Antifungal and Antioxidant Properties of Chitosan Polymers Obtained from Nontraditional Polybius henslowii Sources

Chitin was extracted from Polybius henslowii, a swimming crab, captured in large quantities throughout the Portuguese coast by purse seine vessels as bycatch. After standard chitin extraction procedures, water-soluble chitosan products were obtained via two different methods: (1) N-acetylation with the addition of acetic anhydride and (2) a reaction with hydrogen peroxide. The chemical structure and molecular weight of chitosan derivatives, water-soluble chitosan (WSC) and chitooligosaccharides (COS), were confirmed by Fourier Transform Infrared Spectroscopy (FT-IR) and gel permeation chromatography (GPC). Antioxidant and metal chelation activities were evaluated, and the growth inhibition capacity was tested on four phytopatogens. The chitooligosaccharides from pereopods (pCOS) and shell body parts (sCOS) inhibited all fungal species tested, particularly Cryphonectria parasitica with 84.7% and 85.5%, respectively. Both radical scavenging and antifungal activities proved to be dose-dependent. Chitooligosaccharides with a low molecular weight (2.7, 7.4, and 10.4 Kg·mol−1) showed the highest activity among all properties tested. These results suggested that chitosan derivatives from P. henslowii raw material could potentially be used against phytopathogens or as ingredient in cosmetics and other products related to oxidative stress.

[1]  R. A. Krzeczkowski,et al.  ALASKA KING CRAB: FATTY ACID COMPOSITION, CAROTENOID INDEX AND PROXIMATE ANALYSIS , 1971 .

[2]  M. Johnson.  Variable sensitivity in the microbiuret assay of protein. , 1978, Analytical biochemistry.

[3]  M. Elsabee,et al.  Extraction and characterization of chitin and chitosan from marine sources in Arabian Gulf , 2009 .

[4]  S. Kiatkamjornwong,et al.  Surface-quaternized chitosan particles as an alternative and effective organic antibacterial material. , 2012, Colloids and surfaces. B, Biointerfaces.

[5]  J. Ryland,et al.  Handbook of the marine fauna of north-west Europe , 2017 .

[6]  O. Aruoma,et al.  The characterization of antioxidants. , 1995, Food and chemical toxicology : an international journal published for the British Industrial Biological Research Association.

[7]  H. No,et al.  Preparation and Characterization of Chitin and Chitosan—A Review , 1995 .

[8]  Pengcheng Li,et al.  Antifungal properties of Schiff bases of chitosan, N-substituted chitosan and quaternized chitosan. , 2007, Carbohydrate research.

[9]  F. Velasco,et al.  Deep sea megafaunal assemblages off the northern Iberian slope related to environmental factors , 2011 .

[10]  P. Opanasopit,et al.  In Vitro Antioxidant Activity of Chitosan Aqueous Solution: Effect of Salt Form , 2012 .

[11]  Se-kwon Kim,et al.  Reactive oxygen species scavenging activity of aminoderivatized chitosan with different degree of deacetylation. , 2006, Bioorganic & medicinal chemistry.

[12]  Geoffrey Daniel,et al.  Effect of chitosan on physiological, morphological, and ultrastructural characteristics of wood-degrading fungi , 2008 .

[13]  Joan-Hwa Yang,et al.  Physicochemical characterization of chitin and chitosan from crab shells. , 2009 .

[14]  Y. Jeon,et al.  Antimicrobial effect of chitooligosaccharides produced by bioreactor , 2001 .

[15]  T. Richardson,et al.  Photogeneration of Superoxide Anion in Serum of Bovine Milk and in Model Systems Containing Riboflavin and Amino Acids , 1978 .

[16]  V. Venugopal.  Marine Polysaccharides: Food Applications , 2011 .

[17]  F. Shahidi,et al.  Compositional characteristics of green crab (Carcinus maenas) , 2004 .

[18]  D. Nuss.  Biological control of chestnut blight: an example of virus-mediated attenuation of fungal pathogenesis , 1992 .

[19]  O. Blokhina,et al.  Antioxidants, oxidative damage and oxygen deprivation stress: a review. , 2003, Annals of botany.

[20]  V. Tikhonov,et al.  Metal-chelating chitin derivatives via reaction of chitosan with nitrilotriacetic acid , 1996 .

[21]  M. Goosen,et al.  Antibacterial activity of chitin, chitosan and its oligomers prepared from shrimp shell waste , 2012 .

[22]  R. Thomas,et al.  Antioxidative activity of chitosans with varying molecular weights , 2007 .

[23]  M. Elsabee,et al.  Extraction and characterization of chitin and chitosan from local sources. , 2008, Bioresource technology.

[24]  K. Yao,et al.  Preparation of water-soluble chitosan , 2004 .

[25]  K. Shimada,et al.  Antioxidative properties of xanthan on the autoxidation of soybean oil in cyclodextrin emulsion , 1992 .

[26]  K. Kurita,et al.  Chitin and Chitosan: Functional Biopolymers from Marine Crustaceans , 2006, Marine Biotechnology.

[27]  M. Nishikimi,et al.  Oxidation of ascorbic acid with superoxide anion generated by the xanthine-xanthine oxidase system. , 1975, Biochemical and biophysical research communications.

[28]  J. Arul,et al.  Antifungal Activity of Chitosan on Two Postharvest Pathogens of Strawberry Fruits , 1992 .

[29]  Pengcheng Li,et al.  Relevance of molecular weight of chitosan and its derivatives and their antioxidant activities in vitro. , 2005, Bioorganic & medicinal chemistry.

[30]  J. Kennedy,et al.  Enhancement of antioxidant activity of chitosan by irradiation , 2008 .

[31]  K. Hu,et al.  Study of the depolymerization behavior of chitosan by hydrogen peroxide , 2004 .

[32]  Yong Xu,et al.  Effects of chitosan on control of postharvest diseases and physiological responses of tomato fruit , 2007 .

[33]  J. Smilanick,et al.  Influence of sulfur dioxide fumigant dose on residues and control of postharvest decay of grapes. , 1990 .

[34]  L. Dahlin,et al.  Chitosan tubes of varying degrees of acetylation for bridging peripheral nerve defects. , 2013, Biomaterials.

[35]  M. Garcia-Vaquero.  Food applications , 2021, Microalgae.

[36]  Ming Kong,et al.  Antimicrobial properties of chitosan and mode of action: a state of the art review. , 2010, International journal of food microbiology.

[37]  A. Domard,et al.  Towards a modular synthesis of well-defined chitooligosaccharides: synthesis of the four chitodisaccharides. , 2010, Carbohydrate research.

[38]  W. Prinyawiwatkul,et al.  Physicochemical and functional properties of chitosans prepared from shells of crabs harvested in three different years , 2009 .

[39]  C. Chou,et al.  Antioxidative activities of water-soluble disaccharide chitosan derivatives , 2004 .

[40]  P. Xu,et al.  Antioxidant activity of water-soluble chitosan derivatives. , 2001, Bioorganic & medicinal chemistry letters.

[41]  F. Iemma,et al.  Antioxidant Polymers: Synthesis, Properties, and Applications , 2012 .

[42]  Chitosan,et al.  Chitin and chitosan : sources, chemistry, biochemistry, physical properties, and applications , 1989 .

[43]  Joan-Hwa Yang,et al.  Antioxidant properties of chitosan from crab shells , 2008 .

[44]  Nalan Gökoðlu,et al.  Determinaton of proximate composition and mineral contents of blue crab (Callinectes sapidus) and swim crab (Portunus pelagicus) caught off the Gulf of Antalya , 2003 .

[45]  M. N. R. Kumar.  A review of chitin and chitosan applications , 2000 .

[46]  Anne S. Meyer,et al.  Application of enzymes as food antioxidants , 1995 .

[47]  J. Filipović,et al.  Sorption of zinc by novel pH-sensitive hydrogels based on chitosan, itaconic acid and methacrylic acid. , 2011, Journal of hazardous materials.

[48]  G. Bauer,et al.  Reactive Molecule Species and Antioxidative Mechanisms in Normal Skin and Skin Aging , 2014, Skin Pharmacology and Physiology.

[49]  Yumin Yang,et al.  Radical scavenging activity of chitooligosaccharide with different molecular weights , 2006 .

[50]  N Ito,et al.  Studies on antioxidants: their carcinogenic and modifying effects on chemical carcinogenesis. , 1986, Food and chemical toxicology : an international journal published for the British Industrial Biological Research Association.

[51]  Yimin Qin.  The chelating properties of chitosan fibers , 1993 .

[52]  J. Ryland,et al.  Handbook of the Marine Fauna of , 1995 .

[53]  C. Cerdá,et al.  Oxidative stress and DNA damage in obesity-related tumorigenesis. , 2014, Advances in experimental medicine and biology.

[54]  A. Golshani,et al.  Disruption of protein synthesis as antifungal mode of action by chitosan. , 2013, International journal of food microbiology.

[55]  Eric A. Decker,et al.  Role of ferritin as a lipid oxidation catalyst in muscle food , 1990 .

[56]  Haliza Katas,et al.  Antifungal Activity of Chitosan Nanoparticles and Correlation with Their Physical Properties , 2012, International journal of biomaterials.

[57]  M. Childs,et al.  Shellfish: proximate composition, minerals, fatty acids, and sterols. , 1990, Journal of the American Dietetic Association.

[58]  R. Z. Alvarez.  Crustáceos decápodos ibéricos , 1968 .

[59]  Manuela Pintado,et al.  Valorisation of natural extracts from marine source focused on marine by-products: A review , 2010 .

[60]  Joydeep Dutta,et al.  Perspectives for chitosan based antimicrobial films in food applications , 2009 .

[61]  J. Terao,et al.  HPLC method for evaluation of the free radical-scavenging activity of foods by using 1,1-diphenyl-2-picrylhydrazyl. , 1998, Bioscience, biotechnology, and biochemistry.

[62]  Krzysztof,et al.  INTERNATIONAL ORGANISATION FOR STANDARDISATION , 2006 .

[63]  F. Sheu,et al.  Effect of molecular weight of chitosans on their antioxidative activities in apple juice , 2007 .

[64]  F. Maynou,et al.  Feeding guilds of western Mediterranean demersal fish and crustaceans: an analysis based in a spring survey , 2002 .

[65]  H. No,et al.  Antibacterial activity of chitosans and chitosan oligomers with different molecular weights. , 2002, International journal of food microbiology.

[66]  Bao Yang,et al.  Preparation of water-soluble chitosan from shrimp shell and its antibacterial activity , 2009 .

[67]  A. Ghaly,et al.  Unconventional Approach for Demineralization of Deproteinized Crustacean Shells for Chitin Production , 2007 .

[68]  J. Desbrières,et al.  An infrared investigation in relation with chitin and chitosan characterization , 2001 .

[69]  F. Sánchez,et al.  Trophic ecology of the swimming crab Polybius henslowii Leach, 1820 in Galician and Cantabrian Seas : Influences of natural variability and the Prestige oil spill , 2008 .

[70]  S. Droby,et al.  Post-Harvest Botrytis Infection: Etiology, Development and Management , 2007 .

[71]  S. Kiatkamjornwong,et al.  Enhancing antibacterial activity of chitosan surface by heterogeneous quaternization , 2011 .

[72]  M. El-kalyoubi,et al.  Physicochemical, functional, antioxidant and antibacterial properties of chitosan extracted from shrimp wastes by microwave technique , 2013 .