Accepted Manuscript Title: Alginate based polyurethanes: A review of recent advances and perspective Author: Khalid Mahmood Zia Fatima Zia Mohammad Zuber Saima Rehman Mirza Nadeem Ahmad PII: DOI: Reference:

S0141-8130(15)00328-1 http://dx.doi.org/doi:10.1016/j.ijbiomac.2015.04.076 BIOMAC 5084

To appear in:

International Journal of Biological Macromolecules

Received date: Revised date: Accepted date:

20-2-2015 25-4-2015 28-4-2015

Please cite this article as: K.M. Zia, F. Zia, M. Zuber, S. Rehman, M.N. Ahmad, Alginate based polyurethanes: A review of recent advances and perspective, International Journal of Biological Macromolecules (2015), http://dx.doi.org/10.1016/j.ijbiomac.2015.04.076 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

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HIGHLIGHTS

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Alginate based polyurethanes: A review of recent advances and perspective

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 Polysaccharide based biopolymers have potential array of commercial applications.

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 Alginate is biocompatible, bioactive, less toxic and low cost anionic polysaccharide.

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 Alginates in combination with polyurethanes form elastomers, nanocomposites, hydrogels

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etc.

 Alginate based polyurethane modernized the food and biomedical industries.

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Alginate based polyurethanes: A review of recent advances and perspective Khalid Mahmood Zia*, Fatima Zia, Mohammad Zuber, Saima Rehman, Mirza Nadeem

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Ahmad*

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Institute of Chemistry, Government College University, Faisalabad 38030, Pakistan

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∗ Corresponding author:

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Tel.: +92 300 6603967;

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Fax: +92 041-9200671

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E-mail address: [email protected] (K.M. Zia),

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[email protected] (M.N.Ahmad)

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Alginate based polyurethanes: A review of recent advances and perspective

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Abstract

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The trend of using biopolymers in combination with synthetic polymers was increasing rapidly

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from last two or three decades. Polysaccharide based biopolymers especially starch, cellulose,

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chitin, chitosan, alginate etc. found extensive applications for different industrial uses, as they are

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biocompatible, biodegradable, bio-renewable resources and chiefly environment friendly.

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Segment block copolymer character of polyurethanes that endows them a broad range of

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versatility in terms of tailoring their properties was employed in conjunction with various natural

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polymers resulted in modified biomaterials. Alginate is biodegradable, biocompatible, bioactive,

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less toxic and low cost anionic polysaccharide, as a part of structural component of bacteria and

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brown algae (sea weed) is quite abundant in nature. It is used in combination with polyurethanes

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to form elastomers, nano-composites, hydrogels etc. that especially revolutionized the food and

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biomedical industries. The review summarized the development in alginate based polyurethanes

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with their potential applications.

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Keywords:

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Alginates; polyurethane; hydrogels; recent advances; future perspectives

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Contents

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1.

Introduction 3

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1.1.

Polysaccharides

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1.2.

Reasons for choosing alginates and polyurethane

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Alginate based polyurethanes (PU-Alg) 3.1. PU-Alg hydrogel

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3.2. PU-Alg blend

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3.3. PU-Alg elastomer

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3.4. PU-Alg nanocomposite 4.

Summary

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References

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2.1. Applications, Developments and Limitations

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Alginates-An overview

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1.

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All through the history, human have much relied on biological materials such as wool (protein

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fibers), leather, cotton (vegetable fiber), wood, silk etc. to meet their needs. Polymeric materials

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play a crucial role both in materials world and modern industrial economics [1, 2]. Polymer

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materials are solid, nonmetallic compounds of high molecular weight [3]. Natural polymers

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(proteins, nucleic acids, polyesters, polysaccharides), semisynthetic (hydro-halogenated rubber,

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cellulose nitrate) and synthetic polymers (PE, PP, PU and PVA etc.) are the three main categories

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when polymers are classified on the basis of origin [4]. Natural polymers are further divided into

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two main categories i.e. homologous biopolymers such as proteins and heterologous biopolymers

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such as glycoproteins i.e., consists of carbohydrate and protein monomers [5].

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Proteins and nucleic acids are available in large quantities from renewable resources. The

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trademark associated with natural polymers is their biodegradability, bioactivity, easy availability

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and nontoxic nature. With the progress in the research area of chemistry, biology, materials and

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modern sciences, a vast array of novel synthetic polymeric materials have been introduced from

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last ten decades. Synthetic polymers such as nylon, polyethylene and polyurethanes have

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transformed daily life, are derived from non- renewable fossil fuel resources [6]. Petroleum

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derived synthetic polymers have been widely used in composites are not readily biodegradable

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and resistant to microbial degradation thus accumulated in the environment and become a major

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source of waste disposal [7, 8]. Another problem is fossil fuel and petroleum prices volatility that

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forced to replace commercial synthetic polymers with natural biodegradable polymers such as

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polyesters, proteins and polysaccharides [9-19]. Sustainability of resources cannot be achieved if

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we will continue to use non-renewable resources.

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Polyurethanes, from a synthetic class of polymers are receiving much attention as one

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of the most biocompatible material. Due to their easy availability and propensity to modify their

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properties, polyurethanes are used for various applications e.g. coatings, sealants, adhesives,

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elastomers, foams, textile finish [20] and for biomedical applications due to having good

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biocompatibility [21, 22]. Use of natural polymers for PUs modification gained interest as they

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make them more environmentally green material. Much research has been conducted on

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polysaccharides, proteins and lipids based PUs with their respective applications in different

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industrial fields especially for biomedical applications. The structure of PU results to form a

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phase segregated structure, which make them available for their use in various ways such as

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adhesives, coatings, biomedical materials and elastomers [23, 24]. PU elastomers (PUEs) are have

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the capacity to use in various applications because they are moldable, injectable and recyclable

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[25].

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Morphological pattern of PUEs have been presented in the established literature. The

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effect of the diisocyanate structure and chain extender (CE) length using , -alkane diols on 5

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the crystallinity, surface morphology and thermo-mechanical properties of PUEs have also

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been investigated [26-28]. Published materials are also available on the synthesis,

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characterization and application of chitin based PUs [29-31]. In vitro biocompatibility and

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cytotoxicity of chitin/1, 4-butanediol blends based PUEs have been comprehensively reported

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[32, 33]. Some documents are available on the structural characterization of chitin-based

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PUEs and their shape memory characteristics [34, 35]. XRD studies and surface

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characteristics of UV-irradiated and non-irradiated chitin-based PUEs have also been

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presented elsewhere [36-41]. The microstructure of a PU b1ock is generally known to be

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composed of different phases, i.e., it is based on domains which have been built of hard

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urethane-type segments and on soft polyol segment [34]. A wide class of materials can be

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obtained by controlling variables such as the functionality, chemical composition and the

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molecular weight of the different reactants.

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Natural bio-macromolecules serve as basic template for cell growth, are usually biocompatible,

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whereas, synthetic polymers can impart other toxic compounds or impurities that do not allow cell

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growth. Compared with natural polymers, however, synthetic polymers have much better thermal

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and mechanical properties [42]. The increasing interest in new polymeric material based on

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blends of 2 or more natural bio-macromolecules and blends of natural bio-macromolecules and

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synthetic polymers can establish a new form of materials called bio-artificial or biosynthetic

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polymeric materials with improved mechanical properties and biocompatibility compared with

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those of individual polymeric component [43-47].

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1.1. Polysaccharides

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Bio-macromolecules are diverse and important class of polymeric materials formed in nature

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during the growth cycles of organisms such as animals, bacteria, green plants and fungi hence

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also referred as one of the main class of natural biodegradable polymers [48]. Bio-

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macromolecules have potential array of applications in almost all segments of the economy and

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can be used as adhesives, absorbents, lubricants, soil conditions, cosmetics, drug delivery

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vehicles, textile, good strength structural materials etc., [6]. Polysaccharides are the most

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abundant organic materials found in nature and are present in all living organisms where they

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carry out one or more of their diverse functions [49]. In comparison with other biopolymers, these

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molecules are characterized by their chemical diversity, presence of large number of functional

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groups, strong hydrophilicity and their rigidity [50]. Polysaccharides are ubiquitous can be

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classified as either homo-polysaccharides or hetero-polysaccharide and found in algae (e.g.

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alginate), plants (e.g. starch, cellulose, glucomannan, pectin, guar gum), microbes (e.g. dextran,

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xanthan gum), and animals (chitosan, chondroitin) [51-53].

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Polysaccharides have some special characteristics which are not available in other natural

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polymers which includes; water solubility, flow behavior, gelling potential and/or surface and

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interfacial properties depending upon the difference in monosaccharide composition and linkage

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type [54]. Polysaccharides have been used for decades in various industrial applications, e.g.

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pharmaceuticals, biomaterials, foodstuff and nutrition, and biofuels, growing understanding and

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deeper investigations of the importance of polysaccharides in life science are driving the

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development of polysaccharides for novel (bio-molecular) applications [55-61].

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1.2. Reasons for choosing alginates and polyurethanes

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Alginates have a potential array of commercial applications, as they are widely used in the food

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and textile industries as thickeners, stabilizers, gel-formers, film-formers etc. [62]. Due to the

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abundance of algae in water bodies, there is a large amount of alginate material present in nature

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with its excellent biocompatibility, biodegradability, non-toxicity, chelating ability and relatively

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low cost [63-64]. Hence, there is significant additional potential to design sustainable biomaterials

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based on alginates. Alginate can be easily modified in any form such as microspheres,

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microcapsules, sponges, hydrogels, foams, elastomers, fibers, etc., This property can increase the

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applications of alginate in various fields such as tissue engineering and drug delivery [65].

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Significant research has been conducted on application of alginate as a bone tissue engineering

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material [66-69], therapeutic cell entrapment [70-73], nanoparticles of alginates for drug delivery

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systems and for enzyme immobilization [74]. Notable amount of research article has been

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published covering different aspects of alginates. Further PU has shown excellent characteristic

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regarding biocompatibility with the body cells. Following study has clearly demonstrate the

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potential of PU regarding its use without any cytotoxicity. In one of the reported method,

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preparation of regenerated silk fibroin solution (SF) Cocoons of B. mori silkworm was

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degummed 3 times in 0.5% (w/v) Na2CO3 solution at 98–100C for 30 min, rinsing with distilled

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water to separate proteins and waxes [75].

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2.

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In the very first, alginate was reported by the British chemist E. C. C. Stanford in 1881. Alginate

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an anionic and hydrophilic polysaccharide is one of the most abundant biosynthesized natural

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materials that is derived primarily from two sources, marine plants i.e. brown sea weed (40% of

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dry matter) and bacteria. Commercially, alginates species are derived primarily from brown

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algae, included Laminaria hyperborea, Ascophyllum nodosum and Macrocystis pyrifera.

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Alginates isolated from bacteria such as Azotobacter and Pseudomonas species are usually not

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economically feasible for commercial applications and limited to small-scale research studies [76-

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77].

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In structural presentation, alginate contains linear blocks of (1→4)-linked β-D-mannuronic acid

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(M) and α-L-guluronic acid (G) monomers. Typically, the blocks are composed of three different

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forms of polymer segments: consecutive G residues, consecutive M residues and alternating MG

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residues. The copolymer composition, sequence and molecular weights vary with the source and

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species that produce the copolymer, also reflected in their properties. Viscosity depends upon

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molecular size, the affinity for cations and gel forming properties are mostly related to the block

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structure of guluronic acid residue. The contents of G-blocks mainly contributed to gel strength

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and stability [67, 71, 78-83].

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Alginates have four reactive sites for contribution in a chemical reaction including carboxylic acid

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and hydroxyl functional groups, and two relatively not sustainable bonds, i.e. 1→4 glycosidic and

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internal glycolic bonds. The characteristics, e.g., hydrophilicity, solubility, and chemical and

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biological properties of alginate derivatives may be modified by creating new functional groups

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into the alginate backbone [84]. Carboxyl groups and hydroxyl groups laterally on the backbone

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of the alginate enable remarkably several modification approaches to enhance or tailor the

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properties such as physicochemical, biological, mechanical, and other desired properties [85].

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Sodium alginate is water soluble and when it trickled into a solution containing Ca2+ ions, each

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Ca2+ ion knocks away the two Na+ ions. The alginate molecule contains loads of OH group that

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can be coordinated to cations (Fig. 1a).

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Fig.1.

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(a) Cations form of calcium alginate, (b) Gel formation of calcium alginate in solution [86].

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When alginate is coordinated to Na+, it’s a very flexible chain and when Na+ is replaced by Ca2+

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however, each Ca2+ ion (black dots in the (Fig. 1b) coordinates to two alginate chains, linking

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them together. The flexible chains become less flexible and form a huge network – a gel within

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seconds after the alginate mixture is dripped into the water bath with the Ca2+ ions [86]. Due to its

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hydrophilic nature, alginate takes a good impression (Fig. 2) in a moist environment and can use

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as dental material [87].

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Fig. 2. 9

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Alginate based impression material for dental applications [87]

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2.1. Applications, Development and Limitations

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Alginate forms a solid gel under mild handling conditions which allows it to be used for

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entrapping cells into beads and shapes [88]. Interestingly , cell encapsulation of some types of

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alginate beads may actually enhance cell survival and growth . In addition , alginate has been

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explored for use in liver, nerve, heart, and cartilage tissue engineering [89-93].

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Pharmaceutical, food (as additive) and technical applications (such as in print paste for the

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textile industry) are quantitative hand the market for alginates. Alginate beads immobilized

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on PU matrix increase the degradation of O-phthalates by enhancing the activity of Bacillus

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sp. cells . Widely used phthalate is a plasticizer used in resins causing serious terrorism

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threats formulation intended to environment [ 94] .

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In some recent studies, the MW of alginates (MW 30,000–690,000) and the mole fraction (FM

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0.69–0.86) of mannuronate residues present in alginate molecular chains were also identified as

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key factors relating to the immunological activity of alginates [95]. Unfortunately, in the

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literature, some drawbacks associated with alginates are poor cell adhesion and mechanical

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weakness have been reported. As remedy to overcome these draw backs, the strength and cell

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behavior of alginate have been enhanced by mixtures with other materials, including the natural

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polymers agarose and chitosan [93, 96]. Alginates based blends, copolymers and composites have

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been presented in the established literature (Table 1).

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Table 1

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Different techniques for the synthesis and characterization of various alginate-based materials

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and their prospective applications in various fields

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Functionalization of polyurethanes with natural polymers especially polysaccharide found to be a

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suitable process for biomaterials development. Alginate-based polyurethanes are perhaps more

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interesting options because alginates retain advantages like low cost, abundance and range of

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applications [172-177].

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3.1. PU-Alg hydrogel

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PU–alginate gel compositions are potential material for biomedical application and food industry

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with various constituent ratios based on an anionic PU (APU) water dispersion (WD) and sodium

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alginate (AG) prepared by crosslinking with Ca+ ions. By optimizing the degree of crosslinking,

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by varying the composition ratio and Ca2+ quantity, systems with controlled thermo and pH-

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sensitivity, swelling ratio, and strength indexes can be obtained. It is worth to mention that the

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alginate contents increased the tensile strength of the material films. Mixtures of APU and AG

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formed structural non-Newtonian stable systems with higher viscosity in comparison with initial

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components in the absence of divalent cation [175].

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The mechanical strength of alginate hydrogel is subject to biodegradation and swelling [178,

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179]. Numerous attempts have been made to control the swelling degree of alginate based

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materials by modifying its structure with various methods such as blending, copolymerization

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etc., [179]. Because of the crystalline character of PU, it contain high tensile strength and anti-

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swelling property [180]. The PU-grafted Ca+ alginate gel, therefore, can be synthesized by 2-

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hydroxyethyl methacrylate (HEMA) and diehylene glycol (DEG) capped isophrone diisocyanate

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(IPDI) forming crystallizing area in the matrix of polysaccharide (Fig. 3). Grafted PU, side chains

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may affect the arrangement of alginates which may formed highly ordered crystalline region, and

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provid alginate with physical crosslinking points. As a result the thermodynamic properties such

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as stability and anti-swelling stability were improved in PU-g-CaA samples due to intensified

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intermolecular force [179].

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Fig. 3.

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Chemical procedure for synthesis of PU(I) and PU-g-CaA (II) [179]

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One recent application of PU–alginate hydrogels is in molecules imprinting such as sugars, amino

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acids and metal ions. For bovine serum albumin (BSA) imprinting, the PU grafted calcium

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alginate (PU-g-CaA) hydrogel microspheres were synthesized and characterized. It has been

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previously confirmed that the grafted PU side chains have constructed physical cross-linking

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points and improve the mechanical and chemical stability of hydrogel [179] which is therefore

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expected to be benefited for protein recognition which is confirmed by the enhanced imprinting

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efficiency and selective factors obtained at high grafting ratio. Compared with CaA, PU-g-CaA

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MIPs exhibit higher rebinding selectivity and are more capable of recognizing and separating

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target protein molecules, having promising applications as advanced material for chemical

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sensing and bio-separation [181]. Preparation of alginate-based PUs had been a significant

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challenge because of the final polymer’s tendency to the phase separation [175]. Alginate and PU

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are two incompatible polymers with different glass transition temperatures. Nevertheless, the

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development of such methods to improve the compatibility between the two polymers is a

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challenge.

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3.2. PU-Alg blend

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Keeping in view the aim of improving compatibility of two polymers, aqueous PU dispersion

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sodium alginate compositions (PUD/SA) were synthesized. PU dispersions were prepared with

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polytetramethylene glycol (PTMG) and isophorone diisocyanate (IPDI), extended with

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dimethylol propionic acid (DMPA) (Fig. 4a & 4b). Both storage modulus and tan δ versus

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temperature showed identical Tg and other thermal transition for control PUD and its blends with

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sodium alginate. The SEM and EDX showed the presence of alginate and its distribution as

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agglomerations in PU matrix. The surface properties including contact angle values decreased

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with increasing sodium alginate content that ascribed increase in the hydrophilicity of the blends.

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Such transformation was attributed to the presence of hydrophilic carboxylate, hydroxyl and ether

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functional groups attached to the alginate molecules [172]. Another approach for the preparation

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of compatible alginate based polyurethane with desired properties was the synthesis of novel

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soluble alginate-based PUs in common aprotic organic solvent by the reaction of NCO-terminated

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PU prepolymer and tri-butyl ammonium alginate (TBA-Alg) for the first time (Fig. 4c).

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Fig. 4.

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Chemical procedure for the synthesis of (a) cationic aqueous PU dispersion [182], (b) anionic

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aqueous PU dispersion [182], (c) ionic PU dispersion extended with TBA-Alg [183] (d) Non-

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ionic PU dispersion [183].

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The presence of TBA-Alg into the backbone of PU was revealed by specific peaks of uronic acid

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residues in1H NMR. The ionic nature of PU backbone not only effects on thermal properties of

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samples, but also changes the morphology of chemically-bonded alginate. Both polyether and

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polyester based non-ionic PUs extended by TBA-Alg illustrated the distinct alginate i.e.

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aggregate-like structures of alginate into the matrix of PU (Fig. 4d) whereas those ionomers

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extended by alginate were appeared as continuous systems at nanoscale [183].

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The PU segment had a very important impact on the morphology of gel surface as shown in Fig.

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5a & 5b. The Ca+ alginate (CaA) hydrogel microspheres possessed coarse surface and big cavity

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while PU-g-CaA showed a dense and smooth surface. As shown in Fig. 5c, the CaA exhibits

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characteristic 2θ values at 13.1, 25.06 and 39.42, which is due to the stronger hydrogen as well

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as polar intramolecular and intermolecular interactions. In this study, sharp peak observed at

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18.46 correspond to PU-g-CaA in-spite of 39.42, which is attributed to the addition of

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carbamate groups and ether bond. Apart from the above, PU interferes the arrangement of CaA

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forming highly-order crystal region, which indicate that PU was grafted on to the CaA. The

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relationship between reaction temperature and swelling degree of PU-g-CaA is presented in Fig.

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5d. It can be observed that the increase in of reaction temperature results to first swelling degree

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decreased and then increased. Such phenomenon is mainly attributed to PU side chains that

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intense the intermolecular interaction, forming crystal structure and facilitating the loss of inner

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water. Meanwhile, the hydrophobic nature of PU also resist water from inward diffusion.

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Fig. 5.

SEM images of (a)CaA and (b) PU-g-CaA; (c) XRD pattern of CaA and PU-g-CaA; (d) the

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influence of reaction temperature on the swelling degree of PU-g-CaA and CaA microspheres.

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[179]

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3.3. PU-Alg elastomer

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Modification in the chemical structure of PU to improve the incompatibility of alginate based

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PU was previously focused in researches [182-185]. The role of emulsifier on the final

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properties of composites containing PUDs and alginates was relatively a new strategy,

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studied by Daemi et al. [182-183]. Two different anionic and cationic PUs samples using

305

DMPA and N-methyldiethanolamine emulsifiers respectively were synthesized. A series of

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the alginate-based PUEs were formulated by solution blending of the PUDs and sodium

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alginate. The nano-composite elastomers of cationic PUs and SA showed excellent

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miscibility, excellent mechanical properties with high elongation at break and increased

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hydrophilicity that may be due to formation of tertiary ammonium carboxylate salts produced

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from electrostatic interaction between cationic PU and poly-anionic alginate while the

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anionic ones were appeared as the relatively incompatible ingredients and their elongation

312

was significantly dropped because of the immiscibility of the SA and anionic PUs [182].

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Alginates and other natural polysaccharides can be used in different applications in drug

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delivery and control release systems as they can be used as micro and nano encapsulation

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agents [184-185]. Some investigation has been reported for drug delivery application of PU-

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Alg elastomer/hydrogel [186-190], in-vitro test of rat fibroblast cells, the cells grown in cell

317

culture media only and the cells grown in epidermal growth factor (EGF)-loaded AHP treated

318

media were studied. The EGF-treated, EGF-loaded alginate hydrogel, and EGF loaded alginate

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hydrogel polyurethane (AHP) cells were proliferated 2.7, 2.5, and 2.2 times compared with

320

cell only group, respectively [186]. Fig. 6 shows that AHP treated well group was much more

321

packed with cells. However, EGF-treated cells were the most proliferated, hydrogel-treated

322

cells were the next, and AHP-treated cells were the last order. Regarding the EGF release

323

profiles from alginate hydrogel and AHP at four different pH conditions:, the cumulative

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release increased rapidly with time and reached an equilibrium value after a certain time. In

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general, the release behavior of EGF was similar with that of BSA since both of these drugs

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are protein drug [186]. However, EGF release rate from alginate hydrogel only and AHP was

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different. EGF release rate from AHP was slower than that from alginate hydrogel because of

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its composite structure.

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In-vitro test of rat fibroblast cell (a) the cells grown in cell culture media only, (b) the cells

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grown in EGF-loaded AHP treated media for 48 h [186].

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3.4. PU-Alg nanocomposite

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Compatible aqueous cationic PUD–sodium alginate nanoparticles (CPUD/SA) elastomers were

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prepared by solution blending of cationic PUDs based on PTMG and IPDI extended with N-

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methyl diethanolamine (MDEA), 1,4-BDO chain extenders and sodium alginate (SA). Pristine

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CPUD and its nano-composite elastomers with SA showed excellent miscibility that arise from

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different charges of both anionic alginate and cationic PU and hydrogen bonding which was

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supported by DMTA and FTIR results. The prepared composites indicated two interesting nano15

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bead (low molecular weight SA) and nano-rod (higher molecular weight SA) morphologies in

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respect of different molecular weights of sodium alginate samples proved by SEM and EDX. The

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phase separation of PU segments decreased resulting in lower elongation and higher mechanical

342

strength. In the presence of greater amounts of Na alginate. Moreover, with increasing alginate

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content in the elastomers, the thermal stability and hydrophilicity increases because of the

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presence of quite thermally stable uronic acid residues and presence of hydrophilic carboxylate

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and hydroxyl groups [173]. In this progress in another study, anionic water based PU (APU) was

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formed (Fig. 7) as a result of interaction of an isocyanate precursor on the basis of

347

oligooxytetramethylene glycol (MM1000) and aliphatic diisocyanate (HMDI) (1:2) with

348

dianhydride of pyromellitic acid and dihydrazide of dicarbonic acid in acetone solution followed

349

by carboxylic groups transfer to a salt form and consecutive dispersion in water [175].

350

.

M

an

us

cr

ip t

339

Fig. 7.

(a) Scheme of the elementary unit of APU, (b) Schematic performance of alginate unit [175]

d

351

In a study [175], The APU and aqueous solution of alginate (5 wt.% ) were mixed in various

353

compositions and the sample films were cast by pouring the compositions on glass substrates,

354

dried at room temperature for 72 h, and then dried at 60 °C to constant weight in a vacuum

355

oven. The prepared material was used for various potential applications.

356

4.

357

From the last few decades the trend of utilization of polysaccharide in various industrial fields

358

owing to their structural diversity, biodegradability, biocompatibility, abundance, non-toxicity

359

and specific bioactive properties is rapidly increasing. The most abundant marine polysaccharide,

360

alginate, with their inherent well known gelling and stabilizing properties proved to be a potential

361

candidate for synthetic modified biomaterials. However certain limitations associated with this

362

unique polymer can be overcome either by modification in their structure or blending with other

Ac ce p

te

352

Summary

16

Page 16 of 46

natural and synthetic polymers. Polyurethanes/alginate hydrogels, elastomers and nanocomposites

364

systems with novelty in their properties are making the alginates a potent polymer to be explored

365

further.

366

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671 672

Table 1 Different techniques for the characterization of various alginate-based materials and their prospective applications in various fields

ip t

670

673

cr

674 675

us

676 677

an

678 679

M

680

684 685 686

te

683

Ac ce p

682

d

681

31

Page 31 of 46

687 688

TABLE & FIGURE CAPTIONS:

689

Fig. 1

cr

based materials and their prospective applications in various fields

691 692

Different techniques for the synthesis and characterization of various alginate-

ip t

Table 1

(a) Cations form of calcium alginate, (b) Gel formation of calcium alginate in solution [86]

693

us

690

Fig. 2.

Alginate based impression material for dental applications [87]

695

Fig. 3.

Chemical procedure for synthesis of PU(I) and PU-g-CaA (II) [113]

696

Fig. 4.

Chemical procedure for the synthesis of (a) cationic aqueous PU dispersion

an

694

[182], (b) anionic aqueous PU dispersion [182], (c) ionic PU dispersion

698

extended with TBA-Alg [183], (d) Non-ionic PU dispersion [183]. Fig. 5.

SEM images of (a)CaA and (b) PU-g-CaA; (c) XRD pattern of CaA and PU-

d

699

M

697

g-CaA; (d) the influence of reaction temperature on the swelling degree of

701

PU-g-CaA and CaA microspheres [179]

703 704 705 706

Ac ce p

702

te

700

Fig. 6.

In-vitro test of rat fibroblast cell (a) the cells grown in cell culture media only, (b) the cells grown in EGF-loaded AHP treated media for 48 h[186].

Fig. 7.

(a) Scheme of the elementary unit of APU, (b) Schematic performance of alginate unit [175]

707

33

Page 32 of 46

ip t

Table(s)

cr

Table 1

us

Different techniques for the characterization of various alginate-based materials and their prospective applications in various

Ac

ce pt

ed

M an

fields

1 Page 33 of 46

ip t PVA-Alginate

4.

PVA –Alginate

5.

PVA-Alginate

6.

PVA-Alginate

7.

PVA-Alginate

8.

PVA–Alginate

10.

FT-IR, EDAX Potentiometric Kinetic parameters SEM, diffusion, coefficients, stability tests (pH) EDX, FT-IR

Membrane for separation of dimethyl formamide/water mixtures Wound dressing membrane

[97] [98] [99]

Hydrolysis of pineapple waste

[100]

As a matrix for yeast immobilization

[101]

Matrix for immobilization of invertase Encapsulation of γ Fe2O3 magnetic beads for photocatalytic reduction of Cr(VI) Effective removal of N,N-dimethyl formamide from industrial effluents

[102]

XRD, FESEM

For water remediation

[105]

FTIR, SEM , TGA

For removal of divalent mercury from aqueous solutions

[106]

FESM, EDX

Mg −Al LDH-alginate / polyvinyl alcohol [A336][Mtba] / PVA–Alginate

Reference

For phosphate removal

SEM

ce pt

9.

FT-IR, SEM

cr

3.

FT-IR, SEM, DSC, TGA

M an

2.

Sodium Alginate/Poly(Vinyl Alcohol) Alloy PVA-Alginate

1.

Potential applications

us

Techniques used for characterization

Name

ed

Sr. No

[103] [104]

Na-Alg/PVA Composite

FT-IR, SEM

Nano-filtration and/or desalination

[107]

12.

Maghemite PVA–Alginate Beads

FESEM, XRD, FT-IR, XPS, EDX

Cesium removal from radioactive waste water

[108]

13.

PVA–Alginate–Sulfate

FESEM–EDX, HPLC

Matrix for enzyme immobilization

[109]

SEM

For PV dehydration of isopropanol

[110]

FT-IR, SEM, UTM

Employed for PV dehydration, esterification reactions.

[111]

14. 15.

Ac

11.

Glutaraldehyde/ Sodium Alginate - Poly(Vinyl Alcohol) Aluminum-rich zeolite beta incorporated sodium alginate

2 Page 34 of 46

ip t

Sodium Alginate/Poly(Vinyl Alcohol)

FT-IR, XRD, SEM

For drug (diclofenac sodium) delivery systems

[112]

17.

poly(vinyl alcohol)/ sodium alginate

XRD, TGA,DSC

A good candidate for alkaline direct methanol fuel cells applications

[113]

Improved ethanol production

[114]

19.

IC, SEM, EWC, GC

us

Cellulose - Alginate Carboxymethyl Cellulose Sodium Alginate

M an

18.

cr

16.

FT-IR, XRD, DTA , SEM

For separation of benzene–cyclohexane mixtures

[115]

FT-IR, SEM, XRD, DSC, TGA

Biodegradable films

[116]

Potential use for oral insulin delivery

[117]

SEM, GPC, Mercury porosimetry

Scaffolds for VEGF controlled release

[118]

FTIR, SEM, XRD, DTA– TGA

[119]

NCC-Alginate

21.

Chitosan-Alginate (CS/ALG) DLS,SEM, FT-IR

For adsorption of two important synthetic dyes, i.e. Congo red and methyl Violet from water

FT-IR, TGA

For PV dehydration of ethanol

[120]

25.

PLGA / Chitosan Cellulose Alginate

Rheometery, sonication. FESEM, FT-IR, DSC, TGA

An emulsion stabilizer in synthesis of biodegradable polymers.

[121]

26.

PLGA-Alg-RGD MP.

XPS, SEM

Delivery system for vaccination

[122]

27.

Chitosan–Poly (caprolactone)/ Alginate

SEM

For controlled delivering of VEGF

[123]

28.

Chitosan-Alginate

Sonication, SEM. FT-IR, DSC

Drug delivery

[124]

29.

Chitosan-Alginate

Nanogels for vaccine delivery

[125]

30.

Alginate–Chitosan

FT-IR, Optical microscopy

A novel fiber for wound care application

[126]

31.

Chitosan- Alginate

SEM, optical microscopy

Used in the preparation of Pickering emulsion as potent carriers in biomedical area

[127]

23. 24.

Ac

22.

ce pt

Alginate/Chitosan/ PLA-H Poly(Acrylic Acid-CoHydroxyethyl Methacrylate) - Sodium Alginate Sodium alginate-poly(Nisopropyl acrylamide)

ed

20.

3 Page 35 of 46

ip t

Carboxymethyl Chitosan Alginate

SEM

Site selective protein delivery in intestine

[128]

33.

Chitosan/Alginate Nanolayered PET Film

SEM, DSC, TGA, water contact angles

For preparation of multilayer films Coating biomedical appliances or multilayer edible coatings

[129]

34.

Alginate/HPMC

Improved in vitro release of BSA

[130]

35.

Alginate-G-Poly(Sodium Acrylate) And Poly (vinyl pyrrolidone)

SEM, FT-IR

Potential candidate for drug delivery systems and water manageable materials

[131]

36.

Alginate/Chitosan /Titanium

ATR–FTIR, XPS, SEM, XRD, DTA

Potential applications in tissue engineering scaffolds field

[132]

Minocycline loaded Chitosan/Alginate/Titanium Carboxymethyl Chitosan/Organic Rectorite / Alginate Alginate/ Alginate-Resistant Starch

XPS, SEM

Inhibit biofilm formation

[133]

ed

M an

us

cr

32.

Antimicrobial activity for fibrous mats

[134]

40.

Cellulose-Alginate

FESEM, XRD

41.

Aluminum Sulfate-Alginate

42.

Starch-Calcium Alginate

43.

Alginate–Starch

44.

Starch–Alginate

39.

45. 46.

FT-IR, FESEM, XRD

ce pt

38.

Ac

37.

FT-IR, XRD, DSC, SEM

DSC, FT-IR, SEM

FT-IR

Alginate - Sago Starch-AgTGA, SEM, TEM NP Iron/Montmorillonite/Alginat ICP-MS, FT-IR e

As a controlled release carrier for the food grade peptide, nisin. High potential to be used as high Strength packaging materials.

[135]

[136]

As coagulant for wastewater treatment

[137]

For encapsulation of antioxidants

[138]

Bacterial encapsulation

[139]

For agrochemical delivery system

[140]

Potential and economical wound dressing material. Photo-Fenton catalysts for water Disinfection

[141] [142]

4 Page 36 of 46

48.

ip t

SEM, NMR FT-IR, XRD, SEM, ICPOES

Encapsulation and intracellular delivery of a bioactive growth factor

cr

Alginate-GraftPoly(Ethylene Glycol) Calcium Phosphate -Sodium Alginate

us

47.

[143]

Drug delivery carriers

[144]

Membranes for pervaporation Dehydration of ethanol

[145]

Enhance wound healing properties

[146]

FTIR, SEM, TGA, DSC, UTM and contact angle measurements

50.

Alginate/Collagen-I

SEM

51.

Alginate - Thiol-Terminated Peptides

UV-VS, 1H NMR

Potential application for tissue engineering

[147]

52.

Sodium Alginate - Pnipaam

IR , NMR, SEM

For biomedical applications

[148]

54.

ed

UV-VIS, FESEM, AFM

ce pt

53.

Alginate/Polyethyleneimine And Biaxially Oriented Poly(Lactic Acid) Prosopis Juliflora Carbon/Ca/Alginate

M an

49.

Sodium Alginate/Heteropolyacid H14[Nap5w30o110] (HPA)

FT-IR, SEM SEM, FT-IR, Water contact angle FTIR, NMR SEM, DTA–TGA, XRD, PZC

57.

Agnps–Alginate

58.

Sodium Alginate /Superabsorbent Polymer

59.

Ag/Alginate

56.

Ac

Hyaluronic Acid/Sodium Alginate Sodium Alginate Polyacrylamide

55.

Promising alternative to non-biodegradable synthetic food Packaging materials For the adsorptive removal of aniline Blue dye (AB dye)

[149] [150]

For pervaporation dehydration of ethanol–water mixtures

[151]

For drug delivery systems

[152]

FT-IR, SEM

Treatment process for antibacterial finishing and textiles.

[153]

FT-IR, TGA, SEM

Effective recycling of textile dyes from textile effluents

[154]

For tissue engineering scaffolds , soft tissue implants, antimicrobial wound dressings

[155]

UV–vis , FESEM

5 Page 37 of 46

ip t

As an agricultural water retention agent in saline soil

[156]

FT-IR, SEM

cr

62.

FT-IR, SEM, NMR

For biomedical applications

[157]

For deflouridation process

[158]

FTIR, EDAX, SEM

us

61.

Β-Cyclodextrin/Acrylic Acid/Sodium Alginate Polycaprolactone (PCL)/Alginate Alginic Acid/ Metal Coordinated Carboxylated Alginic Acid

M an

60.

Alginate–Zirconium

FTIR, XRD, SEM , EDAX

For deflouridation of water

[159]

64.

Alginate–Lignin

SEM, Micro-CT

Scaffolds for tissue engineering

[160]

65.

Halloysite/Alginate

EDX, FT-IR, FESEM, TGA

66.

Methacrylated alginate/PEG

67.

Alginate–PEGAc

Applications including bioprocessing and tissue engineering. Bioadhesive for clinical use in biomedical applications Novel muco adhesive material for controlled drug release

68.

Calcium phosphate/Alginate

69.

Alginate/HNT

70.

Zno–Alginate

71.

Alginate–Silicate

SEM

72.

Alginate–Chitosan– Poly(lactic-co-glycolic acid)

SEM

For protein delivery system

[168]

73.

Alginate-glass ceramics

SEM, EDAX, AFM, FTIR, XRD

Useful for periodontal tissue regeneration

[169]

74.

Alginate/Polyacrylamide

SEM

Promising biomaterial for cartilage tissue

[170]

ed

63.

SEM

Ac

ce pt

optical microscopy, ESEM, For protein imprinting TEM, SEM, FT-IR Great potential for applications in tissue AFM, TEM, FTIR , XRD, engineering. TGA XRD, XPS

Controlled environment for antimicrobial activity For decolorization of the azo dye, reactive Red 22

[161] [162] [163] [164] [165] [166] [167]

6 Page 38 of 46

ip t cr

SEM, FT-IR, XRD, DSC, PALS

Membranes for enhancement of diffusion and sorption

[171]

ce pt

ed

M an

us

Alginate–Gelatin

Ac

75.

7 Page 39 of 46

Ac

ce

pt

ed

M

an

us

cr

i

Figure(1)

Page 40 of 46

Ac

ce

pt

ed

M

an

us

cr

i

Figure(2)

Page 41 of 46

Ac

ce

pt

ed

M

an

us

cr

i

Figure(3)

Page 42 of 46

Ac ce p

te

d

M

an

us

cr

ip t

Figure(4)

Page 43 of 46

Ac

ce

pt

ed

M

an

us

cr

i

Figure(5)

Page 44 of 46

Ac ce p

te

d

M

an

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cr

ip t

Figure(6)

Page 45 of 46

Ac

ce

pt

ed

M

an

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i

Figure(7)

Page 46 of 46