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Reviewing Chitin/Chitosan Nanofibers and Associated Nanocomposites

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Reviewing Chitin/Chitosan Nanofibers and Associated Nanocomposites polymers Review Reviewing Chitin/Chitosan Nanofibers and Associated Nanocomposites and Their Attained Medical Milestones Iyyakkannu Sivanesan 1 , Judy Gopal 2 , Manikandan Muthu 2, Juhyun Shin 3 and Jae-Wook Oh 3,* 1 Department of Bioresources and Food Science, Konkuk University, Seoul 143-701, Korea; [email protected] 2 Laboratory of Neo Natural Farming, Chunnampet 603 401, Tamil Nadu, India; [email protected] (J.G.); [email protected] (M.M.) 3 Department of Stem Cell and Regenerative Biotechnology, Konkuk University, Seoul 143-701, Korea; [email protected] * Correspondence: [email protected]; Tel.: +82-2-2049-6271; Fax: +82-2-455-1044 Abstract: Chitin/chitosan research is an expanding field with wide scope within polymer research. This topic is highly inviting as chitin/chitosan’s are natural biopolymers that can be recovered from food waste and hold high potentials for medical applications. This review gives a brief overview of the chitin/chitosan based nanomaterials, their preparation methods and their biomedical applications. Chitin nanofibers and Chitosan nanofibers have been reviewed, their fabrication methods presented and their biomedical applications summarized. The chitin/chitosan based nanocomposites have also been discussed. Chitin and chitosan nanofibers and their binary and ternary composites are represented by scattered superficial reports. Delving deep into synergistic approaches, bringing up novel chitin/chitosan nanocomposites, could help diligently deliver medical expectations. This review highlights such lacunae and further lapses in chitin related inputs towards Citation: Sivanesan, I.; Gopal, J.; medical applications. The grey areas and future outlook for aligning chitin/chitosan nanofiber Muthu, M.; Shin, J.; Oh, J.-W. Reviewing Chitin/Chitosan Nanofibers research are outlined as research directions for the future. and Associated Nanocomposites and Their Attained Medical Milestones. Keywords: chitosan nanoparticles; chitin; nanofibers; nanocomposites; synthesis; medical applications Polymers 2021, 13, 2330. https:// doi.org/10.3390/polym13142330 Academic Editor: 1. Introduction Francesco Boschetto Miniaturization has become the recent state-of-the-art technology, resulting in modify- ing material shapes, surfaces, characteristics, and functions [1]. Nanotechnology leads the Received: 30 June 2021 forefront in the arena of miniaturization strategies. The impressive potential applications Accepted: 12 July 2021 of nanotechnology have transformed this field and opened it for many researchers and Published: 16 July 2021 scientists to work on [2]. Nanotechnology today has expanded into different scientific areas, extending from electronics to industrials to cosmetics [3–5]. Nanotechnology has Publisher’s Note: MDPI stays neutral also strongly impacted core areas of human health and welfare. with regard to jurisdictional claims in Polymers of natural origins have been extensively employed not only in the food published maps and institutional affil- industry but also in pharmaceuticals [6]. Chitin, chitosan, alginate, and carrageenan are iations. the most commonly used polysaccharide polymers in various pharmaceutical applica- tions [7–13] and food quality, safety, and preservation. Polysaccharide polymers are sought after owing to their non-toxicity, biocompatibility, and biodegradability [7,8]. Chitin (Ch) consists of repeated N acetyl-D-glucosamine (GlcNAc) units linked by β-(1,4) glycosidic Copyright: © 2021 by the authors. bonds [14]. Naturally, chitin exists in three crystalline polymorphic forms. Within each Licensee MDPI, Basel, Switzerland. form, there are different orientations of the microfibrils: α-chitin has parallel chains, β- This article is an open access article chitin has antiparallel chains, and γ-chitin has a mixture of parallel and anti-parallel chains distributed under the terms and (Figure1)[ 15]. Figure1 displays the representative organisms for each of these polymorphs. conditions of the Creative Commons Attribution (CC BY) license (https:// creativecommons.org/licenses/by/ 4.0/). Polymers 2021, 13, 2330. https://doi.org/10.3390/polym13142330 https://www.mdpi.com/journal/polymers Polymers 2021, 13, x FOR PEER REVIEW 2 of 18 Polymers 2021, 13, 2330 2 of 17 Figure 1. Schematic representation of the three polymorphs of chitin and their respective source organisms. Chitin is insoluble in water; however, water-soluble chitosan (ChS) has been produced Figure 1. Schematic representationafter a chitin deacetylationof the three polymorphs process. AofChS chitin molecule and their contains respective an source –NH2 organisms.group and two –OH radicals in each glycoside residue. Although chitin is naturally produced at a rate of around 1010Chitin tons per is year, insoluble most chitinin water; is thrown however, away water-soluble as commercial chitosan waste [15 (ChS)]. Chitin has is been disposed pro- ofduced as marine after a shellchitin wastes deacetylation or industrial process. wastes A ChS in the molecule magnitude contains of multiple an –NH tons.2 group ChS, and a polymertwo –OH of radicals interest, in is each used glycoside to deliver residue. different Although therapeutic chitin agents, is naturally increasingly produced known at for a itsrate use of around in pharmaceuticals. 1010 tons per This year, is most attributed chitin tois thrown its biocompatibility, away as commercial ability to waste bind [15]. few organicChitin is compounds,disposed of as susceptibility marine shell towastes enzymatic or industrial hydrolysis, wastes and in intrinsicthe magnitude physiological of mul- activitytiple tons. combined ChS, a polymer with nontoxicity of interest, [16 is– 18us].ed These to deliver properties different make therapeutic ChS amenable agents, to in- a widecreasingly variety known of biomedical for its use applications, in pharmaceuticals. including This drug is attributed delivery to and its targeting, biocompatibility, wound healing,ability to tissuebind few engineering, organic compounds, and similar suscep alliedtibility fields. to Moreover, enzymaticChS hydrolysis, is also knownand intrin- for itssic antimicrobialphysiological properties,activity combined as well with as color nontoxicity stabilization, [16–18]. emulsification, These properties antioxidant make ChS ac- tivities,amenable and to dietarya wide fiber-likevariety of properties,biomedical water-retention, applications, including and fat drug entrapment. delivery Chitosan and tar- hasgeting, attracted wound great healing, attention tissue as engineering, a material forand drug similar delivery allied biomedicalfields. Moreover, applications ChS is asalso a promisingknown for materialits antimicrobial specifically properties, for delivering as well macromolecules as color stabilization, [19–21]. emulsification, Therapeutic agents anti- haveoxidant been activities, incorporated and dietary into such fiber-like polymeric prop matrixerties, towater-retention, protect the biologically and fat entrapment. active com- poundChitosan from has degradation,attracted great promote attention controlled as a material drug for release drug anddelivery improve biomedical absorption applica- and therapeutictions as a promising effect. Miniaturization material specifically of chitosan for delivering has also been macromolecules attempted, with [19–21]. ChS-based Thera- nanomaterialspeutic agents have ranging been from incorporated microparticles into such to NP polymeric composites matrix and to nanofilms, protect the showing biologi- enhanced biomedical properties. cally active compound from degradation, promote controlled drug release and improve A nanofiber (NF) is generally defined as a fiber less than 100 nm diameter and an aspect absorption and therapeutic effect. Miniaturization of chitosan has also been attempted, ratio greater than 100:1 [22,23]. Properties of NFs are distinct from that of microfibers, be- with ChS-based nanomaterials ranging from microparticles to NP composites and nano- cause NFs have a characteristic morphology, an extremely high surface-to-volume ratio [24], films, showing enhanced biomedical properties. and optical [25] and mechanical properties. In addition to these, they are biodegradable, A nanofiber (NF) is generally defined as a fiber less than 100 nm diameter and an biocompatible, renewable, and sustainable [26]. The electro-spinning process is well known aspect ratio greater than 100:1 [22,23]. Properties of NFs are distinct from that of microfi- for producing artificial NFs from a wide range of polymers [27,28]. Owing to its linear bers, because NFs have a characteristic morphology, an extremely high surface-to-volume structure, chitin has high crystallinity and is arranged as NFs; these NFs are embedded in a ratio [24], and optical [25] and mechanical properties. In addition to these, they are biode- protein matrix. Crab and prawn shells also have a complex hierarchical structure consisting gradable, biocompatible, renewable, and sustainable [26]. The electro-spinning process is of NFs [29]. well Inknown this currentfor producing review, artificial we briefly NFs run from through a wide the range existing of polymers Ch and [27,28]. ChS based Owing nano- to material synthesis and their applications. The biomedical applications of Ch and ChS Polymers 2021, 13, 2330 3 of 17 nanofibers have been dealt with elaborately in this review. The future perspective of Ch and ChS NFs is discussed and the reason why Ch NFs are less applied for biomedical applications than ChS NFs speculated. 2. Chitin and Chitosan
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