Industrial applications of marine carbohydrates.

CHAPTER EIGHT

Industrial Applications of Marine Carbohydrates Prasad N. Sudha1, S. Aisverya, R. Nithya, K. Vijayalakshmi Department of Chemistry, D.K.M. College for Women, Thiruvalluvar University, Vellore, Tamil Nadu, India 1 Corresponding author: e-mail address: [email protected]

Contents 1. Introduction 1.1 Marine carbohydrates 1.2 General structures and terminology 1.3 Production of carbohydrates by marine organisms 1.4 Analysis of marine carbohydrates 1.5 Carbohydrates in sediments 2. Applications of Marine Carbohydrates 2.1 In cosmetics 2.2 In food and agricultural field 2.3 In pharmaceutics 2.4 In biotechnology and microbiology 2.5 In treatment of industrial effluent 3. Future Directions for Research 4. Conclusion Acknowledgments References

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Abstract Biomaterials have been used increasingly in various fields, such as drug delivery, imaging, and tissue engineering. The main reason justifying the widespread use of biomaterials relies on its valuable and low-cost source of new drugs. Current research goals are focused on identifying more potent and specific compounds with antitumor, immunomodulatory, antihyperlipidemic, anticoagulant, and antiviral activities. The increasing knowledge of structural analysis and chemical modifications enables the use of these marine carbohydrates in a newer way for the human welfare. This chapter focuses on the recent developments related to industrial and biomedical applications using chitin, chitosan, alginate, agar, and carrageenan derivatives and reports the main advances published over the last 10–15 years.

Advances in Food and Nutrition Research, Volume 73 ISSN 1043-4526 http://dx.doi.org/10.1016/B978-0-12-800268-1.00008-1

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1. INTRODUCTION 1.1. Marine carbohydrates Oceans represent vast and exhaustive source of natural products in the globe, harboring the most diverse groups of flora and fauna. Marine microorganisms have developed unique metabolic and physiological capabilities to thrive in extreme habitats and produce novel metabolites that are not often present in microbes of terrestrial origin (Fenical, 1993). Therefore, this rich marine habitat provides a magnificent opportunity to discover newer compounds such as antibiotics, enzymes, vitamins, drugs, biosurfactant, bioemulsifier, and other valuable compounds of commercial importance (Austin, 1989; Jensen & Fenical, 1994; Lang & Wagner, 1993; Romanenko, Kalinovskaya, & Mikhailov, 2001). Marine carbohydrates are the polysaccharides which can be extracted from marine plants and animal organisms or produced by marine bacteria that have been studied for several decades. Some of the major components which have been identified in marine particles over the past decade, including uronic acids (Hung, Guo, Santschi, Alvarado-Quiroz, & Haye, 2003; Mopper et al., 1995), aldoses (Skoog & Benner, 1998), neutral sugars (Mopper et al., 1995), and amino sugars (Muldoon et al., 2001). Recently, the marine-derived proteins are becoming more popular among consumers because of their numerous health beneficial effects that can provide equivalents to collagen and gelatin without the associated risks. Seaweeds are major marine sources having much kind of applications in various fields. There are three different algae present in marine water: green, red, and brown algae. Among these, brown seaweeds are having many types of polysaccharides which play an important role in medical field. In the year of 1913, Killing first isolated the fucoidan from marine brown algae and named as fucoidan (Killing, 1913). Fucoidan are present only in the brown seaweeds with various essential components. The brown algae, Fucus serratus L., consists of L-fucose, sulfate, and acetate in a molar proportion of 1:1:0.1 and small amounts of xylose and galactose (Bilan et al., 2006). The low-molecular-weight fucoidan have potent anticoagulant and fibrinolytic properties with only minor platelet activating effects (Diirig et al., 1976). One of the most abundant biopolymers which were found in the marine organic carbon pool is the carbohydrates, making up 10–70% of organic matter in plankton cells (Romankevich, 1984). The marine carbohydrates form the basis of a

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number of nutraceutical products (from seaweed, microalgae, and shrimp waste) and also of the long established alginate (from seaweed) industry. About 200 g carbohydrates per kg wet weight were found to be an appropriate substrate concentration for microbial conversion processes (Horn, Aasen, & Østgaard, 2000). The field of natural polysaccharides of marine origin is already large and expanding. Marine organisms are constituted by materials with a vast range of properties and characteristics that may justify their potential application within the biomedical field. Moreover, assuring the sustainable exploitation of natural marine resources, the valorization of residues from marine origin, like those obtained from food processing, constitutes a highly interesting platform for development of novel biomaterials, with both economic and environmental benefits. A large number of different types of compounds have been isolated from aquatic organisms, and these have been transformed into profitable products for health applications, including controlled drug delivery and tissue engineering devices. There is a wide range in the relative availability of different carbohydrates in marine environments. Marine algae contain large amounts of not only polysaccharides, notably cell wall structural, but also mycopolysaccharides and storage polysaccharides (Kumar, Sharma, & Kumar, 2005). Extracellular polysaccharides (EPS) are widely secreted by various marine organisms including plants, animals, diatoms, microalgae, and bacteria (Decho, 1990; Gutierrez, Martinez, & Prieto, 1996; Philippis, Margheri, Materassi, & Vincenzini, 1998; Philippis & Vincenzini, 1998). This review attempts to explore the plausible industrial and health benefits of modified marine carbohydrates such as chitin, chitosan, alginate, agar, and carrageenan with particular reference to its nutritional, biocompatibility, and biodegradable properties.

1.2. General structures and terminology One of the most abundant bioactive substances present in the marine organisms is the carbohydrates. The major components of marine organic matter are the carbohydrates, but few molecular-level carbohydrate analyses in seawater have been undertaken owing to the low concentrations of individual compounds. The term saccharide is derived from the Latin word “saccharum” from the sweet taste of sugars. Carbohydrates are hydrates of carbon having the general formula as Cx(H2O)y—where x and y may or may not be equal and range in value from 3 to 12 or more. Another modern

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definition of a carbohydrate is that the compounds are polyhydroxy aldehydes or ketones that offers potential chemical diversity orders of magnitude greater than their protein and nucleic acid counterparts (Turnbull & Field, 2007). Carbohydrates are major components of marine organic matter. The largest identified fraction of organic matter in the ocean is the carbohydrates which accounts for about 20–30% of organic matter in marine surface waters (Benner, Pakulski, McCarty, Hedges, & Hatcher, 1992). It also accounts for about 3–30% of the bulk dissolved organic carbon (Gueuen, Guo, Wang, Tanaka, & Hung, 2006; Hung et al., 2003; Pakulski & Benner, 1994), whereas, in estuarine and marine surface waters, they are considered to be the most labile fractions of bulk organic matter. It may play key roles in the geochemical cycles as reported by several studies (Benner et al., 1992; Burdige & Zheng, 1998; Middelboe, Borch, & Kirchman, 1995; Murrell & Hollibaugh, 2000). Uronic acids (e.g., Mopper et al., 1995), amino sugars (e.g., Kerherve, Charrieizi, & Gadel, 1995), and neutral sugars (e.g., Borch & Kirchman, 1997; Kerherve et al., 1995; Mopper et al., 1995) are the major classes of carbohydrates which have been identified in marine waters. Several investigations of dissolved carbohydrates were done in marine waters (e.g., Haniia, 1970; Iitekot, Brockman, & Michafus, 1981; Liebezeit, Bolter, Brown, & Dawson, 1989), but all of these studies relied on concentration procedures that fractionate the sample and leave an unknown fraction of carbohydrates uncharacterized.

1.3. Production of carbohydrates by marine organisms The carbohydrate content of marine organisms varies greatly in brown and red algae. Carbohydrate may comprise up to 74% of the total organic matter (Romankevich, 1984) while planktonic algae have a carbohydrate generally ranging from 20% to 40% (Parsons, Stephens, & Stickland, 1961) and zooplankton carbohydrate content is 2–4 times lower than that of phytoplankton. The phytoplankton serves as the principle source for carbohydrates found in seawater, particles, and sediments; the photosynthetic conversion of carbon dioxide to biomass is the basis of carbohydrate production. Phytoplankton carbohydrate composition has been surveyed in both field samples and laboratory monocultures. In general, glucose has been found to be the most common monosaccharide probably due to the fact that phytoplankton storage carbohydrates are primarily composed of glucose.


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The major source of carbohydrates to marine sediments is the sinking particles. Methods of analysis of carbohydrates in sediments usually involve extraction, separation and, finally, quantitation of the sugars. Carbohydrates in sediments comprise about 10% of the total organic carbon. Studies of anoxic surface sediments show that amino acids and carbohydrates are major constituents of the organic matter (Burdige & Zheng, 1998). Carbohydrates are remineralized rapidly during epigenetic and diagenetic bacterial activity and that only less than 10% of these compounds are stable enough to be incorporated into the sediment a few centimeters below the sediment/water interface (Degens, Reuter, & Shaw, 1964; Seifert et al., 1990).

1.4. Analysis of marine carbohydrates Analysis of the structural distinctions of carbohydrates can be difficult, however, since the isolation of carbohydrates from solution or from organic matrix is not a trivial problem and determination of carbohydrate structure. Many microorganisms in the marine environment that can degrade can utilize algal carbohydrates as a carbon source for energy. An interesting source for a myriad of different bioactive polysaccharides was the microalgae which can range from various industrial applications to novel food applications. Polysaccharides are polymers of simple sugars (monosaccharides) linked together by glycosidic bonds, and they have numerous commercial applications in products such as stabilizers, thickeners, emulsifiers, food, feed, and beverages (McHugh, 1987). The most representative polysaccharides in marine environment are agar, alginate, carrageenan, chitin, and chitosan. 1.4.1 Agar Agar or agar-agar is a gelatinous substance, obtained from an alga which consists of a mixture of agarose and agaropectin. This was discovered in 1658 by Minora Tanzaemon in Japan, where it is called Kanten. This can be used as a laxative, an appetite suppressant, as a vegetarian gelatin substitute, a thickener in soups, in fruit preserves, ice cream, and other desserts, as a clarifying agent in brewing, and for sizing paper and fabrics (Cregut & Rondags, 2013). The structure of agar was shown in Fig. 8.1. Agar is a gelling agent that is most commonly used in icings, sugar confectionery, canned meat and fish products, diabetic and health foods, and dairy products. Its use, however, is declining as more effective and often cheaper gums become more available. On the opposite cost side, agar is the most expensive industrially produced hydrocolloid. In 1882, Robert Koch first introduced it as a gelling agent in culture media for bacteriological

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Figure 8.1 Structure of agar.

studies. Since this, agar has become a major product initially used for biological research or analyses (Cregut & Rondags, 2013). 1.4.2 Alginates Alginate is a binary linear heteropolysaccharide containing 1,4-linked α-Lguluronic acid and β-D-mannuronic acid. This has been widely used in the field of controlled release, ion exchange, and in the vapor-permeation membrane-separation technique (Kalyani, Smitha, Sridhat, & Krishnaiah, 2008). The structure of sodium alginate is represented in Fig. 8.2. Alginate, an algal polysaccharide, is widely used in the food industry as a stabilizer, or as a thickening or an emulsifying agent. The only alginate derivative used in food is propylene glycol alginate (PGA). PGA was first prepared by Steiner (1947). Alginate when mixed with calcium ions is able to produce a gel structure, which finds use as a thickening agent in the food industry, in drug release systems during pharmaceutical applications. It is one of the important biomaterial used in wound healing and cell culture. Alginates were mainly used in the manufacture of paper and cardboard pharmaceutical, cosmetic creams, and processed foods (Chapman, 1987). The graft copolymers of this alginate polysaccharide have find applications in diverse fields such as pharmaceutical, biomedical, agriculture, and environmental. Polymers with promising applications in the biomedical field as delivery systems of therapeutic agents and the bioseparation devices have been attracting much attention, due to nontoxic nature of alginate. In literature reported, alginate, a natural anionic polysaccharide obtained by extraction from brown algae, is composed of (1–4)-linked β-D-mannuronic acid and α-L-guluronic acid blocks. Due to their gelling ability in the presence of divalent cations, such as calcium and barium, stabilizing properties and high viscosity in aqueous solutions, alginate and its derivatives have been extensively utilized in


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Figure 8.2 Structure of alginate.

biomedical applications of cell transplantation, drug delivery, and bulk agent gels. However, as no hydrolytic or enzymatic chain breakages occur within alginate chains, high-molecular-weight alginate polymers cannot be easily degraded and may be very slow to clear from the body. 1.4.3 Carrageenan Carrageenans are too algal hydrocolloids and are among the cheapest hydrocolloids available with an estimated price of US$10.5 kg1. The main utilization is as a gelling agent for food and cosmetic industries, but carrageenan’s role in pharmaceutical industry as an additive is limited by its variability in structure and properties. However, carrageenans are the most produced gelling hydrocolloids with approximately 50,000 tons per year for a global value estimated of US$527 million, in 2009. Carrageenan is derived from seaweed of the class Rhodophyceae which has no nutritional value and is used in food preparation for its gelling, thickening, and emulsifying properties (Van de Velde, Lourenco, Pinheiro, & Bakkerd, 2002). Carrageenan is added to processed foods because it can bind water and improve palatability and appearance through interaction with other substances in the food (e.g., proteins, sodium or calcium phosphates, starch, galactomannan, and carboxyl methylcellulose) (Piculell, 2006). The structure of different forms of carrageenan is represented in Fig. 8.3. Carrageenans are also used as stabilizers for foams, ice cream, condensed milk, cream, and salad dressings. Carrageenan is widely used in dairy products to improve texture, thickness, and solubility (McHugh, 2003). Carrageenan is also successful in controlling discoloration, maintaining texture through shelf life, and providing antibacterial protection by coating on sliced lychee (Plotto, Narciso, Baldwin, & Rattanapanone, 2006), bananas (Bico, Rapaso, Morais, & Morais, 2009), and mangoes (Plotto et al., 2006).

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Figure 8.3 Different forms of carrageenan.

Plain carrageenans, as well as agar, are mainly used as a food additive, but increasing attention is given to possible biomedical applications, in combination with synthetic polymers. The synthesis of agar-graftpolyvinylpyrrolidone (PVP) and κ-carrageenan-graft-PVP blends by a microwave irradiation method has been reported (Prasad et al., 2006). The physicochemical and rheological properties of the corresponding hydrogels were studied and compared with control agar and κ-carrageenan hydrogels. The novel blend hydrogels were found to be not as strong and showed better spreadability and water-holding capability, so they are potentially useful in moisturizer formulations and active carriers of drugs. The use of blended PVP with agar in hydrogel dressings has also been reported (Lugao et al., 1998).


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In the biomedical area, the use of modified carrageenans has also been explored. Porous nanocomposites were prepared by coprecipitation of calcium phosphates into a κ-carrageenan matrix (Daniel-da-Silva, Lopes, Gil, & Correia, 2007), whose resulting porosity and morphology were suitable for application in bone tissue engineering. The association among carrageenan, nanohydroxyapatite, and collagen resulted in an injectable bone substitute biomaterial, suitable for bone reconstruction surgery (Gan & Feng, 2006). 1.4.4 Chitin and chitosan Chitin was first discovered in mushrooms by the French Professor, Henri Braconnot, in 1811. In 1820s, chitin was also isolated from insects. Chitin contains 2-acetamido-2-deoxy-β-D-glucose through a β (1 ! 4) linkage. Chitin is the most abundant natural fiber next to the cellulose and is similar to cellulose in many respects. The most abundant source of chitin is the shell of crab and shrimp. Chitosan was discovered in 1859 by Professor C. Rouget. Chitosan contains 2-acetamido-2-deoxy-β-D-glucopyranose and 2-amino-2-deoxy-β-D-glucopyranose residues (Bhatnagar & Sillanpaä¨, 2009). Chitin (C8H13O5N)n is a long-chain polymer of a N-acetylglucosamine, a derivative of glucose which was first identified in 1884 (Gonzalez-Davila, Santana-Casiano, & Millero, 1990). Chitin can be found in one of the three crystalline forms α-chitin, β-chitin, and γ-chitin, respectively. α-Chitin is mainly present in shells of crabs, lobsters, and shrimps. The β-chitin was obtained from squid pens in which the chains are arranged in a parallel fashion, while γ-chitin is the form in which the molecules are arranged in both parallel and antiparallel manners. Based on the intermolecular interactions and the packing arrangements, it was finally concluded that the β-chitin was found to be more reactive and versatile (Morganti, 2012). It is the most important inexpensive natural biological polysaccharide occurring in crustaceous shells or in cell walls of fungi which has gained much attention for biomedical and industrial applications, due to its biocompatibility and restorative properties (Borch & Kirchman, 1997). Examples of the potential uses of chemically modified chitin in food processing include the formation of edible films and as an additive to thicken and stabilize foods (Shahidi, Arachchi, & Jeon, 1999) and pharmaceuticals. Moreover, due to its biodegradable nature, chitin has been reported to have some unusual properties that accelerate healing of wounds in humans (Morganti, 2012), and it is also used as a potential biomaterial for artificial skin, suture, and drug carrier (Lee, 1996). Up to now, the biotechnologically produced

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chitin is not commercially available, but it offers new perspectives for the production of high-viscosity chitosan, with a promising potential for applications in biomedicine and pharmacy (Hang, Dunstan, & Dass, 2010). Fermentation of this biowaste using lactic acid bacteria for the production of chitin has been studied and reported. Fundamental knowledge of the interactions among chitin and proteins, polysaccharides, calcium carbonate, enzymes, drugs, cells, and synthetic materials is not only important for elucidating biological processes associated with chitin but also for designing novel chitin-based biomaterials (Wang & Esker, 2014). Chitosan a unique basic linear polysaccharide obtained from the deacetylation of chitin which comprises an unbranched chain consisting of β-(1,4)-2-amino-2-deoxy-D-glucopyranose (Muzzarelli, 1993). When compared to other polysaccharides, chitosan has several excellent properties such as biocompatibility, biodegradability, nontoxicity, good film-forming capacity, and excellent chemical-resistant behavior. Due to these advantages, chitosan has been widely used in membranes on ultrafiltration, reverse osmosis, evaporation, clinics (Badawya & Rabeab, 2009) and surfactants (Ngimhuang, Furukawa, Satoh, Furuike, & Sakairi, 2004), drug delivery systems (Sashiwa, Yajima, & Aiba, 2003), and solid polyelectrolyte formations (Wang, Xu, & Chen, 2007). The diagrammatic representation of formation of chitosan from the chitin is shown in Fig. 8.4. Chitosan is widely used especially in food industry, pharmaceutical industry, and biotechnology. In addition, using chitosan as a carrier, many studies have been conducted with mouse, rat, rabbit, and canine animal models in order to describe in vivo biocompatibility, biodegradability, drug delivery, DNA delivery, and wound healing. Chitosan is mainly used in water purification plants throughout the world to remove oil, grease, heavy metals, and fine particulate matter that cause turbidity in wastewater streams. The decolorization by chitosan which is decrystallized by citric acid is efficient, fast, and cost effective and appears to be a promising method for the treatment of alkaline effluent from textile industry containing mixed dye. Chitosan has also been approved as a food additive in Korea and Japan since 1995 and 1983, respectively (KFDA, 1995; No, Park, Lee, Hwang, & Meyers, 2002; Weiner, 1992). Higher antibacterial activity of chitosan at lower pH suggests that the addition of chitosan to acidic foods will enhance its effectiveness as a natural preservative (No et al., 2002). Chitosan has, in the last decades, been widely used in a variety of applications, both industrially and pharmaceutically, which has been well described in several comprehensive reviews


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Figure 8.4 Chitosan derived from chitin.

(Dodane & Vilivalam, 1998; Felt, Buri, & Gurny, 1998; Illum, 1998; Prabaharan, 2008; Rinaudo, 2006). A large body of research exists on chemical modification of chitosan through derivatization of the amine and/or hydroxyl groups (Amidi et al., 2006; Snyman, Govender, & Kotze, 2003; Thanou et al., 2000). Comparatively, many cellulose derivatives have been produced in a similar way (Philipp et al., 1996). However, the advantage of chitosan in comparison with other polysaccharides (such as cellulose, starch, and galactomannans) is that its chemical structure allows easier modifications at the C-2 position. Specific groups can be introduced to achieve novel polymers for selected applications. Attempts to enhance water solubility of chitosan led to several methods of derivatization. Examples include sulfonation (Bannikova, Sukhanova, Vikhoreva, Varlamov, & Gal’braikh, 2002), quaternarization (Polnok, Verhoef, Borchard, Sarisuta, & Junginger, 2004), carboxymethylation (Wongpanit et al., 2005), and N- and O-hydroxyalkylation (Donges, Reichel, & Kessler, 2000; Richardson &

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Gorton, 2003). Furthermore, a variety of graft copolymerization of chitosan, for example, with lactic acid (Yao et al., 2003), polyacrylic acid (Shim & Nho, 2003), vinyl pyrrolidone (Yazdani-Pedram & Retuert, 1997), 3-Ododecyl-D-glucose (Ngimhuang et al., 2004), and N-isopropylacrylamide (Lee, Ha, Cho, Kim, & Lee, 2004), have been presented and evaluated as practical biomedical materials. Cyclodextrin-linked chitosan is interesting for the viewpoint of pharmaceutics, including drug delivery, cosmetics, and analytical chemistry, and quaternized chitosan has potential as an absorption enhancer across the intestinal epithelium due to its mucoadhesive and permeability enhancing properties (Sashiwa & Aiba, 2004).

1.5. Carbohydrates in sediments Carbohydrates are the major organic compounds produced in the biosphere through autotrophic organisms by photosynthetic methods (Youssef, El-Said, & Shobier, 2013). Due to its more abundant and ubiquitous nature, the carbohydrates play an important role in biogeochemical cycles occurring in the marine water column, sediment–water interface which accounts for 10–85% of the dissolved organic carbon in seawater (Pakulski & Benner, 1994), sediments, and pore waters (Arnosti & Holmer, 1999; Burdige, Skoog, & Gardner, 2000). The major source of carbohydrates to marine sediments is the sinking particles. Methods of analysis of carbohydrates in sediments usually involve extraction, separation, and, finally, quantitation of the sugars. Studies of anoxic surface sediments show that amino acids and carbohydrates are major constituents of the organic matter Carbohydrates are remineralized rapidly during epigenetic and diagenetic bacterial activity and that only less than 10% of these compounds are stable enough to be incorporated into the sediment a few centimeters below the sediment/water interface (Degens et al., 1964).

2. APPLICATIONS OF MARINE CARBOHYDRATES Carbohydrate polymers have current or potential industrial application in many areas such as paper, adhesives, food, textiles, wood, pharmaceuticals, biodegradables, and biorefining. It plays an important role in many biological and biochemical processes such as the maturation, fertilization, cell differentiation, protein folding, and degradation. The marine carbohydrates including glucosamine glycon, chitin, chitosan, fucoidan,


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carrageenan, and alginic acid have a host of bioactivities such as antioxidative, antibacterial, antiviral, antitumor, immunostimulatory, and anticoagulant.

2.1. In cosmetics Generally, algae are mainly used to produce a wide range of metabolites such as carbohydrates, carotenoids, proteins, lipids, or vitamins for health, food and feed additives, and cosmetics and for energy production. The pigment content in microalgae is a specific feature of each species. Its evaluation is essential as an indirect measure of cell growth, as well as a parameter to check the trophic level of waters. Components of algae are frequently used in cosmetics as thickening agents, water-binding agents, and antioxidants. Some microalgal species are established in the skin care market, the main ones being Arthrospira and Chlorella (Stolz & Obermayer, 2005). Microalgae are the microscopic unicellular organisms which have the capability to convert solar energy to chemical energy via photosynthesis. The extracts of microalgae, marine fungi, and bacteria seem to have genuine repairand-maintenance effects in skin cosmetics, fighting UV damage, and age deterioration. Chitosan is used as antiobesity agent, moisturizing agent, emollient, and film former.

2.2. In food and agricultural field Marine organisms have been used for centuries as a resource, mainly for simple fuels, food, and fertilizers. The development of a global high-value industry based on carotenoids from certain microalgae which provides medical or health benefits, in food and aquaculture feeds as antioxidants and colorings for use in nutraceuticals has been seen in the past 40 years. Only in the recent years, the attention has turned to making use of algae (seaweeds and microalgae) and invertebrates as sources of platform molecules, building blocks, and processes for a wider range of industries. Another useful commodity from algae is livestock feed. A large number of algae have been tested for their biochemical compositions to be used as a livestock feed supplement or primary livestock feed. Edible seaweeds have reported to be used as food due to lower calorie, high concentration of minerals, vitamins, and proteins, and a low fat content (Dhargalkar & Verlecar, 2009). Algal biomass may well become a significant component of mixed materials for bioenergy production. The carbohydrates and lipids present in macroalgae and microalgae are raw materials for green fuels, some of which are finding their way into jet fuel and commercial flights using the biorefinery

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approach. Anaerobic digestion of total algal biomass can also provide methane for combined heat and power. EPS produced by marine organisms also have a role as inhibitors of crystal formation in frozen foods and sugar syrups (Colwell, Pariser, & Sindkey, 1986; Sogawa, Kodama, Matsuda, Okutani, & Shigeta, 1998; Sutherland, 1998). Spirulina a well-known blue green alga is still used in food supplements due to its excellent nutrient compounds and digestibility (Kumar et al., 2005). Besides higher content of protein (60–70 wt.%), Spirulina also contains a rich source of vitamins, especially vitamin B12 and provitamin A (β-carotene) and minerals (Thajuddin & Subramanian, 2005). Compared to other microorganisms, Spirulina can be cultivated in high saline water and alkaline conditions which give an advantage to function as a feedstock for livestock feed. In addition, red algae, mainly Porphyra, and brown algae, particularly Laminaria, Undaria, and Hizikiafusiforme, were directly consumed in human food (Besada, Andrade, Schultze, & Gonzalez, 2009). In the human food industry, agar is used mainly as a gelling agent and in a secondary way as a stabilizing agent and for controlling viscosity. It is used as an additive, not as a nutrient. The gelling power of agar is so high that it is used at 1% maximum concentration; for viscosity control and as a stabilizing agent, the proportion used is 1/100 or less. For this reason, the ingested quantities are very small and, because agar is not easily digested by the human body, its calorie contribution is negligible and thus agar can be used in special diet food. Agar digestion by the human body is imperfect; studies have shown that less than 10% of the polysaccharide is assimilated. Therefore, due to the small proportions in which it is used in human food, its importance as a nutrient is very small (http://www.fao.org/docrep/x5822e/ x5822e03.htm). Agar has been used for many centuries as a high performance gelling agent. Its ability to produce clear, colorless, odorless, and natural gels without the support of other colloids has long been exploited by the food industry not only as a stabilizer and gelling agent but also in the manufacturing of confectionery aspics, glazing, icing coatings, piping jellies, salad dressings, etc. (http://indiaagar.com/Agar.aspx). The use of chitosan-based edible films is also used to preserve the microbial quality of pork meat hamburger. Tripathi, Mehrotra, and Dutta (2009) developed a novel antimicrobial coating based on chitosan and PVA and evaluated its effect on minimally processed tomato. These results indicated that the film may be a promising material for food packaging applications. Chitosan is used as a preservative in low-pH foods, either alone or in combination with other preservative systems. The constituents of the food


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matrix appear to have an important effect on the antimicrobial efficacy of chitosan (Rhoades & Roller, 2000). Several workers (Bhale et al., 2003; Caner, 2005; Lee, 1996) have reported that chitosan coating is effective in preserving the internal quality of eggs. Chitosan films as well as chitosan-coated films are used as active packaging, which can increase shelf life by inhibiting microbial growth (Chen, Yeh, & Chiang, 1996; Labuza & Breene, 1989). The use of chitin films to preserve fruits is approved in Canada and in the United States (Shahidi et al., 1999). Other applications of chitinuous products include enzyme immobilization, water purification and clarification, deacidification, and as emulsifying, thickening, and stabilizing agents. The search for robust and energy-sparing enzymes, for food processing and other industrial-scale uses and biocatalytic conversion for green chemicals, is also finding the marine environment a fruitful source of new candidates. Beyond the well-understood hydrocolloids, the seaweeds are now being developed for uses that underpin large sectors of processed foods and drinks, and cosmetics industries. Coating fruits with semipermeable film has generally been shown to retard ripening by modifying the endogenous CO2, O2, and ethylene levels of fruits (El Ghaouth, Arul, Ponnampalam, & Boulet, 1991). Chitosan coating is used to modify the internal atmosphere without causing anaerobic respiration, because chitosan films are selectively permeable to O2 than to CO2 (Bai, Huang, & Jiang, 1988). Therefore, chitosan coating modifies internal atmosphere in the tissue and fungistatic property and thus has a potential to prolong storage life and control decay of fruits. To effectively extend the shelf life of postharvest fruit and vegetable, chitosan-based coating as a relatively convenient and safe measure, is more and more concerned in food industry in recent years. Chitosan has strong antimicrobial and antifungal activities which effectively controls fruit decay Aider (2010). Chitosan forms a coating on fruit and vegetable, and thus the respiration rate of fruit and vegetable was reduced by adjusting the permeability of carbon dioxide and oxygen (Elsabee & Abdou, 2013). Chitosan is also used in many postharvest fruits and vegetables, such as grape, berry, jujube, and fresh-cut lotus root (Perdones, Sańchez-Gonza´lez, Chiralt, & Vargas, 2012; Yu et al., 2012; Xing et al., 2010). Chitin or chitosan is used to control postharvest diseases of many fruits such as pear (Yu, Wang, Yin, Wang, & Zheng, 2008), strawberry (Bhaskara, Belkacemi, Corcuff, Castaigne, & Arul, 2000; Ge, Zhang, Chen, Ma, & Xu, 2010), table grape (Mark, Bikales, over Berger, & Menges, 1985), tomato (Badawya & Rabeab, 2009), citrus (Chien, Sheu, & Lin, 2007), and longan (Jiang & Li, 2001).

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Though chitosan coating has many advantages for the preservation of postharvest fruit and vegetable, as for specific fruit or vegetable, single chitosan coating sometimes demonstrates a certain defect, which includes limited inhibition to especial microorganism that leads fruit to decay, and poor coating structure to adjust the permeability of carbon dioxide and oxygen (Ravi, 2000). To overcome this deficiency of single chitosan coating, there are two main methods to improve the property of chitosan coating. One method is that the chitosan were combined with organic compounds such as essential oil, organic acid, or inorganic compound including metal ions and inorganic nanomaterial, as well as biological control agents. The other method is that the single chitosan coating was applied with physical remedies containing heat treatment, hypobaric treatment, gas fumigation, and modified atmosphere packaging. After applying improved chitosan-based coating, the preserving effects were increased in most of the cases compared with single chitosan (Jianglian & Shaoying, 2013). Chitosan with a partial positive charge possess acid-binding properties (Imeri & Knorr, 1988) and to be effective in aiding the separation of colloidal and dispersed particles from food processing wastes (Knorr, 1985). These properties make chitosan an attractive processing aid in fruit juice production. Chitosan is also used to improve the quality and shelf life of milk. Ha and Lee (2001) investigated the effectiveness of water-soluble chitosan to minimize the microbial (bacterial and yeast) spoilage of processed milk. Complete inhibition of microbial growth was observed in the bananaflavored milk containing chitosan. In agriculture, chitosan is used as a coating for fertilizers, pesticides, herbicides, nematocides, and insecticides for their controlled release to soil which is done in order to reduce environmental damage caused by excessive use of these agrochemicals. Chitosan films are used to coat seeds and leaves to prevent microbial infection (Li, Dunn, Grand Maison, & Goosen, 1992).

2.3. In pharmaceutics Algal organisms are rich source of novel and biologically active primary and secondary metabolites. These metabolites may be potential bioactive compounds of interest in the pharmaceutical industry (Rania & Hala, 2008). Biopolymers produced by marine organisms are being increasingly investigated for several biomedical applications (d’Ayala, Malinconico, & Laurienzo, 2008; Rinaudo, 2008). The polysaccharides derived from marine materials have been widely used in the development of drug delivery


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devices, especially with the shape of spheres of different sizes. The most probable marine-derived polymers used in the preparation of drug delivery particles are the chitosan and alginate. These two main polysaccharides (alginate and chitin) extracted from marine plants (algae kelp) and crab shells, respectively, have an extensive history of use in basic sciences, pharmacy, and medicine. The existence of bioactive compounds in algae is to be expected due to co-occurrence of these organisms in aquatic natural communities, where an inhibitory interaction occurred between producers and competitors within the same habitat. Microalgae contain numerous bioactive compounds that can be harnessed for commercial use. They have emerged as important sources of proteins and value-added compounds with pharmaceutical and nutritional importance. The microalgae have a significant attraction as natural source of bioactive molecules, because they have the potential to produce bioactive compounds in culture, which are difficult to produce by chemical synthesis. Some other novel molecules, which are obtained from the microalgae, marine fungi, and bacteria, have the exciting potential in medicine for cancers, immune disorders, and resistant microbial infections. A toxin named as holothurin is the earliest biologically active substance of marine origin which was extracted by Nigrelli from a marine organism, the Actinopyga agassizi (Nigrelli, Stempien, Ruggirei, Liguori, & Cecil, 1967). Holothurin showed some antitumor activities in mice. After this invention, the search for drugs and natural products of interest from marine organisms has continued. Also, the replacement of the existing polysaccharide polymers such as carrageenan by the porphyridium polysaccharide was used in biomedical applications. Chitin and chitosan have been proposed as biomaterials having a range of biomedical and industrial applications because of their potential beneficial biological activities (Shigemasa & Minami, 1995), such as antimicrobial activity and stimulation of healing. Chitosan is a viscous solution and is easily gelled upon mixing with heparin solution, resulting in an insoluble hydrogel (Fujita et al., 2004, 2007). In drug delivery systems, the modification of chitosan is a powerful tool to control the interaction of the polymer with drugs, enhances the load capability, and tailors the release profile of the drug carriers. It is an acknowledged polymer for drug delivery in the colonic part, since it can be degraded by the microflora present in the human colon. Also, it has the potential of serving as an adsorbent enhancer across intestinal epithelial cells for its mucoadhesive and permeability enhancing property ( Janes, Calvo, &

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Alonso, 2001; Kowapradit et al., 2008). It is also proved to enhance insulin absorption across human intestinal cell without injuring them. The performance of chitosan on the cited applications was mainly due to responsible properties such as excellent chelation behavior, antimicrobial activity, high adsorption, controllable biological activity, hydrogels forming ability, film-forming ability, nontoxicity, biodegradability, and biocompatibility (Honarkar & Barikani, 2009; Rinaudo, 2006; Silva, Mano, & Reis, 2010). Polysaccharide-based biomaterials plays an emerging role in several biomedical fields such as tissue regeneration, particularly for cartilage, drug delivery devices, and gel entrapment systems for the immobilization of cells. The ability of chitosan to be processed into porous structure is used in cell transplantation and tissue regeneration. Three-dimensional biodegradable chitosan nanohydroxyapatite composite scaffolds were reported for bone tissue engineering application (Thein-Han & Misra, 2009). The thermogelling chitosan/glycol phosphate solutions prepared by Chenite, Chaput, and Wang (2000) can form a gel in body temperature and are attractive as injectable implant system in tissue engineering. These liquid gels are able to fill any space or shape of a defective site, leaving cells and therapeutic agents and are incorporated prior to the injection within the solution and the systems can be implanted in the site without surgery. In wound healing, an ideal dressing should protect the wound from bacterial infection as well as promote healing (Wu et al., 2003). Chitosan-based materials, produced in varying formulations, have been used in a number of wound healing applications. Chitosan induces wound healing on its own and produces less scarring (Azad, Sermsintham, Chandrkrachang, & Stevens, 2004; Ueno, Mori, & Fujinaga, 2001; Ueno et al., 1999). When used in wound management, chitosan and its derivatives turn into gel, when they come into contact with body fluids and reduce friction between the dressing material and the wound. They also accelerate wound healing with their hemostatic properties and stimulate macrophage. The increase in the antimicrobial activity is observed with carboxymethyl chitosan, which makes the essential transition metal ions unavailable for bacteria or binds to the negatively charged bacterial surface to disturb the cell membranes (Liu, Guan, Yand, Li, & Yao, 2001). In the field of ophthalmology, chitosan is used in the making of therapeutic contact lenses and eye dressing. Chang, Niu, Huang, and Kuo (2007) proposed the use of polyethylene glycol (PEG)-g-chitosan for cell adhesion applications, while Wang et al. (2007) successfully used this copolymer to coat a poly(dimethylsiloxane)


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microchip intended for biomolecule (amino acids and proteins) separation, using an in situ method. In the latter experiment, the coating increased surface hydrophilicity and suppressed adsorption of biomolecules. Radhakumary, Prabha, Nair, and Suresh (2009) suggested the application of chitosan-comb-graft-polyethylene glycol (PEG) monomethacrylate as a new biomaterial for hemodialysis and immunoisolatory membranes. This material was found to have discriminating permeability capacities (permeable to low-molecular-weight solutes like creatinine, glucose, and urea and impermeable to high-molecular-weight solutes like albumin). Li et al. (2009) reported the possibility of making films of mPEG-g-chitosan by preparing a composite film with suitable hollow and high capacity of water adsorption, which could have potential application in wound healing and tissue engineering. Aly, Abdel-Mohsen, and Hebeish (2010) showed innovative multifinishing using O-PEG-g-chitosan/citric acid aqueous system for preparation of medical textiles. The cotton treated with the copolymer has been evaluated as healthcare worker uniforms and medical products, acquiring antimicrobial and anticrease properties. Usually, chitosan manufactured from squid pen by spin casting technology is used in contact lenses. They have good tensile strength, elongation, modulus, tear strength which are essential in the making of contact lenses. Also, ocular bandage lenses are made from chitosan-based materials, as they possess antimicrobial, wound healing, and film capability properties (Markey, Churchill, & MacDonald, 1989). Targeted chitosan nanoparticles have been developed to specifically deliver therapeutics or contrast agents to tumor or metastasis for cancer treatment and diagnosis. So far, several studies have investigated PEGylation of chitosan to improve its affinity to water and organic solvents. PEG is a neutral, water-soluble, and nontoxic polymer which has been employed for pharmaceutical and biomedical applications (Harris & Zalipsky, 1997). PEG is a synthetic polymer approved by the FDA for internal consumption and injection in a variety of foods, cosmetics, and drug delivery systems (Cavalla, 2001). Magnetic chitosan nanoparticles, as multifunctional nanocarriers, were loaded with bleomycin and proved to be a very effective as targeting system by Kavaz, Odabas, Gu¨ven, Demirbilek, and Denkbas (2010). After systematic administration of these systems into the body, they circulate in the blood stream and specifically bind to the targeting cancerous cells or tumor sites due to the incorporation of signaling molecules in their constituents (Hang et al., 2010).

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Recent studies have demonstrated that chewing the chitosan oligomer containing gum effectively inhibited the growth of carcinogenic bacteria in the saliva (Hayashi, Ohara, & Ganno, 2007) and also the growth of periodontic bacteria (P. gingivalis) in saliva. The chitosan-containing gum chewing has a greater antibacterial effect and it also increases salivary secretion (Hayashi, Ohara, Ganno, Ishiazaki, & Yanagiguchi, 2007). Also due to the antibacterial properties of chitosan, it is an important component in skin care creams, shampoos, and hair sprays. As chitosan is the only natural cationic gum that becomes viscous on being neutralized with acids, it is used in creams, lotions, and as nail lacquers (Mark et al., 1985). Recently, asymmetric chitosan membranes were developed for the guided tissue regeneration using the two-step phase separation (Kang et al., 2007). Chitosan’s functional groups allow it to interact with many materials, which allow it to be used in conjunction with materials such as hydroxyapatite or other calcium-based minerals to form composites that have multiple applications within the orthopedic and periodontal industries. These calcium–chitosan composites can be used as a coating in conjunction with joint prostheses. As the chitosan is degraded, new bone can be deposited adjacent to the prosthesis to stabilize the implant within bone. An additional use for chitosan in orthopedics includes a direct replacement of bone or hard tissue. It is also a natural bioadhesive used to improve bone cement which is used to secure implants as well as to fill bone cavities (Foda, El-Laithy, & Tadros, 2007; Khor & Lim, 2003; Senel & McClure, 2004). Another recent article shows the finding of the occurrence of silica–chitin fiber composite in skeletons of marine sponges. This is the first report of a silica–chitin’s composite biomaterial found in nature. From this perspective, the view that silica–chitin scaffolds may be key templates for skeleton formation (Ehrlich et al., 2007). This structural information could be useful in developing scaffolds for tissue engineering and other applications. In an vitro study on the degradation and biocompatibility of poly(L-lactic acid)/chitosan (PLLA/ CS) fiber composites, excellent adhesion between osteoblast and PLLA/CS fabrics was observed, indicating good biocompatibility of the fabrics with osteoblast and its possible use as supporting materials for chest walls and bones (Zhang, Hua, Shen, & Yang, 2007). Chitin fiber is also employed to fabricate novel biomimetic nanostructured bicomponent scaffolds consisting of chitin and silk fibroin nanofibers by an electrospinning process. Chitosan is suitable for nerve regeneration based on its biocompatibility and biodegradability. Haipeng et al. (2000) reported that neurons cultured on the chitosan membrane can grow well and that chitosan tube can promote repair


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of the PNS. Yuan, Zhang, Yang, Wang, and Gu (2004) found that chitosan fibers supported the adhesion, migration, and proliferation of SCs, which provide a similar guide for regenerating axons to Bungner bands in the nervous system (Sudha, Aisverya, Rose, Venkatesan, & Kim, 2013). Some research work, on Aloe vera gel with the alginate film, to explore its therapeutic properties, which includes antibacterial, antiseptic, anti-inflammatory, and its ability to stimulate the fibroblast proliferation and the collagen synthesis (Atiba et al., 2011; Choi & Chung, 2003; Pellizzoni, Ruzickova, Kalhotka, & Lucini, 2012). Jayakumar, Menon, Manzoora, Naira, and Tamura (2010) have reported that the chitosan encapsulated ZnS nanoparticles were further functionalized with D-mannose to yield mannosylated ZnS of size 120 nm. In vitro cytotoxicity of the synthesized nanomaterials assessed using MTT assay suggests low cytotoxicity of the mannosylated ZnS nanoparticles toward both normal and cancer cell lines. Active targeting of cancer cells was attempted using the mannosylated nanoparticles. Alginate has been used in a number of biomedical applications, such as wound dressing, tissue engineering, and drug delivery. Several reports have suggested that certain alginate dressings (e.g., Kaltostat) can enhance wound healing by stimulating monocytes to produce elevated levels of cytokines such as interleukin-6 and tumor necrosis factor-α Thomas, Harding, and Moore (2000). Production of these cytokines at wound sites results in proinflammatory factors that are advantageous to wound healing. On the other hand, since carrageenan (CG) is negatively charged above its pKa value, it can spontaneously associate with positively charged polyions to form polyelectrolyte complexes (Zhang, Du, Wang, & Zhang, 2010). Tapia and co-workers employed polyelectrolyte complexes of CS and κCG as prolonged drug release matrix. However, the high capacity of κCG to absorb water into tablets induced premature disintegration of tablets instead of matrix swelling. Recent studies showed that, when CS–CGsbased tablets were transferred from simulated gastric fluid to simulated intestinal fluid, in situ polyelectrolyte film could be formed on the surface of tablets, and the polyelectrolyte film could further control drug release (Li et al., 2013). Thus, CS–CG nanoparticles have potential applications not only in drug delivery but also in tissue engineering and regenerative medicine (Li, Ni, Shao, & Mao, 2014). In addition to the aspects described earlier, the utilization of CG in the pharmaceutical field is being broadened. For instance, besides as a novel pelletizing agent, CG can also be used as an efficient drug release modifier for ethyl cellulose-coated pharmaceutical dosage forms.

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2.4. In biotechnology and microbiology Marine biotechnology has an increasingly important role in the future bioeconomy. In order to maximize the impact of public funding for research and innovation in marine biotechnology, the Europe is now at the verge of creating a higher level of interlinking and aligned national research programs. Marine biotechnology mainly consists of two aspects. It uses the products and processes of marine organisms in modern industrial biotechnology, and applies the biotechnology in the marine context in areas such as environmental monitoring and bioremediation. By controlling the growth conditions of variety of microorganisms in a bioreactor while tailoring the production of biologically active compounds, it is possible to obtain different number of polysaccharides using biotechnology as the powerful tool. The knowledge of biochemical processes which was adapted in extreme marine environments is the basis for discoveries in biotechnology. This was the actual current opinion of most of the scientific community throughout the world in the fields of biotechnology that could benefit from miming the extremophiles are very broad and cover the search for new bioactive compounds for pharmaceutical, industrial, agricultural, environmental, and medical uses. Microalgae are employed in agriculture as biofertilizers and soil conditioners. The majority of cyanobacteria are capable of fixing atmospheric nitrogen and are effectively used as biofertilizers. Cyanobacteria play an important role in maintenance and build-up of soil fertility, consequently increasing rice growth and yield as a natural biofertilizer (Song, Martensson, Eriksson, Zheng, & Rasmussen, 2005). The agricultural importance of cyanobacteria in rice cultivation is directly related with their ability to fix nitrogen and other positive effects for plants and soil. After water, nitrogen is the second limiting factor for plant growth in many fields and deficiency of this element is met by fertilizers (Malik, Ahmed, & Rizki, 2001). Agarose forms an inert matrix which is principally used in nucleic acid and protein separations. Other very important applications, besides electrophoresis, are chromatography, gel affinity, ionic exchange, immunodiffusion, biocatalytic support, and its use in solid culture media and growth of protein crystals (http://www.hispanagar.com/ applications.htm). Thadathil and Velappan (2014) have reported biological control using microorganisms or its component to repress plant disease offers an alternative to chemical fungicide and also it is an ecofriendly approach for controlling agricultural pathogens. Several research groups reported the in vitro antifungal activity of chitosanases; they can be used to improve the resistance


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of plants against different phytopathogenic fungi. A chitosanase from Bacillus cereus D-11 inhibiting the hyphal growth of Rhizotonia solani 27-kDa chitosanase from Amycolatopsis sp. CsO-2 inhibiting hyphal growth of Rhizopus oryzae. The major component present in excreted EPS is the glucose and the galactose, mannose, arabinose being the other components. Various marine organisms, including plants, animals, diatoms, microalgae, and bacteria widely secreted the EPS (Decho, 1990; Gutierrez et al., 1996; Philippis & Vincenzini, 1998; Philippis et al., 1998). The EPS produced by the marine organisms have been explored for various biotechnological applications, such as anticoagulants (heparin analogs), antitumor agents, and wound dressings for eye and joint surgery. Apart from medical applications, EPS are also important as gelling agents (in cell and enzyme technology and foods), foam stabilizers (in beer and fire-fighting fluids), emulsion stabilizers (in food and thixotropic paints), flocculants (in water clarification and ore extraction), and hydrating agents (in cosmetics and pharmaceuticals).

2.5. In treatment of industrial effluent Wastewater is actually the water produced by different domestic and industrial activities which contains various inorganic, organic, and biological contaminants that are of environmental significance. Nutrients, trace metals, and gaseous inorganic materials are the major sources of chemical-inorganic pollutants. The source of biological pollutants includes pathogenic bacteria and the source of physical pollutants includes suspended solids and dissolved solids. These contaminants can create health hazards if discharged without proper care and treatment into streams or oceans. Especially the rapid increase in industries has led to the complexity of toxic effluents. Industrial wastewater treatment covers the mechanisms and processes used to treat waters that have been contaminated in some way by anthropogenic industrial or commercial activities prior to its release into the environment or its reuse. Some form of pretreatment was done to the wastewater obtained from industrial process prior to discharge to a sewer. This form of pretreatment was mainly done to minimize corrosion and clogging of sewer lines and to prevent reductions in biological treatment process efficiency by toxic effects from toxic concentration of organic and inorganic substances. The efficient removal of toxic metals from wastewater is an important matter and a number of technologies such as precipitation, reduction, and ion exchange were developed.

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Coagulation or flocculation process was conducted for the treatment of industrial wastewater to achieve maximum removal of chemical oxygen demand (COD), total dissolved solids (TDS), and total suspended solids (TSS). Therefore, the effect of coagulant dose, polyelectrolyte dose, pH of solution, and addition of polyelectrolyte as coagulant aid and found to be important parameters for effective treatment of beverage industrial wastewater was investigated by Amudha and his coworkers. Chitosan, a biological cationic polymer, was used in treating dairy wastewater, agriculture, food processing, medicine, cosmetics, wastewater treatment, and biotechnology (Tokura & Nishi, 1995). Reactive dyes are widely used for textile dyeing, paper printing, leather dyeing, color photography, and as additives in petroleum products. Contamination of water resources with dyes is not desirable, since colored effluents may contain toxic, carcinogenic, and mutagenic chemicals. Approximately, 10,000 different dyes and pigments are used in industry. Chitin and chitosan both have efficiency in removing dyes from wastewater. Chitosan chelation is the procedure of choice for dye removal from aqueous solution. The amine groups on chitosan bind metal cations at pH close to neutral. At low pH, chitosan is more protonated and therefore it is able to bind anions by electrostatic attraction (Guibal, 2004). Chitosan’s functional groups and natural chelating properties make chitosan useful in wastewater treatment by allowing for the binding and removal of metal ions such as copper, lead, mercury, and uranium from wastewater. It can also be utilized to remove dyes and other negatively charged solids from wastewater streams and processing outlets. Chitosan grafted with poly(acrylonitrile) has been further modified to yield amidoximated chitosan (Kang, Choi, & Kweon, 1996), a derivative having a higher adsorption for Cu2+, Mn2+, and Pb2+, compared to crosslinked chitosan. The adsorption capacity had a linear dependence on pH in cases of Cu2+ and Pb2+. However, a slight decrease in the adsorption capacity was observed in case of Zn2+ and Cd2+ (Kang, Choi, & Kweon, 1999). Chitosan has been modified with different mono as well as disaccharides. Yang, Lin, Wu, and Chen (2003) have also reported the metal uptake abilities of macrocyclic diamine derivative of chitosan. The polymer has high metal uptake abilities, and the selectivity property for the metal ions was improved by the incorporation of azacrown ether groups in the chitosan. Chitosan was successfully coated on PET granules through a dip and phase inversion process and the coated granules were examined for the performance and mechanism of humic acid removal through a series of batch adsorption tests. With its positive charge, chitosan can be used for coagulation and recovery of proteinaceous materials present in food processing


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operations (Knorr, 1991). Chitin and chitosan are also good adsorbents for removal of phenol and other pollutants from industrial wastewaters (Milhome et al., 2009). In addition to this, when chitosan was modified with some organic compounds, such as aldehydes and organic acids, it was found that the modified products with salicylaldehyde, cinnamaldehyde, benzaldehyde, and carbohydrate showed better Fe and Cu metal ions uptake. Comparatively, carbohydrate modified chitosan showed lower metal ion uptake, which they attributed to the higher ability of carbohydrate to be leached out of the chitosan matrix due to its higher solubility in water. In yet another study, chitosan was cross-linked using glutaraldehyde in the presence of magnetite. The amino sugars of chitin and chitosan are the major effective binding sites for metal ions, forming stable complexes by coordination (Chui, Mok, Ng, Luong, & Ma, 1996). The electrons present in the amino and N-acetylamino groups form dative bonds with transition metal ions, and some of the hydroxyl groups in these biopolymers may act as donors. Hence, deprotonated hydroxyl groups can be involved in the coordination with metal ions (Lerivrey, Dubois, Decock, Micera, & Kozlowski, 1986). Different degree of deacetylation (DD) chitosan was prepared in different DD and is used for the removal of a Reactive Black M-2R (RBM) from aqueous solution (Li & Ding, 2011). The deacetylated chitosan (HDC) beads, cross-linked HDC-TPP beads, and chemical cross-linked HDC-ECH were used in the adsorption behavior of anionic dye (congo red or direct red 28) and cationic dye (methylene blue or basic blue 9) (Thein Kyaw, Sander Wint, & Myo Naing, 2011). Chitosan–charcoal composite was applied as a media to treat tannery effluent containing chromium (Siraj et al., 2012). The literature shows a new composite chitosan biosorbent was prepared by coating chitosan on to perlite ore and investigated for Cu(II) and Ni(II) removal. Maximum removal of Cu(II) and Ni(II) on chitosan coated on perlite was at pH 5.0. The maximum monolayer adsorption capacity of chitosan coated on perlite was 196.07 mg/g for Cu(II) and 114.94 mg/g for Ni(II). From the literature, it is clear that chitosan can be used to remove numerous trace metals (Cu(II), Pb(II),U(VI), Cr(III), Cr(VI), Ni(II), Cd(II), Zn(II), Co(II), Fe(II), Mn(II), Pt(IV), Ir(III), Pd(II), V(V), and V(IV)) from wastewater. Chitosan has been used in a variety of forms, which include chitosan beads, flakes, and membranes (Deans & Dixon, 1992; Findon, Mckay, & Blair, 1993; Mckay, Blair, & Findon, 1989; Onsøyen & Skaugrud, 1990). The removal of Cr(VI) ions from aqueous solutions has been investigated using chitosan/starch blend. Several metals are preferentially adsorbed in

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acidic media, while chitosan can dissolve in acidic condition. To overcome such a problem, some cross-linking agents such as glutaraldehyde (Ruiz, Sastre, & Guibal, 2000), epichlorohydrin (Ngah, Endud, & Mayanar, 2002), and ethylene glycol diglycidylether (Li & Bai, 2006) are used to stabilize chitosan in acid solutions. But glutaraldehyde is the most widely used because it does not have much diminishing adsorption capacity (Ngah et al., 2002). This method is used to ensure good mechanically and chemically stable beads, but it has been found to have negative effect on the adsorption capacity of the chitosan. The main reason for the loss of adsorption capacity is that amine groups are involved in the cross-linking reaction (Martinez et al., 2007). Chitosan membranes as sorbents for trace elements determination in surface waters have been tried by Elisaveta, Mladenova, Grigorova, and Irina (2011), and the authors have successfully used their membranes as an efficient sorbents for the preconcentration and they have recommended their membranes for solid-phase extraction of Cd(II), Eu(II), Ni(II), and Pd(II) from surface water. In the case of biopolymers, chitin, chitosan, and nylon 6 are widely employed as biopolymers. As an adsorbent for the removal of heavy metals from water, biopolymer has been studied. Chitosan is one of them (Navarro, Guzman, Saucedo, Revilla, & Guibal, 2003). Chitosan has the ability to form complexes with metals. It has a better adsorption capacity for metal ion. It has severe limitations in its use in acidic media because of its solubility in acid (Llorens, Pujola, & Sabate, 2004; Nomanbhay & Palanisamy, 2005). In order to increase the copper sorption capacity of raw chitosan beads, Gandhi, Kousalya, Viswanathan, and Meenakshi (2011) modified chitosan into protonated chitosan beads, carboxylated chitosan beads, and grafted chitosan beads (GCB). They showed a significant sorption capacity of 52, 86, and 126 mg/g, respectively, while raw chitosan beads displayed only 40 mg/g. They conclude that GCB showed higher sorption capacity toward Cu(II) ions. The SiCS composite was used for the chelation of divalent copper and lead from aqueous solutions using batch method (Gandhi & Meenakshi, 2012). Although the amount of available literature data for chitin/chitosan, alginate, and carrageenan application in water and wastewater treatment is increasing at a tremendous pace, there are still several gaps which need to be filled.

3. FUTURE DIRECTIONS FOR RESEARCH In future, efforts are made to improve these novel biomaterials for further enhancement in their application results. Moreover, designing of new scaffolds from other natural polymer such as alginate, gelatin would be


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possible for soft tissue engineering such as skin. Chitin/chitosan has a great potential in a variety of biomedical, industrial applications, and chitosan physicochemical and mechanical properties utilized in fabricating particles and films can be modulated for specific purposes. Efforts should be made to prepare nanofibrous scaffolds from other natural polymers including silk for hard and soft tissue engineering. And the best use of these marine sources in the field of food, cosmetics industries, in effluent treatment, and in medical field should be made.

4. CONCLUSION This review summarizes the industrial and biomedical applications of marine carbohydrates such as chitin-, chitosan-, alginate-, agar-, and carrageenan-based nanomaterials in tissue engineering, wound dressing, drug delivery, and cancer diagnosis. In addition, this review also opens up the novel applications for which these natural biopolymers can be put to use in a variety of nanostructural forms and sizes. Nanostructured composite scaffolds can be developed as promising tissue engineered constructs or for wound healing. Multifunctional use of chitin- and chitosan-based nanomaterials has been proved to aid simultaneous cancer targeting and drug delivery. We expect that this chapter provides insights on the use of these marine carbohydrates for researchers working to discover new materials with new properties for the valuable applications of these materials.

ACKNOWLEDGMENTS The authors are grateful to authorities of D.K.M. College for Women and Thiruvalluvar University, Vellore, Tamil Nadu, India, for the support. Thanks are also due to the editor Dr. Se-Kwon Kim, Marine Bio Process Research Center, Pukyoung National University, South Korea, for the opportunity to review such an innovating field.

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