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Akhilesh V Singh*, Lila K Nath1, Anudwipa Singh2 Department of Pharmaceutical Sciences, Dibrugarh University, Dibrugarh-Assam, India-786004 2 Jyothismathy Institute of Pharmaceutical Sciences, Karimnagar, Andhra Pradesh, India

ABSTRACT In recent years among polysaccharides, starch is receiving utmost attention due to its usefulness in different industrial products in modified form. Native starches in its derivative forms open a wide scope in pharmaceutical, food and non-food based industries. Modification in the native starches are done to overcome different shortcomings like freeze thaw stability, solubility, retrogredation, paste clarity etc. Common modes of modifications are esterification, etherification, phosphorylation, pregelatiniztion etc. In this review article an attempt has been done to explore present and future industrial prospects of modified starches.

KEYWORDS Modified starch, Pharmaceutical, Food, Non-Food application.

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INTRODUCTION Starch constitutes most of the dry matter accumulating in the plant systems, next to cellulose and chitin [1]. Starch comprises a mixture of two polysaccharides: amylose (a linear polysaccharide) and amylopectin (a branched polysaccharide). The molecules of amylose consist of weakly branched polysaccharide chains composed of glucose residues linked by valence bonds. Amylose dissolves in warm water with the formation of a transparent unstable solution. Amylopectin has a more complicated structure of branched chains. The content of this polysaccharide in starch varies within broad limits, ranging from 30 to 100%. It is not only the primary source of food for the humans, but can also be regarded as renewable resource that may be utilized in much industrial application. Starch is found in seeds (i.e. corn, maize, wheat, rice, sorghum, barley, or peas) and in tubers or roots (i.e. potato or cassava) of the plants. Most of the starch produced worldwide is derived from corn, but other types of starch such as cassava, sweet potato, potato, and wheat starch are also produced in large amounts. The worldwide production of starch in 2008 is estimated to be around 66 million tons. Most of the starch is produced in the USA, second and third starch producer regions are Europe and Asia. China will be a formidable competitor to US and Europe. Demand for starch by food and non-food industries in Asia is likely to grow by 4 - 6 percent per year in low and middle income countries in this region. Over time, demand for starch by non-food industries will tend to grow faster than demand for starch by food industries. Value added modified starch derivatives remains very attractive area due to high margins and numerous food and industrial applications. There are excellent opportunities to grow this business because of the growth in health, nutritional and functional needs of the changing consumer appetite as we move forward in the global economies. This is a comprehensive report with lot of data and insights in to modified starch products, market segments and future developments and how one can position in the changing global markets. Detail analysis of modified starches in food and industrial sectors provide in depth insights into the use and potential for modified starches. Carbohydrate economy is moving forward with the pace of new knowledge and technologies developing at a great momentum. Several developments underway are using the biotechnology that will introduce new technologies and products that will potentially change the scene for modified starches. Most notable are natural high phosphate starch that can potential replace chemical modifications especially starting with paper and other industrial application then in foods. National Starch, leading modified starch producer has introduced new line of natural starches to replace chemically modified starches. New hybrids via biotechnology will further enhance natural starches to be utilized to meet consumer demands [2]. Corn with amylase and other enzymes in the grain that can be activated to improve processing economics of the way we process carbohydrates or to create new carbohydrates with novel properties are moving forward. Modified starches are utilized in hundreds or even thousands of food, industrial, biofuels, bioplastic applications. Unmodified starches have limited usage due to its inherent weakness of hydration, swelling and structural organization. To enhance viscosity, texture, stability among many desired functional properties desired for many food and industrial applications, starch and their derivatives are modified by chemical, physical and biotechnology means. Due to change in market demand and rapid economic growth research on production of modified starch and starch derivatives developed very quickly around the world. Native starch is used as texture stabilizer and regulator in food industry but limitation such as low thermal resistance; thermal decomposition and shear resistance limit its use in industrial

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application. Modification of starch, involves the alteration of the physical and chemical characteristics of specific industrial applications. Starch modification is generally achieved through derivatization such as esterification, etherification, cross linking, acid hydrolysis, enzymatic hydrolysis heat treatment and grafting of starch [3]. The recent report on modified starches and its future scope predicted that total consumption will grow to almost 75 million tons by 2012 and the demand for starch by food and non-food industries in Asia is likely to grow by 4 - 6 percent per year in low and middle income countries in this region [4]. Despite numerous studies that have been undertaken over many years to elucidate the role of Modified starch in pharmaceutical, food and nonfood industry based application, starch remains an outstanding inscrutable molecule to be explored. Modified starches are utilized in hundreds or even thousands of food, industrial, biofuels, bioplastic applications. Unmodified starches have limited usage due to its inherent weakness of hydration, swelling and structural organization. To enhance viscosity, texture, stability among many desired functional properties desired for many food and industrial applications, starch and their derivatives are modified by chemical, physical and biotechnology means. MODIFICATION OF STARCH Unprocessed native starches are structurally too weak and functionally too restricted for application in pharmaceutical, food and non-food technologies. Modifications are necessary to create a range of functionality. Modification can be chemical, physical and enzymatic. Starch modification can be introduced by altering the structure and affecting the structure including the hydrogen bonding in a controlled manner to enhance and extend their application in industrial prospective. The modification takes place at the molecular level. Modified starches are typically used in food systems around the globe. They are mainly added to primarily thicken, stabilize or, texturally influence a food product. In actual context, they can used as multi-functional form in different industry. TYPES OF MODIFIED STARCHES Most native starches for use in industry are modified in controlled manner. They can be summarized as followed:(i) Pregelatinized starch: It is the simplest starch modification, prepared by cooking the slurry, roll drying, spray drying or, extrusion process. It maintains starch integrity while provide cold water thickening. (ii) Cross-linked starch: Cross linking is the most important modified form that used in industry. It involves replacement of hydrogen bond present between starch chains by stronger, permanent covalent bonds. Distarch phosphate or, adipate are the most commonly used cross-linked starch. Cross-linked starches offer acid, heat and shear stability over the native starch. (iii) Oxidized starch: It is obtained by reaction with sodium hypochlorite or peroxide [5].These are mainly used as surface sizing agent or coating binder and available in different viscosity grade. (iv) Cationic starch: Cationic starches are produced by reacting native starches with tertiary or, quarternary amines, using wet or dry production processes [6]. They are mainly used in paper forming process.

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(v) Anionic starch: Anionic starches are prepared by reaction with phosphoric acid and alkali metal phosphates or by making derivative with carboxymethyl group. (vi) Thinned starch: These are produced through depolymerization reaction by hydrochloric acid or other acids. (vii) Acetylated starch: Starch after treatment with acetic anhydride produces starch esters which are useful in biodegradable applications [7]. In particular, high DS starch acetates provide thermoplasticity, hydrophobicity and compatibility with other additives. (viii) Dextrins: Dextrination is the heating of powdered starch, mostly in the presence of small amounts of acids, at different temperatures and with different reaction times. Dextrins are used as adhesives in paper and textile based industry. (ix) Grafted starch: Grafted starches are produced by free radical copolymerization with ethylenically unsaturated monomers. Starch grafted with synthetic polymers are most utilized starches from different botanical origins were grafted with 1, 3 butadiene, styrene, acrylamide, acrylonitrile and Meth acrylic acid using free redox reaction[8,9]. (x) Starch ethers: Starch ethers are produced by a nucleophilic substitution reaction with an ethylenically unsaturated monomer, followed by acid-catalyzed hydrolysis for viscosity adjustment [10]. (xi) Physically modified starch: Native starch can be modified with mechanical treatment, using spray drying technique, annealing technique [11, 12] (xii) Enzyme modified starch: Starch modified with amylase enzyme produces derivative with good adhesion property and mainly used in coating the food with colorant [13]. MATERIALS AND METHODS APPLICATION IN PHARMACEUTICAL/MEDICAL INDUSTRY In recent years, pharmaceutical companies around the world widely using modified starches of various kinds in various stages of drug development technology and development. Excipient plays a very important role in solid dosage formulation by imparting mechanical strength, stability and tablet disintegration. Pharmaceutical excipient: Native starches were well explored as binder and disintegrant in solid dosage form, but due to poor flowability there utilization restricted. Most common form of modified starch i.e. Pregelatinized starch marketed under the name of starch1500 are now a days most preferred directly compressible excipients in pharmaceutical industry. Recently modified rice starch, starch acetate and acid hydrolyzed diascorea etc. was well established as multifunctional excipient in pharmaceutical industry [14-16]. Tablet Superdieintegrant: They are generally employed for immediate release tablet formulations, where drug should be available within short span of time to the absorptive area. Sodium carboxymethylaed starch, which is well established and marketed as sodium starch glycolate generally used for immediate release formulation. Some newer sources of starch has been also modified and evaluated for the same [17-18]. Controlled/Sustained release polymer : Two decades earlier modified starch was first evaluated as sustained release polymer. Modified starches in different forms such as Grafted,

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acetylated and phosphate ester derivative have been extensively evaluated for sustaining the release of drug for better patient compliances [19-23]. Plasma volume expander: Starch modified with ethylene oxide produces hydroxyethyl starch, which is now mainly used as plasma volume expander. This is mainly useful for the patients suffering from trauma, heavy blood loss and cancer treatment.


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APPLICATION IN FOOD INDSUSTRY It has been almost decades since commercial production of starch for food and industrial application was initiated. Native starch is utilized in the food industry in a number of forms, but we shall concerns about modified starches in food industry which is mainly used to enhance paste consistency, thickening, smoothness and clarity and also to impart cold storage stability and freeze thaw stability in comparison to its native counterpart. Most modified starches involve introduction of low levels of substituent group through the interaction of hydroxyl group. Food industry generally recommends modified starches with less degree of substitution (0.2 to 0.0001 or, less) . Modified starches are used in different food types like baked food, baby foods, snacks, confectionaries etc. [24] Frozen Food: To stabilize the food products starches are used in frozen bottle foods to provide freeze-thaw stability and retrogradation. Flavor Encapsulation: Modified starches are used to encapsulate or, preserve the flavor of the food products. Octenylsuccinylated derivatives and other starch hydrolyzates are used as flavor encapsulation. Dairy Products: Modified starches are used in a wider way to the dairy products; it provides variety of effects, including enhanced viscosity, cuttability, mouthfeel and stability. In puddings, starch is used to enhance viscosity and smoothness. Starches are used in yogurts and sour cream to control syneresis and enhance thickness. Canned Food: Canning process preserves food for up to several years by achieving a temperature sufficient to destroy or inactivate food poisoning or spoilage microbes. Starch is most commonly used to thicken, stabilize and enhance the mouthfeel of canned foods such as puddings, pie- fillings, soups, sauces and gravies. Highly cross-linked starches are used for this purpose. APPLICATION IN NON-FOOD INDUSTRY Modified starches are now a well established polymer which is used other than contemporary food based industries like textile, paper, petrochemicals etc. Paper Industry Starch is used as a flocculants and retention aid, as a bonding agent, as a surface size, as a binder for coatings and as an adhesive in paper industry [25]. Current consumption of industrial corn starch for paper and paperboard production in the US exceeds 2.5 billion pounds (1.1 million metric tons) of which 40% is chemically modified starch. Textile Industry Textile industry is another major user of modified starches in different ways. It is specifically used for warp sizing preparatory to weaving, for sizing or finishing the cloth after it is woven, and in printing certain types of fabrics. Modified starches are also used in large quantities in laundering, both in commercial establishment and in home.


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Plastic Industry Starch offers several prospective advantages as a raw material for plastics applications because it is renewable, biodegradable and obtained from a variety of plant sources and is a low-cost material. Addition of polyvinyl produces thermoplastic starch and addition of polystyrene produces biodegradable. Granular starch can be used as a filler to enhance biodegradation of commodity plastics, such as conventional and linear low density polyethylene and high density polyethylene, polypropylene and polystyrene [26]. Petroleum Industry The petroleum industry has found that modified starch imparts desirable characteristics to the mud used in drilling oil wells, and thousands of wells have been drilled using such mixtures (sand, water and pregelatinized starch). Numerous modified starches have been prepared and their suitability studied for various oilfield applications such as filtrate-loss control, mud-rheology modification, shale stabilization, enhanced oil recovery (EOR), drag reduction, and water shutoff, and some of these starches have been widely used in this area [27-28]. FUTURE PROSPECTIVE Modified starches have a very promising industrial prospects on application basis, due to its more biocompatible and environmental friendly nature as compared to synthetic polymers. Moreover, now a days food, textile, paper and petroleum based industries consuming more modified starches as compared to pharmaceutical industry which requires more regulatory standards to be used in drug development. Many developing countries like China and India are using nearly same as their western counterparts due to rapid industrial growth in this regions. So, in upcoming years we will see much more utilization of modified starches in unexplored areas of industrial applications. There are excellent opportunities to grow this business at gross root level because of the growth in health, nutritional and functional needs of the changing consumer appetite as we move forward in the global economies CONCLUSION Value addition in native starch produces derivatives remains very attractive area due to high margins and abundant food and industrial applications. This is a critical review on industrial prospects of modified starch products that are utilized in different food and non-food based industry globally. REFERENCES
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