(Citrus Sinensis) Peels
Transcription
(Citrus Sinensis) Peels
CHARACTERIZATION OF PECTIC SUBSTANCES EXTRACTED FROM ORANGE (Citrus sinensis) PEELS By Wisal El Musafa Elsiddig Mohamed B.Sc. (Agric) Honours University of Khartoum 1995 A dissertation Submitted In Partial Fulfillment of the Requirements for the Degree of Master of Science in Food Science and Technology Supervisor Dr. Babiker Elwasila Mohamed Department of Food Science and Technology Faculty of Agriculture University of Khartoum June - 2005 DEDICATION To the soul of my Father, To my dear family.. Mother, brothers and sisters To my dear friends and colleagues With love and respect j|átÄ Acknowledgement I would like to express my gratitude and thanks to my supervisor Dr. Babiker El Wasila Mohamed for his helpful and constructive supervision which was vital to the success of the research. My thanks and recognition are extended to Ustz. Huda Abdalla Mohamed, Food Industries Department, Industrial Research and Consultancy Centre. My thanks and appreciation are extended to every body who helped me during this study. Above all, my thanks and praise to Allah who gave me patience and will to accomplish this work. ABSTRACT Pectic substance of two types of orange peels (yellow and green) were investigated. Samples were obtained from the local market. The orange fruits were washed, peeled and then the peels dried and ground. The study involved chemical composition, alcohol insoluble solids of orange peels and isolation of orange peels pectic substances, which were assayed and characterized for their moisture, ash, alkalinity, protein, acetyl content, methoxyl content, total carboxyl groups, anhydrogalacturonic acid, equivalent weight, calcium, magnesium, degree of esterification, intrinsic viscosity and molecular weight. Results showed that yellow and green orange peels contained 6.72% and 7.92% moisture, 2.90% and1.85% ash, 5.84%and 6.65% protein, 8.30% and 9.47% fibre, 3.08% and 2.75% oil, 0.43% and 0.40% titrable acidity, 60.09mg/100gm and 34.95mg/100gm ascorbic acid, 11.01% and 5.03% reducing sugar, 16.62% and 7.77% total sugars, 0.78mg/100g and 0.83mg/100gm calcium, 0.19mg/100g and 0.18mg/100gm magnesium and 50.55% and 60.74% alcohol insoluble solids respectively. The results showed that alcohol insoluble solids of the two types contained 2.92% and 5.63% moisture, 4.09% and 4.48% ash, 7.65% and 7.49% protein, 14.84% and 16.06% pectin, 0.22mg/100gm and 0.21mg/100gm calcium and 0.12mg/100gm and 0.11mg/100mg magnesium respectively. The results obtained, indicated that green orange peels contain relatively higher percentage of pectin compared to yellow orange peels. Total pectin was found to be 14.48% for yellow type and 16.06% for green type. The methoxyl content was 8.95% and 8.87% respectively. The acetyl content was found to be 0.44%, for yellow peels and 0.46% for green type. The degree of esterification was estimated to be 73.8% for yellow type and 72.47% for green type. The total carboxyl groups were found to be 1.96meq/gm for yellow type and 1.98meq/gm for green type. The anhydrogalacturonic acid content was 68.99% and 69.49%, respectively. The equivalent weight was estimated to be 974.60 and 920.73 respectively. The viscosity was 2.2/g/dl and 2.07g/dl respectively. The molecular weight was estimated to be 4.2 × 104 for yellow type and 4.03 × 104 for green type. The ash content was 3.14% and 3.37% respectively. The protein content was 3.57% and 3.44% respectively. The calcium content was found to be 0.28mg/100gm for yellow type and 0.3mg/100gm for green type. The magnesium content was estimated to be 0.09mg/100gm and 0.07mg/100gm, respectively. The results, obtained in this study, indicated that both quantity and quality of pectin obtained from orange peels (yellow and green) are suitable for the commercial production of pectins. ﺑﺴﻢ اﷲ اﻟﺮﺣﻤﻦ اﻟﺮﺣﻴﻢ ﺧﻼﺻﺔ اﻷﻃﺮوﺣﺔ ﺃﺠﺭﻴﺕ ﺍﻟﺩﺭﺍﺴﺔ ﻋﻠﻰ ﻨﻭﻋﻴﻥ ﻤﻥ ﻗﺸﻭﺭ ﺍﻟﺒﺭﺘﻘﺎل ﻫﻤﺎ :ﺍﻷﺼـﻔﺭ ﻭﺍﻷﺨـﻀﺭ ﻭﻗـﺩ ﺃﺴﺘﺠﻠﺒﺕ ﺍﻟﻌﻴﻨﺎﺕ ﻤﻥ ﺍﻟﺴﻭﻕ ﺍﻟﻤﺤﻠﻲ ﻟﺘﻘﻴﻴﻡ ﺍﻟﻤﻭﺍﺩ ﺍﻟﺒﻜﺘﻴﻨﻴﺔ .ﻏﺴﻠﺕ ﺜﻤﺎﺭ ﺍﻟﺒﺭﺘﻘﺎل ﻭﺠﻔﻔـﺕ ﺍﻟﻘﺸﺭﺓ ﺜﻡ ﺴﺤﻨﺕ. ﺸﻤﻠﺕ ﺍﻟﺩﺭﺍﺴﺔ ﺘﺤﺩﻴﺩ ﺍﻟﻤﻜﻭﻨﺎﺕ ﺍﻟﻜﻴﻤﻴﺎﺌﻴﺔ ﻭﺍﻟﻤﻜﻭﻨﺎﺕ ﻏﻴﺭ ﺍﻟﺫﺍﺌﺒـﺔ ﻓـﻲ ﺍﻟﻜﺤـﻭل ﻟﻘﺸﺭﺓ ﺍﻟﺒﺭﺘﻘﺎل ﻭﺇﺴﺘﺨﻼﺹ ﺍﻟﻤﻭﺍﺩ ﺍﻟﺒﻜﺘﻴﻨﻴﺔ ﻤﻥ ﻗﺸﺭﺓ ﺍﻟﺒﺭﺘﻘﺎل ﻟﻤﻌﺭﻓﺔ ﺨﺼﺎﺌﺼﻬﺎ ﺍﻟﻜﻴﻤﻴﺎﺌﻴﺔ ﻤﻥ ﺤﻴﺙ ﺍﻟﻤﺤﺘﻭﻱ ﺍﻟﻤﻴﺜﻭﻜﺴﻴﻠﻲ ،ﺍﻟﻤﺤﺘﻭﻯ ﺍﻷﺴﺘﻴﻠﻲ ،ﺩﺭﺠﺔ ﺍﻷﺴـﺘﺭﺓ ،ﻤﺤﺘـﻭﻯ ﺤﻤـﺽ ﺍﻷﻨﻬﻴﺩﺭﻭﻴﻭﺭﻭﻨﻙ ،ﺍﻟﻌﺩﺩ ﺍﻟﻜﻠﻲ ﻟﻤﺠﻤﻭﻋﺔ ﺍﻟﻜﺎﺭﺒﻭﻜﺴﻴل ،ﺍﻟﻭﺯﻥ ﺍﻟﻤﻜﺎﻓﺊ ،ﺍﻟﻠﺯﻭﺠﺔ ،ﺍﻟـﻭﺯﻥ ﺍﻟﺠﺯﻴﺌﻲ ،ﺍﻟﻜﺎﻟﺴﻴﻭﻡ ،ﺍﻟﻤﺎﻏﻨﺯﻴﻭﻡ ،ﻨﺴﺒﺔ ﺍﻟﺭﻤﺎﺩ ﻭﻨﺴﺒﺔ ﺍﻟﺒﺭﻭﺘﻴﻥ. ﺃﻅﻬﺭﺕ ﺍﻟﺩﺭﺍﺴﺔ ﺃﻥ ﺍﻟﻨﻭﻋﻴﻥ )ﺍﻷﺼﻔﺭ ﻭﺍﻷﺨﻀﺭ( ﻤﻥ ﻗﺸﺭﺓ ﺍﻟﺒﺭﺘﻘﺎل ﻴﺤﺘﻭﻱ ﻋﻠﻰ %6.72ﻭ %7.92ﺭﻁﻭﺒﺔ %2.9 ،ﻭ %1.85ﺭﻤﺎﺩ %5.84 ،ﻭ %6.65ﺒﺭﻭﺘﻴﻥ%8.30 ، ﻭ %9.47ﺃﻟﻴــﺎﻑ %3.08 ،ﻭ %2.75ﺯﻴــﺕ %0.43 ،ﻭ%0.4ﺍﻟﺤﻤﻭﻀــﺔ60.09 ، ﻤﻠﺠﻡ100/ﺠﻡ ﻭ 34.95ﻤﻠﺠﻡ100/ﺠﻡ ﻓﻴﺘﺎﻤﻴﻥ %11.01 ،Cﻭ %5.03ﺴﻜﺭﻴﺎﺕ ﻤﺨﺘﺯﻟﺔ، %16.62ﻭ %7.77ﺴﻜﺭﻴﺎﺕ 0.78 ،ﻤﻠﺠﻡ100/ﺠﻡ ﻭ 0.83ﻤﻠﺠﻡ100/ﺠﻡ ﻜﺎﻟﺴﻴﻭﻡ0.19 ، ﻤﻠﺠﻡ100/ﺠﻡ ﻭ 0.18ﻤﻠﺠﻡ 100/ﺠﻡ ﻤﺎﻏﻨﺯﻴﻭﻡ ﻭ %50.55ﻭ %60.74ﻤﻭﺍﺩ ﻏﻴﺭ ﺫﺍﺌﺒـﺔ ﻓﻲ ﺍﻟﻜﺤﻭل ﻋﻠﻰ ﺍﻟﺘﻭﺍﻟﻲ. ﻜﻤﺎ ﺃﻭﻀﺤﺕ ﺍﻟﻨﺘﺎﺌﺞ ﺃﻥ ﺍﻟﺠﺯﺀ ﻏﻴﺭ ﺍﻟـﺫﺍﺌﺏ ﻓـﻲ ﺍﻟﻜﺤـﻭل ﻟﻠﻨـﻭﻋﻴﻥ ﺍﻷﺼـﻔﺭ ﻭﺍﻷﺨﻀﺭ ﻴﺤﺘﻭﻯ ﻋﻠﻰ %2.92ﻭ %5.63ﺭﻁﻭﺒﺔ %4.09 ،ﻭ %4.48ﺭﻤـﺎﺩ%7.55 ، ﻭ %7.49ﺒــﺭﻭﺘﻴﻥ %14.48 ،ﻭ %16.06ﺒﻜﺘــﻴﻥ 0.22 ،ﻤﻠﺠــﻡ100/ﺠــﻡ0.21 ، ﻤﻠﺠﻡ100/ﺠﻡ ﻜﺎﻟﺴﻴﻭﻡ ﻭ 0.12ﻤﻠﺠﻡ 100/ﺠﻡ ﻭ 0.11ﻤﻠﺠﻡ 100/ﺠـﻡ ﻤـﺎﻏﻨﺯﻴﻭﻡ ﻋﻠـﻰ ﺍﻟﺘﻭﺍﻟﻲ. ﻜﻤﺎ ﺩﻟﺕ ﺍﻟﻨﺘﺎﺌﺞ ﺃﻥ ﻗﺸﺭﺓ ﺍﻟﺒﺭﺘﻘﺎل ﺍﻷﺨﻀﺭ ﺘﺤﺘﻭﻯ ﻋﻠﻰ ﻨﺴﺒﺔ ﺃﻋﻠﻰ ﻤﻥ ﺍﻟﺒﻜﺘـﻴﻥ ﻤﻘﺎﺭﻨﺔ ﺒﻘﺸﺭﺓ ﺍﻟﺒﺭﺘﻘﺎل ﺍﻷﺼﻔﺭ .ﻭﻟﻘﺩ ﻭﺠﺩ ﺃﻥ ﻤﺤﺘﻭﻯ ﺍﻟﺒﺭﺘﻘـﺎل ﺍﻷﺼـﻔﺭ ﻤـﻥ ﺍﻟﺒﻜﺘـﻴﻥ %14.48ﺒﻴﻨﻤﺎ ﺍﻟﺒﺭﺘﻘﺎل ﺍﻷﺨﻀﺭ ) %16.06ﻋﻠﻰ ﺃﺴﺎﺱ ﺍﻟﻭﺯﻥ ﺍﻟﺠﺎﻑ( .ﺃﻤـﺎ ﺍﻟﻤﺤﺘـﻭﻯ ﺍﻟﻤﻴﺜﻭﻜﺴﻴﻠﻲ %8.95ﻭ 8.87ﻟﻠﺒﻜﺘﻴﻥ ﻤﻥ ﺍﻟﻌﻴﻨﺘﻴﻥ ﻋﻠﻰ ﺍﻟﺘﻭﺍﻟﻲ ﻭﻟﻘﺩ ﻭﺠـﺩ ﺃﻥ ﺍﻟﻤﺤﺘـﻭﻱ ﺍﻷﺴﺘﻴﻠﻲ %0.44ﻟﻠﻨﻭﻉ ﺍﻷﺼﻔﺭ ﻭ %0.46ﻟﻠﻨﻭﻉ ﺍﻷﺨـﻀﺭ .ﻗـﺩﺭﺕ ﺩﺭﺠـﺔ ﺍﻷﺴـﺘﺭﺓ ﺒـ %73.8ﻭ %72.47ﻟﻠﻌﻴﻨﺘﻴﻥ ﻋﻠﻰ ﺍﻟﺘﻭﺍﻟﻲ .ﺍﻟﻌﺩﺩ ﺍﻟﻜﻠﻲ ﻟﻤﺠﻤﻭﻋﺔ ﺍﻟﻜﺎﺭﺒﻭﻜـﺴﻴل ﻓﻬـﻭ 1.96ﻤﻠﻡ ﻤﻜﺎﻓﻲ ﻟﻜل ﺠﺭﺍﻡ ﻟﻠﻨﻭﻉ ﺍﻷﺼﻔﺭ ﻭ 1.98ﻤﻠﻡ ﻤﻜﺎﻓﻲ ﻟﻜل ﺠﺭﺍﻡ ﻟﻠﻨﻭﻉ ﺍﻷﺨـﻀﺭ ﻭﻭﺠﺩ ﺃﻥ ﻤﺤﺘﻭﻯ ﺤﻤﺽ ﺍﻷﻨﻬﻴﺩﺭﻭﻴﻭﺭﻭﻨﻙ %68.99ﻭ %69.49ﻟﻠﻨﻭﻋﻴﻥ ﻋﻠﻰ ﺍﻟﺘﻭﺍﻟﻲ. ﻗﺩﺭ ﺍﻟﻭﺯﻥ ﺍﻟﻤﻜﺎﻓﺊ ﺒـ 974.60ﻟﻠﻨﻭﻉ ﺍﻷﺼﻔﺭ ﻭ 920.73ﻟﻠﻨﻭﻉ ﺍﻷﺨﻀﺭ ،ﺃﻤﺎ ﺍﻟﻠﺯﻭﺠـﺔ ﻓﻬﻲ 2.21ﺠﻡ/ﺩﻴﺴﻠﺘﺭ ﻭ2.09ﺠﻡ/ﺩﻴﺴﻠﺘﺭ ﻟﻠﻌﻴﻨﺘﻴﻥ ﻋﻠﻰ ﺍﻟﺘﻭﺍﻟﻲ ﻭﻗﺩﺭ ﺍﻟﻭﺯﻥ ﺍﻟﺠﺯﺌـﻲ ﺒــ 4.2 x 104ﻟﻠﻨﻭﻉ ﺍﻷﺼﻔﺭ ﻭ 4.03 x 104ﻟﻠﻨﻭﻉ ﺍﻷﺨﻀﺭ .ﻜﺎﻨﺕ ﻨـﺴﺒﺔ ﺍﻟﺭﻤـﺎﺩ ﺘﻌـﺎﺩل %3.14ﻭ 3.37ﻟﻠﻨﻭﻋﻴﻥ ﻋﻠﻰ ﺍﻟﺘﻭﺍﻟﻲ ﻭﻨﺴﺒﺔ ﺍﻟﺒﺭﻭﺘﻴﻥ %3.57ﻭ %3.44ﻋﻠﻰ ﺍﻟﺘـﻭﺍﻟﻲ. ﻜﻤﺎ ﻭﺠﺩ ﺃﻥ ﻤﺴﺘﻭﻯ ﺍﻟﻜﺎﻟﺴﻴﻭﻡ 0.28ﻤﻠﺠﻡ 100/ﺠﻡ ﻟﻠﻨﻭﻉ ﺍﻷﺼﻔﺭ ﻭ 0.30ﻤﻠﺠﻡ 100/ﺠﻡ ﻟﻠﻨﻭﻉ ﺍﻷﺨﻀﺭ ﻭﻗﺩﺭ ﻤﺤﺘﻭﻯ ﺍﻟﻤﺎﻏﻨﺯﻴﻭﻡ ﺒـ 0.09ﻤﻠﺠﻡ 100/ﺠﻡ ﻭ 0.07ﻤﻠﺠﻡ 100/ﺠﻡ ﻟﻠﻨﻭﻋﻴﻥ ﺍﻷﺼﻔﺭ ﻭﺍﻷﺨﻀﺭ ﻋﻠﻰ ﺍﻟﺘﻭﺍﻟﻲ .ﻴﺘﻀﺢ ﻤﻥ ﺘﻠﻙ ﺍﻟﻨﺘـﺎﺌﺞ ﺍﻟﻤﺘﺤـﺼل ﻋﻠﻴﻬـﺎ ﺃﻥ ﺍﻟﺒﻜﺘﻴﻥ ﺍﻟﻤﺴﺘﺨﻠﺹ ﻤﻥ ﻗﺸﺭﺓ ﺍﻟﺒﺭﺘﻘﺎل )ﺍﻷﺼﻔﺭ ﻭﺍﻷﺨﻀﺭ( ﻤﻨﺎﺴﺏ ﻹﻨﺘﺎﺝ ﺍﻟﺒﻜﺘﻴﻥ ﺍﻟﺘﺠﺎﺭﻱ ﻤﻥ ﺤﻴﺙ ﺍﻟﻜﻤﻴﺔ ﻭﺍﻟﻨﻭﻋﻴﺔ. LIST OF CONTENTS Page Dedication………………………………………………………………………………….. i Acknowledgement ………………………….…………………………………………… ii Abstract ……………………………………………………………………………………… iii Arabic Abstract …………………………...……………………………………………… iv List of Contents ………………………..………………………………………………… v List of Tables………………………………….…………………………………………… ix CHAPTER ONE: INTRODUCTION………...……………………………… 1 CHAPTER TWO: LITERATURE REVIEW…….……………………… 4 2.1 History of citrus culture………..………………………………………………… 4 2.2. Origin and history of orange………..………………………………………… 5 3.2 Characteristics of some orange varieties………..………………………… 7 2.4 Uses of orange fruit………..……………………….……………………………… 8 2.5 Chemical composition of orange peel………..…………………………… 10 2.6. Pectic substance………..…………………………………………………………… 12 2.6.1 Structure and composition of pectic substances…………………… 15 2.6.2. Properties of pectic substances………..……..…………………………… 16 2.6.3. Extraction of pectic substance………..…………………………………… 19 2.6.4. Uses of pectin………..……………………………………..…………………… 21 2.6.5. Sources of the pectin substances………..………………………………… 23 2.6.6. Properties of orange peel pectin………..………………………………… 24 CHAPTER THREE: MATERIALS AND METHODS……..……… 26 3.1. Materials………..…………………………….……………………………………… 26 3.1.1. Chemicals………………………………..………………………………………… 26 3.1.2. Raw material…………………………....………………………………………… 26 3.2. Analysis of orange peels………….…..………………………………………… 26 3.2.1. Proximate analysis………..………………….………………………………… 26 3.2.2. Alcohol insoluble solids (AIS) ………..…………………………….…… 26 3.2.3. Titrable acidity………..…………………….…………………………………… 27 3.2.4. Ascorbic acid content…….….……..………………………………………… 28 3.2.5. Sugars………..……………………………………………………………………… 29 3.2.5.1. Reducing sugars…………………….………………………………………… 29 3.2.5.2. Total sugar………..…………………………..………………………………… 29 3.2.6. Calcium and magnesium…………...………………………………………… 30 3.3. Preparation and analysis of alcohol insoluble solids………..……… 31 3.3.1. Preparation of alcohol insoluble solids (AIS) ………..…………… 31 3.3.2. Analysis of alcohol insoluble solids………..………………………… 31 3.3.2.1. Proximate analysis………..………………………………………………… 31 3.4. Isolation of orange peels pectins………..…………………………………… 32 3.5. Quantitative analysis of the isolated pectin………...…………………… 33 3.5.1. Moisture………..….…………………………..…………………………………… 33 3.5.2.Ash………..…………………………………………………………………………… 33 3.5.3. Ash alkalinity……………………….…..………………………………………… 34 3.5.4. Equivalent weight……………...……..………………………………………… 34 3.5.5. Methoxyl content………..……………………………………………………… 35 3.5.6. Acetyl content………..………………………..………………………………… 36 3.5.7. Anhydrouronic acid (AUA) content………..…………………………… 37 3.5.8. Viscosity………..…………….………………………..…………………………… 37 3.6. Statistical analysis……………………….………………………………………… 39 CHAPTER FOUR: RESULTS AND DISCUSSIONS ……………… 40 4.1 Chemical composition of orange peels………..………………..………… 40 4.2. Analysis of alcohol insoluble solids (AIS) ………..…………………… 45 4.3. Properties of orange peels pectin substances…………………………… 48 4.4. Conclusions and recommendations………………………………………… 58 4.4.1. Conclusions………..………….…………………………………………………… 57 4.4.2 Recommendations……………………..………………………………………… 58 REFERENCES………………………...………………………………………………… 59 LIST OF TABLES Table Title 1. Analysis of orange peels grams/100 grams (on dry weight basis) …………...……………………………….……………………………… 2. 3. No. 41 Analysis of alcohol insoluble solids (AIS) grams/100 grams (on dry weight basis) …………….…............……….………… 46 Properties of orange peels pectic substances……….……..…… 51 LIST OF FIGURES Fig. Title 1. The effect of party number and lactation stage on moisture content of camel milk……………………………………………………… 2. 45 The effect of party number and season on total solids content of camel milk………………………………………………………………… 9. 44 The effect of lactation stage and season on moisture content of camel milk…………………………………………………………… 8. 36 The effect of party number and season on moisture content of camel milk…………………………………..………………………………… 7. 33 The effect of party number and lactation stage on moisture content of camel milk……………………………………………………… 6. 31 The effect of party number and lactation stage on lactose content of camel milk……………………………………………………… 5. 28 The effect of party number and lactation stage on ash content of camel milk………………………………………………………………… 4. 26 The effect of party number and lactation stage on total solid content of camel milk……………………………………………………… 3. No. 47 The effect of lactation stage and season on total solid content of camel milk………………………………………………………………… 48 CHAPTER ONE INTRODUCTION The sweet orange (Citrus sinensis) constitutes one of the world’s most popular and recognizable fruit crops .Sweet oranges are regarded as high source of ascorbic acid and other fruit acids. Physically, citrus fruits consist of 40-50% juice, 20-40%rind and 20-35% pulp and seeds. Chemically, they contain 86-92%water, 5-8% sugar and 1-2% pectin lesser amounts of acids, protein, essential oils and minerals(janick et al., 1981). The global market for juice and juice product was estimated to be about 50 billion liters in the late 1990 in the United State of America alone, the retail commercial value of the 20 billion liters of juice and juice products exceeded 18billion US$ (Bates et al.,2001). In production of juices and concentrates large amounts of solid wastes accumulate consisting of peels, pulp, seeds, stem, skin, cores and pits (Tressler and joslyn, 1961). In fruit processing industry seeds and peels are discarded as waste at present. The problems arising from disposal of waste stress the needs of research to develop an acceptable commodity from waste (Srirangarajan and Shrikhande, 1979). However, researchers have explored possibilities of using these components in other ways (Braddock and Crandall, 1981) for examples, the pigmented part of peel has been suggested as a potential source of natural carotenoids (Wilson et al., 1971; Braddock and Kesterson, 1974). Over 400 by-products can be made from citrus in addition to juice (Bates et al.,2001). The utilization of solid wastes either directly as cattle feed or after drying or fermentation and either utilization for production of various by-products is more economical (Tressler and joslyn, 1961). Pectin has been manufactured from citrus peel for more than 50 years. All citrus contain pectin and richest sources are lime, lemons, oranges (Bates et al., 2001) and grapefruit (Mohamed, 1999). Tropical developing countries may have a locally owned pectin in manufacturing operation, but it is typically hard pressed to compete imported pectin unless the native operation is given governmental protection. Typically pectin are co-located with large-scale juice operations that run at least30000 metric ton (MT) per year of fruit. A handful of manufacturers make the majority of pectin. Curiously, all of pectin used in the United States of America is imported, principally from Europe, central and south America (Bates et al., 2001). In the Sudan, citrus peels are normally thrown as waste during processing of citrus products since no pectin industry exist in the Sudan the utilization of citrus peels as a source of pectin might be economically sound and reduces its importation (Mohamed, 1999). Previous work indicated that appreciable amounts of pectin can be obtained from grapefruit peels (Mohamed, 1999) and therefore the objective of this work is to extend the knowledge in this area of research. This can be achieved through extraction and characterization of pectic substances from orange peels. CHAPTER TWO LITERATURE REVIEW 2.1 History of citrus culture Citrus is the largest fruit crop in the world with about 60.000.000 metric ton (MT) grown (Bates et al., 2001). Citrus is grown in two belts on both sides of Equator from about 20-40 degrees of latitude (Soost and Roose, 1996; Bates et al., 2001). The place of origin of nearly all species of citrus fruits was probably the southern Himalaya mountain. Columbus brought citrus seeds to the western hemisphere in 1493 and planted them first on the island of Hispaniola, now called Haiti (Bates et al., 2001). Citrus became commercialized in Americans in the late 1800s. In the early to mid 1900s the principal producing states were Florida, Texas and California in United States(Bates et al., 2001). The total area covered by citrus plantation is 2.9 million hectares. Fifty percent of citrus growing occurs in northern and central America and Mediterranean region. South America, the far east and southern hemisphere, including South Africa and Australia are responsible for 25%, 50% and 5%, respectively (Soost and Roose, 1996). Citrus is botanically a large family whose dominant members are the sweet orange (Citrus sinensis), mandarin or tangerine orange (Citrus reticulata), grapefruit (Citrus paradisi), lemon (Citrus limon) and lime (Citrus aurantifolia)(Bates et al., 2001). In the Sudan, the first records of citrus introduction are of the Merowe garden in the old Dongla province as reported by Mohamed (1999). Citrus production in the Sudan is mainly located along the narrow strips of the alluvial soils of the main River Nile, Blue Nile, White Nile, Gezira province, Kordofan, Gebal Marra and the Southern region. Citrus crop at present constitute a good source of cash for farmer, especially in the areas where relatively high population intensities exist, e.g. the central region and Khartoum province. Consequently, both private and public sectors were stimulated to expand citrus production (El-Hassan, 1989). 2.2. Origin and history of orange: The location of the origin of the sweet orange is controversial china, India, Bhutan, Burma and Malaysia are among the countries of origin. The path of sweet orange culture may have first flowed from Yunnan to upper Burma (Speigel- Roy and Goldschmidt, 1996). In the sixth and seventh centuries, Muslim armies overran a vast territory stretching from India to Spain, orange and other citrus trees decorate trail. Arab traders introduced further varieties of citrus fruit to Europe in the middle ages. The Portuguese introduced variety of sweet orange from India which quickly replaced a bitter form (Mcphee, 1967). The numerous health benifits of citrus become apparent to Europeans during the age of exploration. Portuguese, Spanish, Arab and Dutch sailors planted citrus trees along trade routes to prevent scurvy (Mcphee, 1967; Soost and Roose, 1996; Solley, 1997). As an order each sailor on a Spanish headed for the Americans had to carry100seeds with him (Mcphee, 1967). Orange and tangerines account for approximately 70% of global citrus production (Janick et al., 1981). Orange production far outstrips the production of all others citrus. Brazil leads the world’s orange production with 19 million MT in 1996 to 1997 (Bates et al., 2001). The orange plantings in the Sudan are primarily centred in narrow strips of silt soils along the River Nile and its tributaries, the Blue and white Niles and in Kassala area where the soils are deep and fertile. The orange yield and quality in these soils are very satisfactory. However, the small arable land hindered further expansion of orange in these traditional orange production areas. At present policy for the agricultural development in the Sudan, calls for an active role of horticultural production in the national economy. The policy has encouraged many citrus growers to look for high yielding varieties that are adapted to the irrigated heavy clay soils of central Sudan, which form the vast cultivable land of the country, to meet the present and future expansion of orange plantings. To achieve these goals, intensive research programmes on different citrus species have been initiated in the central region of Sudan with its huge resources of water and arable land (Hamid et al., 1999). 3.2 Characteristics of some orange varieties: It has long known that there are three main groups of orange, the sweet orange, the mandarin and sour orange. The most important physical characteristic of orange to be considered are size, color, shape, rind, seeds, flesh and falvour (Kotschevar, 1961). The physical properties of Valencia orange were reported by Kotschevar (1961). Valencia orange was reported to have a large size and a pale to yellow orange colour with tendency to show green. The shape is slightly oval and the rinds are smooth. The number of seeds per fruit was found to be between 2 to 5 and the flavour was excellent. The quality of citrus involves good tastes, good appearance, high nutritive value and sufficient stamina to reach the consumer in attractive condition. The factors governing these are width, rind thickness, number of seeds, juice volume, acidity, total soluble solid (TTS) and ascorbic acid content (Hamid et al., 1999). The properties of specific cultivars of orange (Hamlin, Butter, Complall, Olinda, Jaffa, Diller, Forst and Sinnari) were reported by Hamid et al. (1999). The range of rind thickness was found between 4.1 and 6.5mm. One of the main quality attributes in citrus fruit is amount of juice and its composition. The volume of juice per fruit ranged from 64.4 to 78.4ml, where as the juice percentage by weight varied from 29-40%, with Olinda and Sinnari leading and Jaffa Trailing in both aspects. The taste of citrus correlates well with (TSS): Acid ratio. Forst had highest ascorbic acid content. The quantitative amount changed according to the fruit variety, fertilizer applied, irrigation practices and region of growth (Nour et al., 1981). The California Valencia orange juice contained the amino acids alanine, asparagine, arginine, proline, serine and possibly lysine and glutamine (Nour et al., 1981). 2.4 Uses of orange fruit: Oranges are primarily eaten fresh or prepared as frozen juice concentrate (Janick et al., 1981). The basic type of orange juice are chilled orange juice, frozen concentrate orange juice and hot back juice (Bates et al., 2001). Other products of orange are canned orange juice for infants, powder orange juice (Tressler and Joslyn, 1961), Jam and marmalade (EL-Mubarak et al, 1977; Fellows, 1997). Orange juice powder is sold for use in food manufacturing, adding flavour, colour and nutritive elements to bakery goods. Orange slices and orange peel are candied as confection. Granted peel is much use as flavouring and essential oil is employed commercially as food, soft-drink and candy flvaour and for other purpose (Morton, 1987). Citrus peel and other juice extractor residues have traditionally been dried and marketed as cattle feed (Kesterson and Braddock, 1976; Janick et al., 1981) and molasses as well as flavouring perfumes, pharmaceuticals and soap. The extract of rinds and seeds include pectin and oil. When fermented, orange juice produce vinegar (Janick et al., 1981). originally, citrus uses include beautification, embalming, protection from poisons and curing fever and colic (Solley ,1997). Before Europeans viewed oranges as food, the people use their trees, flowers and fruits as ornaments, seasoning and for aromas (Mcphfee, 1967). Orange peel albedo is a good source of dietary fiber (Branddock and Crandall, 1981). Orange waste can be utilized for production of fungal protein (Labeneiab et al., 1979) and could be used as source of pectic substance (EL_Mubarak et al., 1977). 2.5 Chemical composition of orange peel: The peel, which consist of an outer flavedo and inter albedo, serves to protect edible portion or inner pulp of the fruit. Two flavedo component which may indirectly affect the quality of juice are chromaplasts and oil vesicles. The chromaplasts contain carotenoids .Beneath the flavedo is white spongy layer called albedo. Within this layer a number of important constituent namely flavanones, limonin, pectin and fiber are present( Nelson and Tressler, 1980). The composition of citrus fruit is affected by such factors as growing conditions various treatments and practices, maturity, root stock and variety (Tressler and Joslyn,1961). The moisture content of fruit and vegetables varies from 6696% and its variable even in some variety depending upon locality and other environmental factors. Protein contents depend on variety, agricultural practices and availability of nitrogen in soil (Mohamed, 1999). Protein content of dry citrus peel is reported to be 6% (Braddock and Crandall, 1981). The free sugars in citrus peel are predominantly sucrose, glucose and fructose although the xylose is present in trace amounts (Ting and Attaway, 1971). The amounts of soluble carbohydrates of peel and pulp of citrus fruit are correlated with stage of fruit maturity (Mohamed, 1999). As the alcohol-soluble fraction of the peel increase, there is a corresponding decrease of the alcohol-insoluble solids which are mainly the cell wall and cytoplasmic constituents. Ting and Attaway (1971) reported 6.81% total sugar content of sweet orange peel and pith. The proportion of some constituents of citrus are greatly influenced by maturity e.g. the amount of water-soluble sugar and water-soluble pectin increase with increasing maturity. Carbohydrate separate into alcohol-soluble solids and alcohol insoluble solid. The alcohol soluble solids (ASS) consisted largely of sugars, mainly reducing sugars, together with small amount of low polymer galacturonides and such substance as essential oils, waxes, organic acids and flavonids. The alcohol insoluble solids (AIS) comprise the cell wall component, principally pectic substance, hemicelluloses and cellulose (Kefford, 1959). Essential oils are contained in specialized gland, imbedded mainly in the outer rind but also in extremely small amounts in juice vesicles. The fat content of orange peel is 2.25% (Monselise, 1980). The main acids of the citrus peel are oxalic, malic, malonic with some citric (Ting and Attaway, 1971).The concentration of ascorbic acid in citrus fruit is affected by a number of factors such growing conditions, root stock, position of fruit on the tree and maturity, (Tressler and Joslyn, 1961). Ascorbic acid is present in relatively high amount in mature citrus fruit. Concentrations are much higher in rind (Monselise, 1980). 2.6. Pectic substance: According to Pilink and Voragen (1970) the American chemical society has given the following definition:Pectic substance is a group designation for those complex, colloidal carbohydrate derivatives which occur in, or are prepared from plants and contain large proportion of anhydrogalacturonic acid unit which are thought to exist in chain-like combination. The carboxyl groups of polygalacturonic acid may be partly esterified by methyl groups and partly or completely neutralized by one or more bases. The terms used in the field of pectin research are very general. Protopectin is applied to the water insoluble parent pectic substance which occurs in plants and which upon restricted hydrolysis yields pectin or pectinic acid. The term pectinic acid is used for colloidal poly galacturonic acids containing more than a negligible proportion of methyl ester groups. Pectinic acids under suitable condition are capable of forming gels with sugar and acid or, if suitably low in methoxyl content, with certain metalic ions. The general term pectin designates those water-soluble pectin of varying methyl ester content and degree of neutralization which are capable of forming gels with sugar and acid under suitable conditions. Pectic acids are pectic substance mostly composed of colloidal poly galacturonic acid and essentially free from methyl ester groups. The salts of pectic acid are either normal or acid pectates. Physiological life of fruit processing and storage of fruit products are accompainied by changes in pectin content and pectin structure. These may involve degree of esterification, molecular weight, neutral sugar component and acetylation. These changes may be enzymic or chemical in nature (Pilink and Voragen, 1970). Changes in pectic polymers have been described in many process such as canning, lactic fermentation and heat treatment, but very little is known about change due to alkaline treatment as shown by Jimenez et al., (1996). From the literature reviewed by Abdelrahman (2002), it can be concluded that during storage of sugar beet, water soluble pectin increased and total pectin decreased and this can be attributed mainly to enzymic degradation, namely polygalacturonase and pectin methyl esterase. Cooking helps increasing the solubility of pectic substance. Pectic polysaccharides are important determinants of fruit texture (Jimenez et al., 1996). Pectins degradation during processing ultimately affects the tissue texture i.e. the firmness of tissue may be off set to a certain degree. The firmness in clingstone peaches is related to retention of protopectin (Mohamed, 1999). The texture change during ripening of fruits involves the cell wall degradation, which consists of a dissolution of the pectin-rich middle lamella region. At biochemical level, the important modification that can be observed during ripening are loss of neutral sugar, an increase in pectin solubility and progressive depolymerization of the pectins (Batisse et al., 1996). Pectic enzymes contribute to development of desirable texture produced during ripening of plant (Owen, 1985). Mangoes undergo a very rapid softening of the mesocarp as they approach full ripeness. This dramatic softening is presumably due to the release of depolymerizing enzymes which rapidly attack the constituents of cell walls in the mesocarp, including the pectic substances (Nour, 1978). Several studies revealed that the major cleavage reaction leading to vegetable softening was B-eliminative depolymerization of intercellular pectins (Smits et al., 1995). Many fruits and vegetables transformation processes, involve treatments with calcium to preserve their firmness (Labelle, 1971; Howard and Buescher, 1990). Calcium in plants is normally found in the cell wall forming calcium bridges between the residues of galacturonic acid belong to adjacent pectic chains. The calcium-pectin complex formed acts as an intercellular cement to give firmness to vegetable tissues. The presence of calcium, in addition to favouring insuitability of pectic material, inhibits its degradation by polygalacturonase (Burns and Pressy, 1987). During the normal fruit maturation process the calcium cations are Tranlocated to the growing zones in the plant (Marchiner, 1986). This has been linked to the solubilization and degradation of the pectic material of the middle lamella, causing the softening of the fruits (Lidster et al., 1978; Filslycaon and Buret, 1990). 2.6.1 Structure and composition of pectic substances: Pectic substance are heteropolysaccharide. They consist of galacturonan, araban and galactan of which the central component was galacturonan. The main galacturonan is composed of α-D-(1-4) galacturonic acid with varying a mount of methyl ester groups on the carboxyl groups. Some of carboxyl groups are free acid and some are neutralized with various ions (MCcready, 1970). Many pectins have neutral sugars covalently linked to them as a side chains (Pilnik and Voragen, 1970) including arabinose, galactose, rhamnose, xylose and other sugar (McCready, 1970). Earlier work reviewed by Mohamed (1999) confirmed the presence of the neutral polymers. A mixture of pectic substance including pectic acid was extracted using ammonium oxalate and partial acid hydrolysis of pectic acid furnished L-rhamnose, Larabinose, D-galactose, D-galactouronic acids, 2 methyl-L-xylose and some other monomers. Further evidence for L-arabinose as constitutent sugar in pectic substances was confirm by Foglitti and Percheron (1968) from carnation roots and Aspinall et al., (1968) from lemon peel. Sugars separated by partial acid hydrolysis of pectic fractions of grapefruit peel are arabinose, galactose, rhamnose and xylose together with galacturonic acid (Mohamed, 1999). The neutral Sugar isolated from pumpkin pectin are arabinose, galactose and rhamnose together with galacturonic acid (Eltinay et al, 1982). The non galacturonic, materials constitute one-third of pectic materials weight. The characteristic properties of pectin gelation, film formation and high viscosity in dilute solution are derived from the polygalacturonide chain and non-galacturonide materials act as diluent . These non-galacturonide materials are covalently bound as branch chain expect rhamnose which is believed to be interrupting the main polygalacturonic chain as weak interceptions (Mohamed, 1999). 2.6.2. Properties of pectic substances: Pectic substances have many unique physical and chemical properties primarily owening to carboxyl group (McCready, 1970). They posses many colloidal characteristics (Mohamed, 1999). The pectic solutions of lime, orange and grape peels were characterized by determination of their equivalent weight, acetyl content, methoxyl content, anhydrouronic acid, moisture, ash content and calcium (El-Mubarak et al., 1977). In addition El-tinay et al. (1982) studied ash alkalinity, protein, degree of estrification and total carboxyl group in pumpkin pectic substances. Pectins are soluble in water and form viscous solution. The viscosity depending on molecular weight and being influenced by degree of esterification, pH and electrolyte concentration (MC cready, 1970). Positive correlation between the viscosity and pectin has been evidenced by Nso et al. (1998). The relative viscosity of pectin solution varies with concentration in a manner similar to that other ionizable hydrophilic colloids and certain salts (Abdel-rahman, 2002). The intrinsic viscosity of some fruit and vegetable pectin ranged from 0.75 dl/g to 5.9 dl/g (Fishman, 1991). Pectin extracted from mango fruits. Nour (1977) showed very low intrinsic viscosity compared with commercial citrus pectin.The intrinsic viscosity in mango pectin ranged from 0.86 dl/g to 1.43 dl/g (Abdelrahman, 2002) and guava pectin from 0.2 dl/g to 0.5 dl/g (Eltinay et al, 1979). Acetyl content comprises an integral constituent of peel pectin although it is not an essential constituent of pectin in general. Pectin from fruit differ from that sugar beet in being practically devoid of acetyl group (Abdelrahman, 2002). The acetyl content of citrus pectin is 0.32% (lime), 0.46% (orange), 0.314% (sweet orange). Alexandar and Sulebele (1980), 0.455 – 1.634% (grapefruit)(Mohamed, 1999) and 0.215 – 0.314% in mango pulp pectin (Abdelrahman, 2002). One aspect of difference among the pectic substances in their degree of esterification (DE) which decrease somewhat as plant ripening takes place. The DE is defined as the number of esterified Dgalacturonic acid residues per total number of D- galacturonic residues x 100 (Owens, 1985). The DE of some fruits is reported guava pectin is 69.3 – 80.6% (ELtinay et al., 1979) and that of citrus pectin is 67% (Nour, 1977) while mango pulp pectin is reported to be 87.0% (Abdelrahman, 2002). Pectin with DE above 70% tends to form a jelly more rapidly or at higher temperature than one with 50– 70%, pectin with low degree of esterification i.e. less than 50% are not commonly used to make high solid gels, because they tend to precipitate so rapidly and form irregular gels (Abdel-rahman, 2002). All pectic substances contain methoxyl groups in varying amount depending upon the source and method of preparation (Abdelrahman, 2002). The methoxyl content of guava pectin is found to be 3.32% (Eltinay et al., 1979). The ash content of pumpkin pectin is reported to represent 3.42 – 4.84% (Eltinay et al., 1982). The anhydrouronic acid content of pumpkin pectin ranged between 71.6% and 76.8% (Eltinay et al., 1982) and guava pectin between 23.1 and 26.4% (Eltinay et al., 1979). The most important property of pectin and indeed the characteristic property is the ability to form gels. High methoxyl pectin in aqueous solution form gels in presence of secondary gelling agents of non- Electrolyte character, such as sucrose, solutions of some cations such as calcium to form gels of different character in the absence of secondary gelling agents. The quality of pectin as a gel forming agent is a function of methxyl content and distribution of methoxyl groups,anhydrouronic acid, molecular weight and size of polymer, content, nature and distribution of non-uronide residues and the acetyl content (Nour, 1978). 2.6.3. Extraction of pectic substance: It was well known that pectic substances exist in fruits and vegetables as protopectin. The highest concentration of protopectin is found in growing tissues. This is changed to soluble pectinic acids during growth or ripening of plant tissue due to the slow action of plant acids or more rapid action of the pectic enzymes. The efficiency of extraction methods is related to time, temperature and pH at time of extraction (Baker, 1948). Hot alcohol extraction of plant material separates the carbohydrates into soluble and insoluble fractions. The soluble fraction is made of mono- and disaccharides together with starch and dextrin and other low molecular weight compounds. The alcohol insoluble fraction includes the higher molecular weight compounds, these are cell wall compounds together with protein and some inorganic matter (Sinclair and Crandall, 1953). The high temperature would inactivate the enzyme especially pectinases. In most plant tissues, pectic substances are present insoluble forms (Aspinall et al., 1968) .The latter required acids or agents for its extraction. Grinding the tissue with 0.05N HCl at 80ºc for 30 minutes results in exhausting the tissue and probably complete extraction of pectic material. Acid extraction is preferred because it lowers the amount of hemicellulose in the extract (Whistler and Smart, 1953). However, The acid will bring about continuous degradation and hydrolysis of pectic substances and hence keeping the extraction time to a minimum is recommended (Mohamed, 1999). Total extraction of pectic substances is also accomplished by certain salts, such as ammonium oxalate, that dissolve the calcium pectate through double decomposition. The alkaline extraction of pectic substances is rarely used. complete extraction of pectic substance was achieved by the use of sodium hexametaphosphate solution which can form a calcium complex (Boothby, 1980). The extraction of pectiv is followed by purification through filtration or by the addition of appropriate enzymes system (Whistler and Smart, 1953). Many organic solvents can be used for precipitation such as alcohol and acetone which produce a firmer and easily handled product. The alcohol precipitate usually contains 20– 50% of non uronide matter as ash, nitrogenous constituents, hemicelluloses and glucosans. As pectin is a mixture of uronide and non uronide substances, greater variations are expected in its properties (Mohamed, 1999). 2.6.4. Uses of pectin: Pectin is a component of nearly all fruits and vegetables and can be extracted and used in food processing to form characteristic gels in jam, marmalade (Fellows, 1997) and jellies (Bates et al., 2001) as well as for the confectionary industry (Pilink and Voragen, 1970). The use of pectin in jams and jellies preserves has two major purposes: creation of desired texture and binding of water. If the water binding effect is not achieved completely, the final gel will show a tendency to contract and exude juice, known as syneresis (Bates et al., 2001). Besides the jelly formation property of pectin it helps in reducing the boiling time, which in turn assists in preserving the volatile substances and prevent the excessive inversion of sugar (Saeed and Elmubarak, 1974). There are two types of pectin: high methoxyl (HM) pectins that form gels in high solids jam (above 55% solids) in a pH range of 2.0 – 3.5 and low methoxyl (LM) pectins, which do not need sugar or acid to form gel, but instead calcium salt is used (Fellows, 1997). Commercially low methoxyl pectins are used to make low fruit jams and jellies (Pilnik and Voragen, 1970). Pectins are used in many other products such as fruit preparation for yogurt, fruit drink concentrate, fruit juice, fruit/milk desserts and fermented and directly acidified dairy products. Mohamed (1999) reported that pectin is also used in bakery products in which jams are filled into tarts and biscuits. Belo and Lumen (1981) who reviewed the work of several authors reported that pectic substances have important physiological and nutritional effects. There include hypocholesterolemic effect, increased excretion of fecal sterols and lipids, binding of bile salts and anti-diarrhea effect. 2.6.5. Sources of the pectic substances: Pectic compounds are present in all fruits and vegetables (Matz, 1962, Searle et al., 1992). They are found in middle lamella of plant cells (Matz, 1962; Owen, 1985). The pectic substances of fruit are located in middle lamella as cementing material and on the cell wall (Matz, 1962). Searle et al. (1992) reported the content of pectic substances in some fruits and vegetables such as grapes (0.2–1%), apples (0.5– 1.6%), lemon (3– 4%), lemon seeds (6%), grapefruit (1.6–4.5%) and sugar beet pulp (30%). Kertesz (1951) showed pectin content of some fresh fruits on fresh weight basis such as pears (0.5–0.7%), tomatoes (0.1–0.5%) and banana (0.7 – 1.2%). The production of highly polymerized pectin is largely dependent upon the quality of pectic substances in sources material (Baker, 1948) as well as methods of handling and storage of these byproducts previous to use (Baker, 1948). All citrus contain pectin and the richest sources are limes, lemons, oranges and grapefruit (Baker, 1948; Bates et al., 2001) and pulp of apple (Fellows, 1997). Lime peel is an important source of pectin containing 15– 30% pectin on dry weight basis (Padival et al., 1979). Mohamed reported 2.6 gm/100gm pectin content from grapefruit peels on fresh weight basis .Fruit such as apple contains abundant pectin in cores and skin (Baker, 1948) whereas in citrus fruits the pectin is chiefly in white part of rind (Hughes , 1964; Bates et al., 2001). Abdelrahman (2002) reported 0.35-0.78 % pectin content from mango pulp. Mango peel is available in large quantities in mango processing industry which could be of a very useful source of raw material for extraction of pectin (Srirangarajan and Shrikhand, 1979). El-shafie (1981) reported that the total pectin on fresh weigh of pumpkin was 0.5%. Pectic substances have long been recognized as an important constituent of tobacco. Numerous reports were reviewed on their extraction and determination in tobacco leaf (Jacin et al., 1967). 2.6.6. Properties of orange peel pectin: Eaks and Sinclair (1980) reported a range of 18.2– 23.0% total pectin from Valencia orange peel on dry weight basis. Belo and Lumen (1981) found the total pectin of orange ablbedo to be 27.88%. Elmubarak et al. (1977) studied some properties of pectin from orange and reported 7.16% moisture, 1.4% ash, 1474 equivalent weight, 0.524% Acetyl content, 3.90% methoxyl content, 33.91% anhydrogalacturonic acid, 1.03% calcium, 2.77 intrinsic viscosity and 5.00 x 104 molecular weight. Eltinay et al., (1982) characterized the commercial citrus pectin as follows: 5.18% moisture, 0.09% ash, 0.034% acetyl content, 66.9% degree of esterification, 77.9% anhydrogalacuronic acid by carbazole method and 72.8% by the titrimetric method, 3.87 meq/g total carboxyl, 74.8 equivalent weight, 3.20 dl/g intrinsic viscosity and 5.57 x 104 average molecular weight. CHAPTER THREE MATERIALS AND METHODS 3.1. Materials: 3.1.1. Chemicals: All chemicals and reagents, used in this study, were of analytical grade. 3.1.2. Raw material: Orange (yellow and green)samples were obtained from local market. Peels of the two types were dried at room temperature (about 30ºC), ground, sieved and kept for further analysis. 3.2. Analysis of orange peels: 3.2.1. Proximate analysis: Proximate analysis was done according to AOAC (1975) and AOAC (1990). The parameters determined were moisture, ash, crude protein, fats and crude fibers. 3.2.2. Alcohol insoluble solids (AIS): AIS were determined according to AOAC method (1970) in the manner described by Mohamed (1999). Twenty gram of materials were weighed into 600 ml beaker. Three hundred milliliters of 95% alcohol were added, stirred and brought to boiling. The mixture was simmered slowly for 30 minutes and then filtered through a buchner fitted with an approximate size filtered paper which was previously dried in flat bottomed dish for 2 hours at 100ºC, covered with a tight fit cover and weighed. The residue was then washed with 80% alcohol until washings were clear and coloureless. The paper was then transferred to the previous dish and dried uncovered at 100ºC for 2 hours. The final weight minus the filter paper weight was recorded as weight of alcohol insoluble solids and its percentage was then calculated as follows: Percent AIS = Final weight − filter paper weight × 100 weight of sample 3.2.3. Titrable acidity: The titrable acidity was estimated according to Board (1988) method. Ten grams of material were homogenized in a blender and the volume made up to 250ml with distilled water and filtered. One hundred milliliters aliquouts were taken and titrated with 0.1N sodium hydroxide to pH 8.0 using phenolphthalein as indicator. The results were expressed as percent citric acid as follows: Titrable acidiy % = No. of ml of 0.1N NaOH × c.f. c.f. : conversion factor which is equal to 0.07 citric acid hydrous. 3.2.4. Ascorbic acid content: Ascorbic acid content was determined according to Ruck method (1963) in the manner described by El-obeid (2003). Thirty grams of the sample were blended with about 100ml of 0.4% oxalic acid (4 grams/100ml) for two minutes in a blender. The blended mixture was made up to 500ml in a volumetric flask with 0.4% oxalic acid and filtered. The ascorbic acid in the filtrate was determined by titrating 20ml of the filtrate against 2,6-dichlorophenol indophenol (0.2g/500ml distilled water) of known strength. Ascorbic acid, expressed in mg/100g dry matter, was calculated as follows: Titer ( ml) × dye strength × 100 factor Sample weight × sample volume taken for titration total volume of the sample Ascorbic acid (mg/100g) = Where the factor = Dye strength = 1/titre. The dye was standardized as follows: 50mg of standard ascorbic acid were weighed and made up to volume by 10% oxalic acid in a 250 volumetric flask and 5ml a liquid was diluted with 5ml 10% oxalic acid (50grams oxalic acid/500ml distilled water) and titred with the dye solution to a pink end point. 3.2.5. Sugars: 3.2.5.1. Reducing sugars: Reducing sugar were determined by modified method of Lane and Eynon as described by Schneider (1979). Ten grams were extracted with 200ml ethanol (70%) for 6 hours in a soxhelt apparatus. The solution was then evaporated to 100ml, clarified by adding lead acetate (2ml) and filtered. Sodium oxalate (2g) was added to remove the lead acetate by filtration. The burrette was filled with solution prepared above. Fifteen milliliters of this solution were run into a ten milliliters fehling solution, mixed well and heated to boiling on an electric heater. The solution was kept boiling for 2 minutes and then 3 drops of methylene blue indicator (1gm/100ml distilled water) were added. The titration was completed by addition of sugar solution (drop by drop) until the colour of indicator disappeared and red-brick colour appeared. The reducing sugar were calculated from the table (Pearson, 1970) according to the following equation: Reducing sugar = mg of sugar / 100ml of solution × dilution factor × 100 1000 × weight of sample 3.2.5.2. Total sugars: The total sugars were determined according to the method described by Mohamed (1999). Ten milliliters of HCl :H2O (1 : 1) were added to 50mls sugar extract and left for 8 hours. The solution was neutralized by NaOH (40%), the volume was completed to 100ml and titrated against fehling solution as mentioned above. Total sugars were calculated according to the following equation: Total sugars = mg of sugar / 100ml of solution × dilution factor ×100 1000 × weight of sample 3.2.6. Calcium and magnesium: Calcium and magnesium were determined according to the method described by Pearson (1976) with some modifications. One gram sample was put in a procelin crucible, placed in a muffle furnace and ashed at 600º C overnight. the ash was dissolved in slight excess of dilude nitric acid, transferred to a 50ml volumetric flask and made up to mark with water.A volume of the solution containing 3 – 12 mg of calcium was piptted in to flask , diluted to 50ml, neutralized with M sodium hydroxide and 5ml in excess were added to produce a pH of 12. Murexide (0.2gm ) was added and titrated with versenate solution and stirred throughout the colour change at the end-point from red to violet red. To determine magnesium content. The above solution was titrated at pH 10 after making alkaline with ammonium chloride and ammonium hydroxide buffer and Eriochrome Black T was used as indicator. 3.3. Preparation and Analysis of Alcohol insoluble Solids: 3.3.1. Preparation of alcohol insoluble solid(AIS): AIS were prepared according to the method of Luth et al. (1960) in the manner described by Mohamed (1999). The Orange powder was added to 400ml boiling ethanol (95%) in a wide mouth flasks and boiled for ten minutes. The contents were filtered through filter paper N 0.1 (under suction), washed with sufficient 70% alcohol to remove sugars followed by 95% alcohol to remove other interfering substances and dried at room temperature (about 30ºC). These were ground to pass through 60-mesh and kept in a labeled bottle for further analysis. 3.3.2. Analysis of alcohol insoluble Solids: 3.3.2.1. Proximate analysis: To determine the chemical component of the alcohol insoluble solids, standards A.O.A.C methods (1970) was used. The determination was carried out in triplicate. The components determined were moisture, ash and crude protein. 3.4. Isolation of orange peels pectins: The method of Change and Smith (1973) with some modification was adopted for isolation of total pectic material from orange peels. Hundred grams of alcohol insoluble solids were suspended in 1500ml distilled water and thoroughly mixed. The pH was adjusted to 2.0 with conc. Hydrochloric acid and the mixture was left for30 minutes at room temperature .The mixture was heated in a water bath at 100ºC and left at that temperature for 60 minutes. After cooling the extract was recovered by centrifugation at 3000 rpm for 15 minutes. The cake was suspended in 60ml distilled water, acidified to pH 2.00 with conc. Hydrochloric acid, heated at 100°C in a water bath for 10 minutes and centrifuged again. The liquid recovered was bulked with the first extract before filtering under vacuum through a very rapid qualitative filter paper. The clear filtrate was added to two volumes of 95% ethanol with stirring and left for 12 hours to allow precipitation and Hardening of the pectic material. The precipitated pectic material was recovered on cheese cloth and then washed twice by suspending in 1000 ml 80% ethanol. These suspensions were left for an hour then washed with 95% ethanol followed by acetone. The recovered crude pectin was left to dry in an oven at 60ºC. It was then ground to pass through a mesh No. 60 and kept in labeled bottle for further analysis. 3.5. Quantitative analysis of the isolated pectin: The methods describe by Owens et al. (1952) and Mohamed (1999) were used for the analysis of the isolated pectin. 3.5.1. Moisture: Triplicate samples (1 gm ash), were weighed in dried and weighed aluminum dishes. Samples were then dried for 4 hours at 105ºC (20mm Hg). They were then cooled in a desiccator and weighed to constant weight . The moisture content was calculated as followed: Moisture % = W1 − W2 ×100 S Where: W1 = weight before drying. W2 = weight after drying. S = weight of sample. 3.5.2. Ash: Triplicate samples (1 gm each) were weighed into previously ignited ,cooled and weighed crucibles. Samples were then ignited at 600ºC for 3 hours, cooled and weighed to a constant weight. The ash content was calculated as follows: Ash % = W2 − W0 ×100 W1 − W0 Where: W0 = weight of empty crucible. W1 = weight before ashing. W2 = weight after ashing. 3.5.3. Ash alkalinity: The ash prepared was dissolved in 25ml of 0.1N HCl, heated gently and then titrated with 0.1 sodium hydroxide using phenolphthalein indicator. The alkalinity number of an ash is calculated as the number of milliliters of acid required to neutralized one gram ash. 3.5.4. Equivalent weight: Triplicate samples (0.5 gm each) of pectic substances were weighed into 250ml conical flask and moistened with 5.0 ml ethanol. The product was mixed with one gram sodium chloride and 100 ml of distilled water. The mixture was stirred vigorously and free acidity was determined by direct titration against 0.1N sodium hydroxide using phenol red indicator. A blank containing the same quantities of reagents was used. according to Owens et al., (1952).The equivalent weight was calculated as follows: Equivalent weight = weight of sample ( mg) meq of sodium hydroxide Where: Meq ( Milliequivalent of sodium hydroxide) = normality × titre volume of NaOH This titre is knowm as initial titre (IT) or free acid titre. 3.5.5. Methoxyl content: To the neutralized solution obtained above, 25mls of 0.025N NaOH were added. The mixture was shaken and allowed to stand in stoppered flask at room temperature for 30 minutes. Twenty five milliliters 0.025N HCl were added and the mixture was adjusted to pH 7.5. The titre was corrected for the reagent blank. This titre is known as saponification titre (ST). The methoxyl content was calculated as follows: Methoxyl content % = Meq of NaOH × 31× 100 weight of sample Where: Meq of NaOH = normality of NaOH × titre figure. 31 = formula weight of methoxyl group From the IT and ST obtained the degree of esterification and anhydrouronic acid (AUA) content were calculated as follows: Degree of esterification (DE) = ST × 100 ST + corrected IT The IT was corrected for the ash alkalinity Anhydrouronic acid (AUA) content = 176 ×100 Z Where Z= Weight of sample meq of alkali for free acid × meq of alkali for methoxyl 3.5.6. Acetyl content: Acetyl content was determined according to the method adopted by Pippen et al., (1950) in the manner described by Abdel-rahman (2002). Triplicate samples (0.5 gm each) of pectin were weighed into flask and 25ml of 0.1N NaOH were added. The flask was stoppered, shaken and left overnight. The solution was then diluted to 50ml, from which 20ml were taken and placed in a distillation apparatus. Twenty milliliters magnesium sulphate sulphuric acid solution (100mg magnesium sulphate and 1.5gm of sulphuric acid diluted to 180ml) were added. The solution was then steam distilled and 100ml of distillate were collected. The acetic acid in the distillate was then titrated with 0.05N sodium hydroxide to phenol red end point. The titre was corrected for the reagent blank. The acetyl content (formula weight 43) of sample was calculated according to the following equation: Acetyl content (%w/w) = (net ml of NaOH )(normality of NaOH ) × 4.3 weight of sample (gm) in the a liquot Net ml of NaOH = volume of NaOH required to titre distillate – volume of NaOH required to titre distillate of blank run. 3.5.7. Anhydrouronic acid (AUA) content: AUA content was determined according to McCready and McComb (1952).A solution of pectin of 0.1% concentration was deesterified by holding it in a solution of 0.05N sodium hydroxide and diluted to 0.002%. Two milliters of this solution were added to 12 ml of ice cooled concentrated sulphuric acid in a pyrex test tube. The contents were heated in a boiling water bath for 10 minutes, cooled to 20°C and one ml of 0.15% carbazole in ethanol was added. The contents were mixed thoroughly and left for 25 minutes before colourimeteric determination of the colour intensity at wave length 520nm was made. A standard curve was constructed with known amounts of galacturonic acid ranged from 0 to 3.5mg/2ml (Mohamed, 1999). 3.5.8. Viscosity: Viscosity was determined according to the method of Owens et al. (1952) as described by Mohamed (1999). A 0.1gm of pectic substance was weighed into a beaker and 50ml of distilled water were added and the pH adjusted to 4.8 with 0.1N NaOH. The solution was stirred for 2 hours. Sodium chloride (0.8gm) and sodium hexametaphosphate (0.2gm), known as calgon, in 15ml distilled water were added and stirred for further hour. The pH was then adjusted to 6.0 with 0.1N acetic acid and the solution was transferred to a 100mls volumetric flask and made to volume with distilled water. The viscosity was determined within an hour using ostwald cannon – Fenske No. 1098 at room temperature. The efflux time was determined in the same instrument for the solvent (0.8 NaCl + 0.2% calgon). The relative viscosity was calculated as the ratio of the time of efflux for solution to that for solvent: Relative viscosity (µr) = time (solution) time (solvent) To determine intrinsic viscosity another three concentrations (0.15, 0.10 and 0.05g/100ml) were prepared as mentioned above. The relative viscosity was calculated .To get the intrinsic viscosity the ratio (µr – 1)/c was plotted against C on semi log paper and extrapolated to zero to get intrinsic viscosity where: C = concentration. µr = relative viscosity The average molecular weight was determined from intrinsic viscosity data according to the equation N = 1.4 × 10-6M1.34 Where: N = intrinsic viscosity M = molecular weight. 3.6. Statistical analysis: The data of this study was analyzed using a computer statistical package of social science (SPSS) soft ware version 10.01. T-student test was used to compare between yellow and green types of orange peels. CHAPTER FOUR RESULTS AND DISCUSSION 4.1 Chemical composition of orange peels: The proximate composition of orange peels (yellow and green) was determined and the results were presented in table 1. The results were expressed on dry weight basis. Chemical analysis revealed that the moisture contents were 6.72% for yellow and 7.92% for green. The results showed significant difference (P < 0.05) between peels of the two orange types investigated. Mohamed (1999) reported moisture content of grapefruit peels to range between 75.25%and 75.37 and Morton (1987) obtained 72.5% moisture content of orange peels on fresh weight basis. Ash contents of the two types were 2.59% and 1.84 % respectively. A significant difference (p <0.01) was observed between the two types under study. The values obtained in this work were higher than 1.45 – 1.62 %. for grapefruit peels reported by Mohamed (1999). Ash content values were reported to vary according to many factors such as varietal difference, fertilizers applied, irrigation practices and region (Nour et al. 1981). Table 1: Analysis of orange peels grams / 100 grams (on dry weight basis). Peels of yellow type Peels of green type Level of significance Moisture% 6.72a ± 0.38 7.92 b ± 0.69 * Ash% 2.59a ± 0.25 1.84b ± 0.05 ** Protein 5.84a ± 0.27 6.65 b ± 0.29 * Crude fiber% 8.30a ± 0.61 9.47 b ±0.11 * Volatile oil % 3.08a ± 0.38 2.75 a ± 0.25 Ns Titrable acidity% 0.43a ± 0.038 0.40a ±0.008 Ns Ascorbic acid mg/100gm 60.09a ± 3.55 34.95 b ± 1.04 ** Reducing sugars % 11.01a ± 0.15 5.03 b ± 0.06 ** Total sugars % 16.62a ± 0.17 7.77 b ±0.05 ** Calcium mg/ 100gm 0.78a ± 0.03 0.83a ±0.02 Ns Magnesium mg/100gm 0.19a ± 0.01 0.18a ± 0.01 Ns Alcohol insoluble solids 50.55a ± 0.34 60.74 b ± 0.44 ** Analysis Values are means ± SD of 3 replicates for each parameter. Means within raw with same superscripts are not significantly different. Ns=not significantly different. * =significant (p< 0.05). ** =significant (p < 0.01). Protein contents were 5.84 % and 6.65 % respectively. A significant difference (p< 0.05) was observed between peels of the two types. Protein content of dry citrus peels(6%) reported by Braddock and Crandall (1981) while Morton (1987) reported 1.54% protein content of fresh orange peels. Differences in protein content might be attributed to type of citrus and agricultural practices as well as availability of nitrogen in soil. Volatile oil values of the two types of orange peels were 3.08 and 2.75 % respectively. No significant difference was observed in the two types of orange peels. The values obtained were located within the range of 1.5- 6.50 % reported by Sinclair (1972) for citrus fruit peels. Crude fiber contents of the two types were 8.3 and 9.47 respectively. A significant difference (p< 0.05) was observed between the two types. Crude fibre is the measure of cellulose and lignin contents and is useful in measuring the quality of vegetables (Mohamed, 1999). Titrable acidity of the two types of peels were 0.43% and 0.40% respectively. No significant difference was observed between the two types.A scorbic acid content of the two types of peels were 0.06g/100g and 0.035g/100g respectively. A significant difference (p< 0.01) was observed between the two types. The results of this study were lower than the values reported by Mohamed (1999) and Eaks (1964), they found 0.15-0.185g/100g for grapefruit peels and orange lemon peels respectively. Sanclair (1972) reported that the value of ascorbic acid content was 0.142g/100g of grapefruit peels and also disagree with the work of Morton (1987) who found 0.136g/100g for orange peels on fresh weight basis. Kefford (1959) obtained that ascorbic acid content ranged between 0.036 and 0.182g/100g of orange albedo. Reducing sugar values were 11.01% and 5.03% respectively. A significant difference (p< 0.01) was observed between yellow and green peels. The value of yellow type was higher if compared to the range of 10.2- 10.4% reported by Mohamed (1999) for grapefruit peels. The amount of soluble carbohydrates of peel and pulp of citrus correlated with the stage of fruit maturity (Mohamed, 1999). Total sugar contents of the two types, under study, were found to be 16.62% and 7.77% respectively. A significant difference (p< 0.01) was observed between the two types . Calcium content of the two types investigated was 0.78mg/100gm for yellow and 0.83mg/100gm for green. No significant difference was observed between the two types. These values were located within the range of 0.55- 0.9mg/100gm obtained by Dezman et al. (1984) for grapefruit peels, but higher if compared to the range of 0.69- 0.71mg/10gm reported by Mohamed (1999) for grape fruit peels. Magnesium content of the two types was 0.19mg/100gm for yellow and 0.18mg/100gm for green. No significant difference was observed between the two types of orange peels. These results were comparable to the range of 0.18-0.28mg/100gm reported by Dezman (1984) for grapefruit peels and higher if compared to the value of 0.17mg/100gm reported by Mohamed (1999) for grapefruit peels. Alcohol insoluble solids (AIS) of the two types were 50.55% and 60.74% respectively. The results showed a significant difference (p< 0.01) between the two types. These values were higher than the value of 42.69% and the range of 38.0- 42% reported by Kefford (1959) and Mohamed (1999) respectively. 4.2. Analysis of alcohol insoluble solids (AIS) The chemical analysis results of AIS of yellow and green orange peels were shown in table2. Moisture contents of the two types of AIS were 2.92% and 5.63 respectively. The result showed significant difference (p< 0.01) between the types investigated. Mohamed (1999) reported the moisture content of two types of AIS to be 7.05 and 7.17% for grapefruit peels. The ash contents were 4.09% and 4.48% respectively. No significant difference was observed between the two types. The protein contents of AIS for the two types were 7.65% and 7.49% respectively. Once again no significant difference was seen between the two types. Total pectin contents for the two types studied were 14.84% and 16.06% respectively. The results showed significant difference (P< 0.01) between the two types. These results disagree with the range of 25-25.26% reported by Mohamed (1999) for grapefruit peels and the range of 20- 40% ( on dry weight basis) obtained for citrus peels, reported by Doesburg (1965). The results obtained are comparable with the findings of Alexander and Sulebele (1980) who reported a range of 15- 17 % pectic substance from Indian citrus peels. Iranzo et al. (1980) reported a range of 12.4 – 44%. Pectic substance in spainsh citrus peels. El.tinay et al. (1982) obtained 27.3-32.8% total pectin from pumpkin AIS. Elmubark et al. (1977) obtained values of 4.29% (lime), 4.48% (orange) and 2.17 % (grapefruit) as total pectin on fresh weight basis. Table (2): Analysis of alcohol insoluble solids (AIS) in grams/ 100 grams ( on dry weight besis). AIS of yellow type AIS of green type Level of significance Moisture% 2.92a ± 0.48 5.63b ± 0.12 ** Ash% 4.09a ± 0.05 4.48 b ± 0.20 * Protein 7.65a ± 0.13 7.49 a ± 0.36 Ns Total pectin % 14.84a ± 0.48 16.06 b ± 0.30 * Calcium mg/ 100gm 0.22a ± 0.02 0.21a ± 0.01 Ns Magnesium mg/100gm 0.12b ± 0.01 0.11b ± 0.03 Ns Analysis Values are mean ± SD of 3 replicates for each parameter. Means within raw with same superscripts are not significantly different. Ns= not significantly different. * =significant (p< 0.05). **= significant (p < 0.01). Calcium contents of the two types of AIS were 0.22mg/ 100gm (yellow peels) and 0.21mg/100gm (green peels ). No significant difference was seen between the two types. Mohamed (1999) found calcium contents of AIS from grapefruit peels to be in the range 1.04 to 1.83mg/100gm .Calcium content of pumkin AIS were shown to range between 0.4 and 0.53 mg/100 gm (Eltinay et al., 1982). Magnesium contents were 0.12mg/100gm (yellow peels) and 0.11mg/100gm (green peels). No significant difference was observed between the two types. Mohamed (1999) reported magnesium contents of AIS from grapefruit peels in the range of 0.170.19mg/100gm. Magmesium contents ranged between 0.09 and 0.11mg/100gm were obtained by El.tinay et al. (1982) for pumpkin. 4.3. properties of orange peels pectic substances: Properties of orange peels pectic substances were determined and their results were shown in table 3. Moisture contents of the two types were 7.98% and 8.09% respectively. No significant difference was observed between the two types. The results are in conformity with the range of 7.88- 8.96% for grapefruit peels pectin reported by Mohamed (1999) but, higher if compared to the value of 7.16% reported by Elmubark et al. (1977) for orange peels pectin. The values obtained in this study were also higher than the range of 5.03- 7.04% reported by Abdelrahman (2002) for mango pulp pectin and values of 5.04- 6.3% reported by Saeed (1974) for some Sudanese mango pectin. Ash content of the two types of peels was 3.10% and 3.37% respectively. No significant difference was observed between the two types. The present values fall within the range of 1.56 - 7.65 % (lemon), 0.81- 4.83% (orange) and 0.49 - 8.05% (apple) cited by Abdel-rahman (2002). El-mubark et al. (1977) reported values of 1.7% (lime), 1.40 %(orange) and 1.00% (grapefruit) for ash of pectin. Mango pulp ash in the range of 1..26- 2.02 % was reported by Abdelrahman (2002). The ash content of Indian citrus peels pectin obtained by Alexander and Sulebele(1980) was 2.82 % (lime), 2.96 % (orange), 2.85% (sweet orange)and 3.2% (grapefruit). El-tinay et al. (1979) found ash content from 0.2% to 1% for guava pectin and Mohamed (1999) reported from 1.8 % to 2.0 % for grapefruit peels pectin. Ash alkalinity of pectin was 1.5meq NaoH/gm and 1.49 meq NaoH/gm for yellow and green peels respectively. No significant difference was observed between the two types. Mohamed (1999)found that the alkalinity of ash was 2.48 meq NaOH/gm and 1.56 meq NaOH/gm for grapefruit peels pectin. Ash alkalinity of mango pulp pectin reported by Abdelrahman (2002) ranged between 2.04 meq Na OH/gm to 2.48 meq Na OH/gm. The ash alkalinity is the measure of mineral constituents combined with organic acid groups. Calcium pectate is probably one of the constituents of the cell wall structure (Mohamed, 1999). Protein values were 3.57 % and 3.44 respectively. No significant difference was observed between the two types. These values were higher than those obtained by Mohamed (1999) who reported 0.0399- 0.0405 % protein for grapefruit peels pectin and 0.129% for commercial citrus pectin. Abdel-rahman (2002) reported 0.22- 0.34 % protein for mango pulp pectin. The values of protein contents obtained by El-shafie (1981) were 1.24% (citrus pectin) and 4.2% (pumpkin pectin). Acetyl content of the two types was 0.44% and 0.46% respectively. No significant difference was seen between the two types. These results were inline with the finding of Mohamed (1999) who reported 0.46- 1.63% for grapefruit peels pectin and 0.63 % for commercial citrus pectin and also agreed with the results of El-mubark et al. (1977) who reported 0.43 % (lime), 0.524 % (orange) and 0.55 (grapefruit). Alexander and sulebele (1980) found that the acetyl content of some citrus peels pectin ranged between 0.32 % and 0.46 %. Abdelrahman (2002) reported values from 0.117 % to 0.314 acetyl content in mango pulp pectin. Saeed (1974) reported acetyl content from 0.412 % to 0.55 % for mango marc. The acetyl group in pectin substances have significant role on account of their effect on the jelly forming ability (Abdelrahman, 2002). Methoxyl contents of the two types of orange were 8.95 % and 8.89 % respectively. These results showed no significant difference between the two types. These values agreed with the results obtained by Mohamed (1999)who reported 8.875 % for grapefruit peels pectin and El-shafie (1981) who reported 8.82% for citrus pectin , but higher if compared to the range of 3.9- 4.11 % reported by El-mubark et al. (1977) for citrus pectin, 2.71- 4.13 reported by El-tinay et al. (1978) for guava pectin, 5.72 % reported by Sinclair and Grandall (1949) for grapefruit peels pectin and 7.40- 8.62 % obtained by Alexander and Suelbele (1980) for some citrus pectin.The methoxyl content is an important factor in evaluating the setting time of pectin, sensitivity to polyvalent cations and their usefulness in low solids gels, films and fibre (El-tinay et al., 1979).It is generally true that an increase in methoxyl content and decrease in the molecular weight will decrease the jelly grade. The difference in methoxyl content were far outweighted by the large difference in molecular weight (Change and Smith, 1973). Tables 3: Properties of orange peels pectic substances: pectin of pectin of Level of yellow type green type significance Moisture% 7.98 ± 0.13 8.09 ± 0.28 Ns Ash% 3.14 ± 0.14 3.37 ± 0.13 Ns Ash alkalinity meg Na OH/gm 1.50 ± 0.02 1.49 ± 0.04 Ns Protein 3.57± 0.23 3.44 ± 0.27 Ns Acetyl content 0.44 ±0.07 0.46 ±0.07 Ns Methoxyl content 8.95 ± 0.32 8.87 ± 0.11 Ns Free carboxyl group meq/gm 0.51 ± 0.02 0.54 ± 0.15 Ns Esterified carboxyl group meq/gm 1.45 ± 0.05 1.43 ± 0.02 Ns Total carboxy group meq/gm 1.96 ± 0.04 1.98 ± 0.02 Ns Anhydro lacturonic acid(c) 76.57 ± 1.25 76.16 ± 1.10 Ns Anhydro lacturonic acid (T) 68.99 ± 1.41 69.46 ± 0.62 Ns Equivalent weight 974.60 ± 28.74 920.73 ± 25.67 Ns Calcium mg/ 100gm 0.28 ± 0.02 0.30 ± 0.01 Ns Magnesium /100gm 0.09 ± 0.01 0.07 ± 0.01 Ns Degreeof slerificant ion 73.80 ± 1.07 72.47 ± 0.71 Ns Intrinsic viscosity dI / gm 2.21± 0.77 2.09 ± 0.43 Ns Average molecular weight 4.2 ×104 4.03 ×104 Ns Analysis Values are means ± SD of 3 replicates for each parameter. Ns: not significant different (P > 0.05). C: Carbozole Method. T: Titrimetric method. Free acidity of pectin obtained from the two types of orange peels was 0.513meq/gm and 0.54 meq/gm respectively. No significant difference was observed between the two types. Abdelrahman (2002) found that free acidity was 0.72- 0.84 meq/gm for mango pulp pectin. Esterified carboxyl group of the two types pectin was 1.447 meq/gm and 1.433 meq/gm respectively. The total carboxyl groups of the two types of pectin were 1.96meq/gm and 1.977 meq/gm respectively. No significant difference was observed between the two types in esterified carboxyl groups. The total carboxyl groups , obtained in this study, lies within the higher values from 1.143 meq/gm to 1.23 meq/gm obtained by Abdel-rahman, 2002) for mango pulp pectin and from 0.33 meq/gm to 0 .46 meq/gm reported by El-tinay et al. (1979) and lower if compard to a range 1.52- 2.05 meq/gm reported by Mohamed (1999) for grapefruit peels pectin and 3.87 meq/gm obtained by El-shafie (1981) for citrus pectin. El-tinay et al.(1978) showed that addition of calcium ions caused a decrease in the free carboxyl group content in guava pectin .The carboxyl groups influence the viscosity of pectin solution depending upon the degree of esterification. Solution of fully esterified pectin don’t change appreciably in viscosity with change in pH, but when they contain pectin of lower degree of esterification the viscosity becomes markedly pH dependent (Abdel-rahman, 2002). Anhydrouronic acid (AUA) content obtained by titrimetric method for the two types of pectin was 68.99 % and 69.46 % respectively. No significant difference was observed between the two types. The values of AUA contents, obtained by Carbazole Method, were 76.57% and 76.16% respectively. Mohamed (1999) reported that the value of AUA content for grapefruit peels and commercial citrus pectin were 60.95 % and 68.90 % respectively. The values obtained were lower than that obtained by El-shafie(1981) and Kefford (1959) who reported 77.86 % for citrus pectin and 80.85 % for commercial citrus pectin respectively, but fall within the range of 73.9- 77.4 % for some citrus pectin reported by Alexander and sulebele (1980). Srirangajan and Shrikhande (1979) reported AUA content of 83.5 % for orange, 59.4 % for apple and 61.12 % for mango. The results , in this study, were higher than that obtained by El-mubark et al. (1977) who reported 33.43 % (lime), 33.9 % (orange) and 32.94 % (grapefruit) and abdelrahman (2002) who reported a range of 18.51526.0 % for mango pulp pectin. The quality of pectin is known to depend upon the content of anhydrouronic acid and methxyl group and also the degree of esterification ( Srirangarajan and Shrikhande, 1979). Good quality commercial preparations usually contain not less than 68 % uronic acid. The AUA is the most significant property of pectin. The properties of pectin are better described by the polygalacturonic acid (Mohamed, 1999). Equivalent weights for the two types varied from 920.73 to 974.60. No significant difference was seen between the two types. These values are higher than the range of 620- 749 reported by Mohamed (1999) for grapefruit peels pectin and the value of 749 found by El-shafie(1981) for citrus pectin. The equivalent weights, obtained in this study ,were lower than range of 1389- 2003 reported by Abdelrahman (2002) for mango pulp pectin and the values of 1751 (lime), 1474 (orange) and 1690 (grapefruit) reported by El-mubark et al. (1977). Calcium content of the two types of pectin were 0.28 mg/100gm and 0.30 mg/100gm respectively.Magnesium contents were 0.087 mg/100gm and 0.07 mg/100gm respectively. These values showed no significant difference between the two types in both calcium and magnesium contents .Abdelrahman (2002) reported the calcium and magnecium contents of mango pulp pectin to be 0.0020.004 mg/100gm and 0.820- 0.825 mg/100gm respectively. Mohamed (1999) reported that the calcium content of grapefruit peels pectin ranged between 0.55mg and 0.74mg/100gm and that of citrus pectin was 0.24 mg/10gm. Magnesium content of 0.05 mg/100gm for grapefruit peels pectin and 0.03 mg/ 100gm for commercial citrus pectin was reported by Mohamed (1999). Degree of esterification of the two types studied was 73.80 % and 72.49 % respectively. The results showed no significant difference between the two types. These results were higher than that obtained by Mohamed (1999) for grapefruit peels pectin, zitco and Bishop (1965) for citrus pectin, Alexander and Sulebele (1980) for some citrus and El-tinay et al. (1982) for citrus pectin who reported 51.01- 51.24%, 67.0 %, 56.1- 63.2 % and 66.9 % respectively. The values of this study are lower if compared to the range of 73.9- 86.8 % for pumpkin pectin reported by El-tinay et al. (1982), 76.0 % reported by Srirangarajan and Skrikhande (1977) for mango peels pectin and 87.0 % reported by Abdelrahman (2002) for mango pulp pectin. The intrinsic viscosities for pectin were 2.707 dI/ gm and 2.09 dI/gm for yellow and green peels respectively. No significant difference was observed between the two types. These values are lower if compared to the value of 3.30 dI/gm for commercial citrus pectin (Nour, 1977), a range of 3.2 – 4.4 dI/ gm for some citrus pectin (Alexander and Sulebele, 1980), 3.8dI/ gm for commercial citrus pectin (Mohamed,1999) and the value of 3.9 dI/gm for citrus pectin (Pippen et al., 1950). The values are higher than that obtained by Abdelrahman (2002) for mango pulp pectin, Mohamed (1999) for grapefruit peels pectin and Saeed et al. (1974) for some varieties of mangoe pectin who reported 0.86- 1.43 dI/ gm, 1.5dI /gm and 0.601.22 dI/gm respectively. These results fall within the range of 0.755.9 dI/gm reported by Fishman et al. (1991) for some fruits and vegetables. The average molecular weights of the two types were 4.2x 104 and 4.03x 104 respectively. The average molecular weight of grapefruit peels pectin reported by Mohamed (1999) was 3.162× 104. The present values disagree with the range of 2.0877× 104- 3.0512× 104 reported by Abdelrahman (2002) and were higher than that obtained by Saeed et al. (1974)for mango pectin who obtained 1.6×104- 2.1× 104. These values are lower if compared to values reported by El-shafie (1981), Mohamed (1999) and El-tinay et al. (1982) for citrus pectin who reported 5.951× 104, 5.038× 104 and 5.57× 104 respectively. 4.4. Conclusions and recommendations: 4.4.1. Conclusions: This study was intended to investigate the proximate composition, alcohol insoluble solidsfor orange peels and isolation and characterization of the pectic substances. Two types of orange peels, yellow and green, were used in this investigation. Proximate chemical composition (moisture, ash calcium and magnesium), protein and volatile oil, titrable acidity, ascorbic acid, sugar and alcohol insoluble solids were determined. Alcohol insoluble solid of the two types of orange peels were 50.55% and 60.74% respectively. these values are comparable with the 38 -42% alcohol insoluble solid from grapefruit peels reported from literature. Total pectin contents for the two type of orange peels were 14.74% and 16.06% respectively. Significant differences were observed between the two types of orange peels, except for calcium, magnesium and acidity. The pectic substances were characterized and assessed for ,moisture, ash, ash alkalinity, protein, acetyl content, methxyl content, carboxyl content, degree of esterification, anhydrogalacturonic acid, equivalent weight, calcium, magnecium, intrinsic viscosity and average molecular weights. No significant differences were observed between the two types of orange peels pectin. Methoxy contents of 8.95% and 8.89% were obtained from yellow and green types respectively. Degree of etherification obtained in this study were 73.80% and 72.47% for yellow and green types respectively. these values comparable with the range of 73 – 86.8% for pumpkin pectin obtained from earlier work. From the results, obtained in this study,it can be concluded that the quantity and quality of pectin obtained from orange peels (both yellow and green ) are suitable for commercial production of pectin. 4.4.2 RECOMMENDATIONS: Since the quantity and quality of pectin obtained from peels are suitable for the commercial production of pectin, further work is needed in this regard .This include: 1. Economic feasibility of producing pectin from orange peels. 2. Modification of the pectin extraction procedures application. 3. Trial of functionality of extracted pectin. for easy REFERENCES A.O.A.C. (1970). Association of official analytical chemists. Official Methods of analysis. 11th ed. Washington, DC. Abdel-Rahman, N. A. (2002). Characterization of pectic substances of abu-samaka cultivar in relation to their influence on mango pulp concentrate M. Sc. Thesis. University of Khartoum. Alexander, M. M. and Sulebele, G. A. (1980). Characterization of pectin from Indian citrus peels. J. Fd. 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