated proteins largely due to the action of glutathione (GSH) with the subsequent formation of Snitrosoglutathione (GSNO), reconstituting the protein thiol as a consequence. GSNO has the ability to release NO or function as a transnitrosylationg agent, thus it is considered as a natural reservoir of NO (Besson-Bard et al., 2008; Leitner et al., 2009). Two of the enzymes that are known to metabolize GSNO are S-nitrosoglutathione reductase (GSNOR) and thioredoxin (Feechan et al., 2005; Lamotte et al., 2015). The presence of GSNOR is conserved in bacteria, animals and plants (Liu et al., 2001) and due to its ubiquitous nature, this enzyme was suggested to confer protection against nitrosative stress rather than as a cell signaling factor. In contrast, thioredoxin or thioredoxin reductase denitrosylation reactions seem to be a part of a signal transduction mechanism (Lindermayr and Durner, 2009). GSNOR controls intracellular levels of GSNO and limits NO toxicity through NADH-dependent reduction of GSNO to glutathione disulfide (GSSG) and ammonia (NH3) (Sakamoto et al., 2002). Though highly specific for GSNO, GSNOR seems to modulate the extent of total cellular SNO formation (Liu et al., 2001; Feechan et al., 2005), and thus is regarded as the key enzyme responsible for the modulation of NO-mediated signaling pathways (Cheng et al., 2015). Important Role of NO and SNO in Plant Disease Resistance The function of NO in signaling defense responses during plant-pathogen interactions has been well documented in many experiments conducted years ago. A widespread feature of plant disease resistance is the programmed hypersensitive response (HR), a programmed execution of plant cells at sites of attempted infection that serve to limit the pathogen spread (Delledonne et al., 2001; Mur et al., 2006 ). NO is suggested to play a key signaling role during HR, next to the accumulation of ROS and salicylic acid (Agurla et al., 2014). In animals, many biological effects of NO including apoptosis are mediated by the highly toxic molecule, ONOO-, which is relatively non-toxic in plants (Bonfoco et al., 1995). On the contrary, HR-associated cell death in plants is proposed to be mediated by the relative levels of NO and H2O2 that areformed by the dismutation of O2- by SOD. In many cases, impairment of NO production via genetic mutation or treatment with NO inhibitor will negatively affect H 2O2 accumulation, leading to suppressed HR advancement (Rasul et al., 2012; Vitor et al., 2013; Kulik et al., 2014; Trapet et al., 2014; Qiao et al., 2015). In plants, ONOO- is continuously produced in healthy cells, exposing them to an environment rich in ONOO-. Therefore, plants have developed some 84 PJSRR (2015) 1(1): 82-90 © Universiti Putra Malaysia Press detoxification mechanisms, for example, through the action of peroxiredoxin II E (PrxIIE), a member of the peroxiredoxin family of antioxidant enzymes responsible for lipidoxidation and tyrosine nitration (Romero-Puertas et al., 2007). Interestingly, PrxIIE has been found to be S-nitrosylated during the HR resulting in inhibition of its hydroperoxide-reducing peroxidise activity together with its ability to detoxify ONOO- and also increasing the amount of tyrosine nitration (Romero-Puertas et al., 2007). In conclusion, NO regulates the effect of its own reactive species through S-nitrosylation of crucial components of the antioxidant defence system. NO also controls cell death in plants through S-nitrosylation of Arabidopsis metacaspase 9 and cytosolic glyceraldehyde 3-phosphate dehydrogenase, both of which can act as potential executioners of programmed cell death (Belenghi et al., 2007). The involvement of NO in controlling cell death is further unearthed by the study of one of the mammalian NADPH oxidase homologs in plants, respiratory burst oxidase homolog (RBOH) D (Yun et al., 2011). RBOH is involved in the production of reactive oxygen species (ROS), particularly hydrogen peroxide, which is produced in response to pathogen recognition (Torres et al., 2002). NO was shown to inhibit AtRBOHD activity through S-nitrosylation at Cys-890, thus influencing the inherent effect of ROS during HR-associated cell death in plants. Based on the fact that Cys-890 is evolutionary conserved, it was suggested that S-nitrosylation of this specific residue might regulate the activity of NADPH oxidase in many other eukaryotes. NO is not only thought to function during the development of hypersensitive cell death but also in the establishment of plant disease resistance complementary to and independent of ROS (Wang et al., 2013; Trapet et al., 2014). Administration of NO donors induced the expression of defense-related genes encoding phenylalanine ammonia lyase (PAL), the first enzyme of phenylpropanoid biosynthesis pathway and pathogenesis-related protein 1 (PR-1) (Durner et al., 1998; Vitor et al, 2013). NO action in plants, at least partially, is mediated through the SA-dependent signaling pathway. NO treatment induces GSH accumulation which is required to elevate endogenous SA accumulation (Kovac et al., 2015) that results in induction of PR genes (Durner et al., 1998; Kovac et al., 2015). NPR1, a master regulator of SA-mediated defense genes and a crucial component of disease resistance and signal cross-talk is known to be redox-regulated (Tada et al., 2008), adding an important clue towards understanding NO’s signaling functions (Figure 1). Treatment with GSNO induces NPR1dependent defense response in Arabidopsis (Kovac et al., 2015). S-nitrosylation of NPR1 controls its subcellular localization through oligomer-monomer exchange and thus its transcription co-factor activity. Mutations at critical cysteine residues in NPR1 increased monomer accumulation, constitutive nuclear localization and NPR1-mediated gene expression in the absence of a pathogen (Mou et al., 2003; Tada et al., 2008). Another very interesting example for the regulatory function of NO is S-nitrosylation of AtSABP3, which may interfere with the signal cross-talk as both carbonic anhydrase and SA-binding activities of the protein are inhibited (Wang et al., 2009). 85 PJSRR (2015) 1(1): 82-90 © Universiti Putra Malaysia Press Figure 1: Cross-talk of nitric oxide (NO) in plant cells In addition to the data presented above, the importance of NO and SNO in plant disease resistance were presented through the analysis of a GSNOR knock-out mutant. Loss-of-function mutation in Arabidopsis GSNO reductase 1 (AtGSNOR1) resulted in increased cellular levels of SNOs and compromised all modes of disease resistance (Feechan et al., 2005). GSNO accumulation in the mutant plant is accompanied by a marked decrease in SA content and increased susceptibility to various pathogenic microbes. Interestingly, the mutant showed an increase in HR even in the absence SA and ROS, suggesting that plant cell death mediated by an increase in SNO alone is sufficient to convey resistance in the absence of associated defence responses (Yun et al., 2011). Conversely, enhanced AtGSNOR1 activity results in increased protection against ordinarily virulent microbial pathogens. AtGSNOR1 also positively regulates the signaling network controlled by the plant immune system activator, SA (Feechan et al., 2005). Subsequently, similar results were obtained by Tada et al. (2008) through NPR1 studies. Surprisingly, when using antisense strategy, basal resistance has been reported to increase in atgsnor1 antisense plants, correlating with higher levels of intracellular SNOs and constitutive activation of PR-1 (Rusterrucci et al., 2007), which is the opposite result to that obtained by Feechan et al. (2005). Probably the contradictory reactions of the GSNOR modified plants might be a result of different cellular levels of SNO that change dramatically in atgsnor1 mutants (Feechan et al., 2005) compared to minor changes in the antisense plants (Rusterucci et al., 2007). Nevertheless, both studies underline the physiological importance of SNO formation and turnover in regulating multiple modes of plant disease resistance. The work of Feechan et al. (2005) is supported by a study on the levels of SNO and NO in Arabidopsisthaliana cell suspension cultures (Frungillo et al., 2014). According to the study, antisense GSNOR transgenic lines displayed higher levels of SNO and NO under optimal growth conditions; in accordance with the designated role of GSNOR as a modulator for GSNO. A similar observation was reported in a study with different organs of healthy pepper plants where tissues with the lowest GSNOR activity presented higher GSNO and NO contents (Airaki et al., 2011). In the involvement of GSNO, the postulated mobile 86 PJSRR (2015) 1(1): 82-90 © Universiti Putra Malaysia Press signal modulation by GSNOR in the systemic defense response was also investigated and GSNO was shown to act synergistically with classical defense hormones such as SA and JA (Espunya et al., 2012; Freschi, 2013; Zhou et al., 2015). Collectively, GSNOR would serve as an ideal target for crop improvement through genetic engineering. Conclusion and Perspective Fundamental studies to understand the complexity of S-nitrosylation in the plant biological system especially during the execution of plant stress responses is undeniably crucial since S-nitrosylation provides a distinctive platform for NO to exert its impact on various proteins associated with pathophysiological mechanisms. To date, the number of candidates for S-nitrosylation is increasing and the physiological relevance of the S-nitrosylation process is becoming more evident. 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