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Biomaterials based on a natural polysaccharide: alginate
Marguerite Rinaudo
Biomaterials Applications, 6, rue Lesdiguières, 38000 Grenoble (France)
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    "textoCompleto" => "<span class="elsevierStyleSections"><span id="sec0005" class="elsevierStyleSection elsevierViewall"><span class="elsevierStyleSectionTitle" id="sect0025">Introduction</span><p id="par0005" class="elsevierStylePara elsevierViewall">Marine algae constitute a large source of natural polysaccharides having original physical properties&#46; Algae also contain a large variety of nutriments such as vitamins&#44; salts&#44; iodine&#44; sterols&#8230;<a class="elsevierStyleCrossRef" href="#bib0005"><span class="elsevierStyleSup">1</span></a> There is a large variety of such organisms which are exploited for a long time mainly for food applications&#46; The brown algae &#40;Phaeophyceae such as <span class="elsevierStyleItalic">Fucus&#44; Laminaria&#44; Ascophyllum</span>&#41; contain large amounts of alginate in their cell walls<a class="elsevierStyleCrossRef" href="#bib0005"><span class="elsevierStyleSup">1</span></a><span class="elsevierStyleSup">&#44;</span><a class="elsevierStyleCrossRef" href="#bib0010"><span class="elsevierStyleSup">2</span></a>&#46; The quantity &#40;between 25 and 45&#37; dried weight of crude algae&#41; and quality of the alginates depend on the algae species&#44; the type and age of the tissues and methods used for extraction&#46; They are linear polymers composed of &#40;1&#8594;4&#41;-&#945;-L-guluronic acid blocks &#40;GG&#41; &#40;<a class="elsevierStyleCrossRef" href="#fig0010">Figure 1a</a>&#41;&#44; &#40;1&#8594;4&#41;-&#946;-D-mannuronic acid blocks &#40;MM&#41;&#40;<a class="elsevierStyleCrossRef" href="#fig0010">Figure 1b</a>&#41;&#44; and additionally&#44; of heteropolymeric sequences of M and G &#40;MG blocks&#41; &#40;<a class="elsevierStyleCrossRef" href="#fig0010">Figure 1c</a>&#41;&#46;</p><elsevierMultimedia ident="fig0010"></elsevierMultimedia><p id="par0015" class="elsevierStylePara elsevierViewall">Alginates are mainly used in the food and biomedical domains but in this paper we will focus on bioplastic applications&#44; a less common field developed in the literature&#44; i&#46;e&#46; applications of alginates in the domains of packaging&#44; textiles&#44; paper and wound dressing&#46;</p></span><span id="sec0010" class="elsevierStyleSection elsevierViewall"><span class="elsevierStyleSectionTitle" id="sect0030">Main characteristics</span><p id="par0020" class="elsevierStylePara elsevierViewall">The biological and physical properties of alginates in aqueous media depend not only on the M&#47;G ratio &#40;obtained by proton NMR&#41; but also on the distribution of M and G units along the chain<a class="elsevierStyleCrossRefs" href="#bib0015"><span class="elsevierStyleSup">3&#8211;6</span></a>&#46; Purified alginates have widespread industrial uses especially due to their ability to form hydrogels&#44; beads&#44; fibers or films mainly in presence of calcium attributed to the presence of zones rich in GG blocks following the model of<a name="p93"></a> an egg-box<a class="elsevierStyleCrossRef" href="#bib0035"><span class="elsevierStyleSup">7</span></a>&#46; Nevertheless&#44; it must be mentioned that MM and MG blocks also interact with calcium counterions&#46; A schematic representation of gelation for progressive and cooperative fixation of calcium is given in <a class="elsevierStyleCrossRef" href="#fig0015">Figure 2</a>&#46;</p><elsevierMultimedia ident="fig0015"></elsevierMultimedia><p id="par0025" class="elsevierStylePara elsevierViewall">The stiffness of alginates gels is directly related to the GG block content<a class="elsevierStyleCrossRef" href="#bib0040"><span class="elsevierStyleSup">8</span></a>&#46; Under their monovalent salt form &#40;especially sodium form&#41;&#44; alginates are perfectly water soluble and increase of solvent viscosity upon dissolution causing an interesting thickening character &#40;in relation with the semirigid conformation of this copolymer&#41; which found valuable applications&#46; In addition&#44; the ion-exchange properties of alginates are important due to specific strong interactions with counterions such as Ba&#44; Sr and Ca giving a gel which is reversible in presence of large excess of monovalent salts or complexing agent &#40;EDTA&#44; sodium oxalate&#44; sodium citrate&#41;&#46; Alginic acid or alginate in acidic medium gives also specific gels based on H-bond network <a class="elsevierStyleCrossRef" href="#bib0045"><span class="elsevierStyleSup">9</span></a>&#46; Another important parameter is the distribution of the molar masses and the average molar mass &#40;obtained by steric exclusion chromatography&#41; which also control the viscosity of solution and stiffness of the gels&#46; It is important to mention that specific low molar mass oligomers may be obtained by partial hydrolysis in acidic conditions followed by fractionation at controlled pH to isolate GG and MM blocks<a class="elsevierStyleCrossRef" href="#bib0050"><span class="elsevierStyleSup">10</span></a><span class="elsevierStyleSup">&#44;</span><a class="elsevierStyleCrossRef" href="#bib0055"><span class="elsevierStyleSup">11</span></a>&#46;</p></span><span id="sec0015" class="elsevierStyleSection elsevierViewall"><span class="elsevierStyleSectionTitle" id="sect0035">Alginates applications</span><span id="sec0020" class="elsevierStyleSection elsevierViewall"><span class="elsevierStyleSectionTitle" id="sect0040">Alginates in Foods</span><p id="par0030" class="elsevierStylePara elsevierViewall">Up to now&#44; the main applications of alginates were based mainly on their gel-forming ability and used as food additives in jams&#44; jellies&#8230;&#46; to improve and stabilize the structure of food&#46; In this domain&#44; alginates are also widely used as additives capable of viscosifying&#44; stabilizing&#44; emulsifying solutions<a class="elsevierStyleCrossRef" href="#bib0060"><span class="elsevierStyleSup">12</span></a>&#46;<a name="p94"></a></p></span><span id="sec0025" class="elsevierStyleSection elsevierViewall"><span class="elsevierStyleSectionTitle" id="sect0045">Alginates in biomedical applications</span><p id="par0035" class="elsevierStylePara elsevierViewall">Pharmaceutical industries use purified alginates as stabilizer in solution and dispersion of solid substances&#46; In the biomedical domain&#44; alginates are used for controlled drug release<a class="elsevierStyleCrossRef" href="#bib0065"><span class="elsevierStyleSup">13</span></a>&#44; cells encapsulation<a class="elsevierStyleCrossRef" href="#bib0070"><span class="elsevierStyleSup">14</span></a>&#44; scaffolds in ligament and tendon tissue engineering or to prepare moulds in dentistry &#40;in presence of slow release calcium salt&#41;<a class="elsevierStyleCrossRefs" href="#bib0075"><span class="elsevierStyleSup">15&#8211;17</span></a>&#46;</p></span><span id="sec0030" class="elsevierStyleSection elsevierViewall"><span class="elsevierStyleSectionTitle" id="sect0050">Alginates in packaging</span><p id="par0040" class="elsevierStylePara elsevierViewall">Cooking or warming breaded foods in a microwave oven causes a lack of crunchiness&#46; New products are now proposed for microwave heating by using active packaging &#40;with susceptors&#41;&#46; In that view&#44; a film of alginate gel with high salt concentration was used as an edible susceptor&#46; Better heating and shorter cooking times were demonstrated<a class="elsevierStyleCrossRef" href="#bib0090"><span class="elsevierStyleSup">18</span></a>&#46; Edible films were also prepared as emulsifiable alginate with new barrier properties and good mechanical properties also allowing protecting encapsulated active substances<a class="elsevierStyleCrossRef" href="#bib0095"><span class="elsevierStyleSup">19</span></a>&#46; Incorporation of garlic oil&#44; a natural antibacterial agent gives good edible film<a class="elsevierStyleCrossRef" href="#bib0100"><span class="elsevierStyleSup">20</span></a>&#46;</p><p id="par0045" class="elsevierStylePara elsevierViewall">Vegetale and fruit preservation was favoured by incorporation of stable silver nanoparticles in alginate film<a class="elsevierStyleCrossRef" href="#bib0105"><span class="elsevierStyleSup">21</span></a>&#46; Antibacterial films were obtained by incorporation of extruded white ginseng to ensure healthy foods<a class="elsevierStyleCrossRef" href="#bib0110"><span class="elsevierStyleSup">22</span></a>&#46; Antimicrobial packaging with lactic acid bacteria incorporated in alginate film matrix allows to control the growth of food-borne pathogens in ready-to-eat food<a class="elsevierStyleCrossRef" href="#bib0115"><span class="elsevierStyleSup">23</span></a>&#46; Antiradical properties were obtained with oregano-based film made of polycaprolactone&#47;alginate-calcium film<a class="elsevierStyleCrossRef" href="#bib0120"><span class="elsevierStyleSup">24</span></a>&#46;</p></span><span id="sec0035" class="elsevierStyleSection elsevierViewall"><span class="elsevierStyleSectionTitle" id="sect0055">Alginates in paper industry</span><p id="par0050" class="elsevierStylePara elsevierViewall">Alginate partially complexed with calcium &#40;such as forming a loose gel&#41; mixed with starch was proposed to get high water retention in paper coating&#46; Such advantage is important for size press coating formulation to improve coating rheology&#44; control migration and get coat weight uniformity<a class="elsevierStyleCrossRef" href="#bib0125"><span class="elsevierStyleSup">25</span></a>&#46;</p></span><span id="sec0040" class="elsevierStyleSection elsevierViewall"><span class="elsevierStyleSectionTitle" id="sect0060">Alginates in textiles and medical textiles</span><p id="par0055" class="elsevierStylePara elsevierViewall">A review was recently available which is devoted to processing of alginate fibers for their use as a wound management material<a class="elsevierStyleCrossRefs" href="#bib0130"><span class="elsevierStyleSup">26&#8211;27</span></a>&#46; Wet-spinning is the usual way to produce fibers which may be highly absorbent wound dressing materials&#59; especially&#44; mixed sodium and calcium fibers may be produced&#44; calcium giving the wet integrity and sodium the large absorbency&#46; Alginic acid fibers or silver fibers may also be prepared to enhance anti-microbial properties&#44; zinc fibers to generate immune-modulatory and anti-microbial effects&#46; Due to the process in aqueous and mild conditions&#44; it is also easy to prepare fibers for enzyme immobilization or as support for bioactive molecules<a class="elsevierStyleCrossRef" href="#bib0140"><span class="elsevierStyleSup">28</span></a>&#46;</p><p id="par0060" class="elsevierStylePara elsevierViewall">Alginate calcium fibers were prepared through wet spinning with good tensile strength which can be used for cloth materials&#46; Blending yarns and textile of alginate calcium fibers give good hand feeling and strength&#46; Alginate calcium fibers is an inherent flame-retardant fiber&#46;</p><p id="par0065" class="elsevierStylePara elsevierViewall">Nanoparticles of sodium alginate and 3-&#40;trimethoxysilyl&#41; propyl-octadecyl-dimethylammonium chloride &#40;TSA&#41; with an average size 99nm were loaded onto cotton fabrics by paddry-cure method&#46; Fibers have an efficient antimicrobial activity maintained after 30 laundry cycles &#40;non-leaching antimicrobial agent&#41;<a class="elsevierStyleCrossRef" href="#bib0145"><span class="elsevierStyleSup">29</span></a>&#46;</p></span><span id="sec0045" class="elsevierStyleSection elsevierViewall"><span class="elsevierStyleSectionTitle" id="sect0065">Alginates in hemostatic material and wound dressing</span><p id="par0070" class="elsevierStylePara elsevierViewall">New generation of medical textiles are an important growing field&#44; showing great expansion&#44; in wound management products<a class="elsevierStyleCrossRef" href="#bib0150"><span class="elsevierStyleSup">30</span></a>&#46; The main qualities of fibers and dressings as wound care products include that they are bacteriostatic&#44; anti-viral&#44; fungistatic&#44; non-toxic&#44; high absorbent&#44; non-allergic&#44; breathable&#44; haemostatic&#44; biocompatible&#44; and manipulatable to incorporate medications&#44; with good mechanical properties&#46; Textile structures used for modern wound dressings are of large variety&#58; sliver&#44; yarn&#44; woven&#44; non-woven&#44; knitted&#44; crochet&#44; braided&#44; composite materials&#46; Specialized additives with special functions can be introduced in advanced wound dressings with the aim to absorb odors&#44; provide strong antibacterial properties&#44; smooth pain and relieve irritation&#46; Because of unique properties as high surface area to volume ratio&#44; nanoscale fiber diameter&#44; porosity&#44; light weight&#44; nanofibres are used in wound care&#46; Nanofibers of alginates were produced by electrospinning technique in presence of various synthetic polymers and&#47;or surfactants to improve processability<a class="elsevierStyleCrossRef" href="#bib0155"><span class="elsevierStyleSup">31</span></a>&#46; Calcium alginate fibers have a novel gel-forming capability in that&#44; upon the ion exchange between sodium ions in the contact solution and calcium ions in the fiber&#44; the fiber slowly transforms into a fibrous gel&#46; The gel-forming process for alginate fibers and the gelling behavior of various types of alginate fibers were described&#46;<a name="p95"></a><elsevierMultimedia ident="fig0005"></elsevierMultimedia></p><p id="par0075" class="elsevierStylePara elsevierViewall">The absorption characteristics of alginate wound dressings were analyzed and it was found that alginate wound dressings absorb a large quantity of liquid into the fiber structure&#44; in addition to those held between the fibers in the textile structure&#46; This gives rise to the unique gel blocking properties of alginate wound dressings&#46; In addition&#44; alginate wound dressings also have novel hemostatic and antimicrobial properties as well as the ability to promote wound healing&#46; They are now widely used in the management of highly exuding wounds such as leg ulcers&#44; pressure sores&#44; and surgical wounds<a class="elsevierStyleCrossRef" href="#bib0140"><span class="elsevierStyleSup">28</span></a>&#46;</p><p id="par0080" class="elsevierStylePara elsevierViewall">Haemostasis and tissue repair is an important domain of development of alginate produced as thin filament in the calcium form&#46; In contact with blood&#44; Ca<span class="elsevierStyleSup">&#43;2</span> ions are liberated activating platelet aggregation and reducing coagulation time&#46; Materials are commercialised under different trademarks&#59; as example are&#58; Coalgan from Brothier Laboratories &#40;France&#41; soled as an haemostatic fibers pad for nosebleeds&#44; Algosteril<span class="elsevierStyleSup">&#174;</span> or Sorban<span class="elsevierStyleSup">&#174;</span> are also non-woven dressing absorbing rapidly and retains wound fluid resulting in haemostasis and accelerates wound healing<a class="elsevierStyleCrossRef" href="#bib0160"><span class="elsevierStyleSup">32</span></a><span class="elsevierStyleSup">&#44;</span><a class="elsevierStyleCrossRef" href="#bib0165"><span class="elsevierStyleSup">33</span></a>&#46; Alginates fibers were reinforced by introduction of hydrolysed chitosans &#40;which diffuse into the alginate fiber&#41; allowing to introduce antibacterial properties<a class="elsevierStyleCrossRef" href="#bib0170"><span class="elsevierStyleSup">34</span></a>&#46;</p></span></span><span id="sec0050" class="elsevierStyleSection elsevierViewall"><span class="elsevierStyleSectionTitle" id="sect0070">Conclusion</span><p id="par0085" class="elsevierStylePara elsevierViewall">From this short review&#44; it seems clear that alginates are new industrial polysaccharides which may be used in many other applications than only food industry&#46; Nevertheless&#44; biomedical and pharmaceutical applications of purified alginates seem certainely the most promising development of alginates at present time&#46; At end&#44; it is important to mention the recent synthesis of well defined new biohybrid glycopolymers having guluronic oligomers grafted on a hydrophilic backbone giving also gels in the presence of calcium counterions&#46; For many applications&#44; these copolymers may compete directly with alginates<a class="elsevierStyleCrossRef" href="#bib0175"><span class="elsevierStyleSup">35</span></a>&#46;</p></span></span>"
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        "resumen" => "<p id="spar0005" class="elsevierStyleSimplePara elsevierViewall">In this short review&#44; our objective was to describe few new applications of a natural polysaccharide extracted from algae&#44; the alginates&#46; Firstly&#44; the chemical composition is recalled and the main techniques used for characterization are cited&#46; The role of guluronic acid blocks &#40;GG blocks&#41; is particularly important for gel mechanical properties in presence of calcium counterions&#46; Then&#44; the main applications in food and biomedicine are briefly mentioned followed by tentative applications in packaging&#44; paper&#44; textil and wound dressing which are described&#46; Especially&#44; fine fibers are produced now industrially under mixed sodium&#47;calcium ionic form&#46;</p>"
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        "resumen" => "<p id="spar0010" class="elsevierStyleSimplePara elsevierViewall">En esta corta revisi&#243;n&#44; nuestro objetivo fue describir algunas nuevas aplicaciones de un polisac&#225;rido natural extra&#237;do de algas&#58; el alginato&#46; Primeramente&#44; la composici&#243;n qu&#237;mica es revisada&#44; adem&#225;s de citar las principales t&#233;cnicas utilizadas para su caracterizaci&#243;n&#46; El papel de los bloques de &#225;cido gulur&#243;nico &#40;bloques GG&#41; es particularmente importante para las propiedades mec&#225;nicas del gel en presencia de Ca como contrai&#243;n&#46; Despu&#233;s&#44; se mencionan brevemente las principales aplicaciones en el &#225;rea de alimentos y biomedicina&#44; seguida de aplicaciones experimentales en embalaje&#44; papel&#44; textiles&#44; y vendajes de heridas&#44; las cuales son descritas&#46; Especialmente&#44; fibras finas de alginato son ahora producidas industrialmente en una forma i&#243;nica mixta de sodio&#47;calcio&#46;</p>"
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