chitosan research

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Published: 26 September 2022

Chitin and chitosan derived from crustacean waste valorization streams can support food systems and the UN Sustainable Development Goals

Hamid Amiri ORCID: orcid.org/0000-0003-3891-6471 1 , 2 ,
Mortaza Aghbashlo 3 ,
Minaxi Sharma ORCID: orcid.org/0000-0001-6493-5217 4 ,
James Gaffey 5 , 6 ,
Louise Manning ORCID: orcid.org/0000-0001-9368-9588 7 ,
Seyed Masoud Moosavi Basri 8 ,
John F. Kennedy 9 ,
Vijai Kumar Gupta ORCID: orcid.org/0000-0003-1565-5918 10 , 11 &
Meisam Tabatabaei 12

Nature Food volume 3 , pages 822–828 ( 2022 ) Cite this article

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Crustacean waste, consisting of shells and other inedible fractions, represents an underutilized source of chitin. Here, we explore developments in the field of crustacean-waste-derived chitin and chitosan extraction and utilization, evaluating emerging food systems and biotechnological applications associated with this globally abundant waste stream. We consider how improving the efficiency and selectivity of chitin separation from wastes, redesigning its chemical structure to improve biotechnology-derived chitosan, converting it into value-added chemicals, and developing new applications for chitin (such as the fabrication of advanced nanomaterials used in fully biobased electric devices) can contribute towards the United Nations Sustainable Development Goals. Finally, we consider how gaps in the research could be filled and future opportunities could be developed to make optimal use of this important waste stream for food systems and beyond.

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Towards the scalable isolation of cellulose nanocrystals from tunicates

Since 2015, the United Nations Sustainable Development Goals (SDGs) have been key policy drivers for supporting sustainable seafood systems 1 . In the same year, Yan and Chen highlighted the untapped benefits of crustacean waste as a reserve of chitin (15–40%), protein and minerals, calling for a multi-million-dollar investment to establish the first shell refinery processing pipeline 2 .

With a 2–3% annual growth rate, the yearly global level of crustacean production reached 13.7 million metric tonnes (mmt) in 2015 (Fig. 1 ), resulting in 6–8 mmt of lobster, crab and shrimp wastes 1 . Five years later, crustacean production had increased to an annual rate of 16.6 mmt, with most growth seen in Asian countries (especially China, Indonesia and India, with over a 2 mmt increase) (Fig. 1 ). Crustaceans contain approximately 40% meat, with the remaining 60% being inedible, raising questions within the industry about the scale of crustacean waste accumulation. However, crustacean waste contains chitin, a biocompatible and biodegradable polymer covered by protein and minerals that is invaluable for producing high-tech products such as nerve conduits (for example, Reaxon, manufactured by Medovent).

The production of shrimps and prawns (dark blue), freshwater crustaceans (light blue), and crabs and sea-spiders (orange) in Africa (blue), America (brown), Europe (green), Australia and Oceania (light blue), and Asia (red) in 2015 (left) and 2019 (right). The data were obtained from the Fishery Statistical Collections, Food and Agriculture Organization of the United Nations ( https://www.fao.org/fishery/statistics/global-production ).

Reproducible chemical conversion processes for obtaining well-defined chitosan with specific functionalities (second-generation chitosan) have been developed since the 1970s 3 . Between 2000 and 2015, European grants of nearly €15 million went towards projects exploring chitin- and chitosan-related topics 4 , 5 , with grant values increasing after 2015, eventually reaching €55 million (Fig. 2 ). Topics included chitin extraction within the efficiency borders for high-value production, environmental impacts, economic feasibility and developing a microbial-enzymatic process for converting chitin into glucosamine and N -acetylglucosamine. The ChiBio consortium (with a grant of nearly €4 million), comprising academic and industrial experts, developed a microbial-enzymatic process starting from a two-stage fermentation by Serratia marcescens and Lactobacillus plantarum for demineralization and deproteination followed by enzymatic depolymerization of chitin into basic building blocks—that is, glucosamine and N -acetylglucosamine 6 . In more recent years, protein engineering based on bioinformatics, genome mining, rational design and molecular evaluation has become more prominent in chitosan research, with a move towards a multilevel circular value chain for the eco-efficient valorization of aquaculture and fishery wastes (the Nano3Bio project, with a grant of nearly €12 million) 7 . In 2021, a €19 million project was launched by Italian academics and industrialists to develop a multilevel circular value chain for the eco-efficient valorization of aquaculture wastes within the subsequent five years 8 .

a , The global landscape of chitin- and chitosan-based publications (Scopus database) (right y axis) and research grants (CORDIS, European Commission and US National Science Foundation) (left y axis). b , European Patent Office (EU) and United States Patent and Trademark Office (US) patents. The green shading represents the five-year period predicted by Yan and Chen 2 to witness a multi-million-dollar investment in the first shell refinery processing pipeline.

Here, we examine why this amount of grant funding should be invested in a waste stream, exploring the most recent developments in eco-friendly and circular utilization of crustacean waste. We also look to the future of chitin within and beyond food systems.

Emerging technologies for crustacean waste valorization

Natural materials are reliable and suitable for use both in the environment and inside the human body, with some exceptions due to their allergenic effects for some individuals 9 . Chitin, a water-insoluble polymer with a higher number of d -glucosamine monomers than N -acetyl- d -glucosamine monomers, and chitosan, a water-soluble polymer with a higher number of N -acetyl- d -glucosamine monomers, are two important polymers derived from crustacean waste. The combination of chitin, proteins and calcite crystals can give tissues superior rigidity, flexibility and transparency 10 . Chitin’s acetylation pattern can be adjusted at the molecular level to optimize its properties for various applications 11 . However, without appropriate extraction technologies, the accumulated crustacean wastes derived from different species may not reflect the intrinsic value that can be derived from their composition 12 . Additionally, crustacean waste may be received from different stages of seafood processing in the form of either raw or cooked waste material, where cooking exerts positive effects on the extraction of chitin and its quality 13 . During the past few decades, the chemical processes commercialized (including deproteinization, demineralization, discoloration and even deacetylation) have provided chemically derived chitosan with known and reproducible properties (second-generation chitosan). Besides the unacceptable environmental footprint of the processes involved 14 , the resulting chitosan fails to meet the requirements of high-tech applications with chitin-based products, as its molecular structure and its properties are not tuned to the needs of high-tech applications 15 .

Alternative technologies include the catalytic conversion of chitin by breaking the chitin polymeric structure during an efficient solid-state reaction into mechanochemical chitosan with a low but narrow-range molecular weight, which could tune its properties 16 . A similar solvent-less process has been developed on the basis of a reactive ageing method consisting of repeating cycles of milling and ageing with chitinase and a small amount of water, leading to mechanoenzymatic chitosan 17 . However, the inherent heterogeneity of waste-derived chitosans in terms of the degree of acetylation and the acetylation pattern still considerably limits its use in highly sophisticated applications, which might instead be addressed by using a recombinant fungal chitin decarboxylase 18 .

To address these challenges, a biotechnological solution is presented in the Nano3Bio project, granted by the European Union 7 . The natural chitin was enzymatically degraded into its building blocks ( N -acetylglucosamine and glucosamine), which were used to reconstruct a customized biotechnology-derived chitosan structure with an engineered microbial cell. The cell was developed using either Escherichia coli or Corynebacterium glutamicum as the host 7 . Nanotechnology-based bottom-up approaches can turn the chitin–chitosan structure into chitosan nanocomposites, where the properties of the heterogenic chitosan can then be tuned. Chitosan nanocomposites engineered by adding starch and lignin to chitosan and adjusting their concentrations were successfully utilized as triboelectric nanogenerators for self-powered nanosystems in biomedical and environmental applications 19 . A hydrophobization-induced interfacial-assembly approach has been developed for converting marine chitin into two-dimensional soft nanomaterials for their application as fully biobased electric devices 20 . The ethoxylation of chitin followed by deacetylation produced glycol chitosan with improved water solubility at a wide pH range while maintaining chitosan’s amine groups. These amine groups facilitated the introduction of various hydrophobic moieties, including positively charged nanoparticles (through self-assembly) or targeting moieties with high affinity for cancer-specific receptors, offering promising applications for drug delivery and as nanomedicine for tumour cells, respectively 21 .

The potential of crustacean waste

Economic potentials.

In early research, crustacean shells were utilized whole and without fractionating their ingredients, primarily for environmental remediation purposes. Between 2003 and 2008, JRW Bioremediation LLC was assigned a patent family to utilize the crustacean shell as an electron donor to eliminate contaminants in groundwater 22 , 23 and mine-influenced water 23 .

The shift from first-generation chitosan (that is, a poorly defined blend of chitosans with large batch-to-batch variations) to second-generation chitosan provided important opportunities for crustacean wastes in commodity markets such as agrochemicals (>US$60 billion market value 24 ) and water treatment agents (>US$30 billion market value 25 ). Chitosan is a natural antimicrobial polycation used in pesticide formulations (for example, as an encapsulating agent 26 ), ending up as soil-enriching derivatives through natural biodegradation. In August 2019, the US Environmental Protection Agency published a scientific analysis supporting the addition of chitosan to the list of minimum-risk ingredients of pesticides 27 , promoting chitosan-based pesticides and broadening their opportunities in the agricultural market. As a polycation, chitosan can be utilized to formulate chitosan–lignosulfonates as a biocide enhancer 28 . Moreover, the chelating properties of chitosan make it a potential biodegradable coagulant/flocculant to be used in wastewater treatment processes instead of metallic salts and synthetic polyelectrolytes 29 , with environmental benefits such as non-toxicity, biodegradability and ecological acceptability 29 . Agratech International Inc. also utilized/valorized and patented the hydrophobic potential of chitosan in developing chitosan-coated hydrophobic glass 30 , 31 .

Originating from the food processing chain, crustacean wastes have high potential to be utilized as food packaging films or fruit preservatives, as well as food additives and dietary supplements. Owing to its film-forming properties, chitosan was first suggested as a biocompatible, biodegradable and non-toxic raw material for food packaging. However, due to the poor mechanical and UV protection properties of chitosan, chitin in the form of nanocrystals or nanofibres has taken center stage as a biocompatible food packaging raw material 4 . Supplementing chitin nanostructures with sensitive additives such as konjac glucomannan 32 or curcuma oil 33 could play an important role in the future of “smart food packaging films” 34 . Chitosan is a potential edible preservative coating for fruit and vegetables owing to its antimicrobial properties. However, its application should be limited because of the health side effects when included in daily diets 35 , 36 .

The use of chitosan as a dietary supplement for bodyweight reduction is the most important human exposure to chitosan. In 2005, the US Food and Drug Administration (GRN 170) noted that “chitosan was non-toxic to humans and other test animals”, but using chitosan as a regular diet ingredient is questionable due to the doubt on “whether or not chitosan would interfere with fat-soluble vitamin and mineral status in humans, when the substance was consumed on a chronic basis as part of a general diet” 35 . In 2017, a six-month feeding study conducted by the US National Toxicology Program revealed that the lowest observed effect level for chitosan exposure is 1% (approximately equivalent to 450 mg kg −1 or 31.5 g d −1 for a 70 kg individual) in males and 9% (approximately equivalent to 6,000 mg kg −1 ) in females 36 . With the Food and Drug Administration’s approval and the relatively high lowest observed effect level, chitosan has great potential to be used in dietary supplements (with a market value of >US$220 billion 37 ).

The biotechnologically derived chitosan termed as ‘third-generation’ may pave the way for high-tech applications of chitosan, mostly in biomedical engineering (with an approximate market value of US$250 billion 38 ) and tissue engineering. For example, bridging peripheral nerve defects (an issue for around 300,000 people per year in Europe) could be achieved with engineered chitosan with a degree of acetylation of 5% 39 . Nanotechnology-derived chitosan and derivatives also promise highly sophisticated biomedical and environmental applications such as self-powered nanosystems 19 , fully biobased electric devices 20 and tumour-targeting nanoparticles 21 (Fig. 3 ).

a – d , (1) The outmost layer represents first-generation chitin–chitosan, also referred to as un- or less-processed chitin–chitosan. (2) The second layer represents the applications of second-generation chitosan, including in water treatment (as a bioflocculating agent) ( a ), agriculture (as a biofertilizer and biopesticide) ( b ), biodegradable packaging ( c ) and the textile industry ( d ). e – h , (3) Two layers are designated by 3, representing the applications of third-generation chitosan. The outer 3 illustrates the applications of biotechnologically derived chitosan, including in composites for nerve conduits ( e ), haemostatic dressings ( f ) and wound gauzes ( g ). The inner 3 represents the applications of nanotechnology-derived chitosan, including laser‐processed chitosan for triboelectric power generation and two-dimensional soft nanomaterials for fully biobased electric devices ( h ), and tumour-targeting glycol chitosan nanoparticles for drug delivery (cancer nanomedicine) ( i ). The innermost circle presents the structure of chitin–protein fibrils and represents the future potentials for more advanced generations of chitosan and their applications.

SDG realization

Farmed crustaceans account for nearly 10% of aquaculture production by volume and over 24% by value globally 40 , generating 8 mmt of waste annually. Emerging technologies for the valorization of crustacean wastes could therefore align well with the ambitions of SDG-12 (responsible consumption and production) and several targets categorized within different goals, including SDG-2 (food security, improved nutrition and promotion of sustainable agriculture), targets 2.2, 2.3 and 2.4; SDG-3 (good health and well-being), targets 3.1, 3.2, 3.3 and 3.9 (crustacean-waste-based medical and pharmaceutical products); SDG-6 (crustacean-waste-based flocculating agents for clean water and wastewater treatment); SDG-7 (sustainable energy), targets 7.2 and 7.b (crustacean waste as energy resources for small island developing states); SDG-11 (sustainable cities and communities), target 11.6 (crustacean-waste-based preservatives, coagulation agents and dietary supplements); SDG-13 (climate action—crustacean-waste-based agrochemicals and fertilizers), target 13.1; SDG-14 (life below water), target 14.3 (crustacean-waste-based marine oil spill treatment agents); and SDG-15, target 15.3 (life on earth—crustacean-waste-based biostimulants, biofungicides and biopesticides).

Although several chitosan-based medical products are commercially available (such as hydrogels and wound-healing bandages), more products are expected soon, contributing to the development of safer technologies to achieve good health and well-being (SDG-3). Chitosan-covered gauze can be used as an inexpensive uterine packing material for more effective control of postpartum haemorrhage through reducing the risk of infection 41 , directly contributing to the realization of target 3.1 (“reduce the global maternal mortality ratio”). Chitosan oligosaccharides have been investigated in trials using rats for their neuroprotective effects on hypoxic–ischemic brain damage, a major cause of newborn morbidity and mortality in recent years 42 . Extending these findings to develop new products is expected to contribute to the realization of target 3.2 (“end preventable deaths of newborns”). Furthermore, the immunostimulatory properties of chitosan reported since the 1980s 43 , along with its ability to efficiently penetrate through mucosal surfaces, have been applied in vaccine delivery nanoparticles against infection with hepatitis B 44 and SARS-CoV‑2 45 . Developing chitosan-based vaccines with improved immunization against communicable diseases directly contributes to the realization of target 3.3 (“end the epidemics of AIDS, tuberculosis, malaria and neglected tropical diseases and combat hepatitis, water-borne diseases and other communicable diseases”) 46 . Iron-loaded chitosan pectin microparticles have recently been suggested as an iron delivery system, where chitosan as a cationic structure in conjunction with pectin as an anionic counterpart forms a unique polyelectrolyte complex for efficient iron delivery 47 . Such evidence marks the high potential of chitosan to play key roles in the future of iron delivery and food supplementation systems, addressing the ambition of target 2.2 (addressing global nutrition gaps).

As a nitrogen-containing renewable organic resource with over 10 5 mmt of annual production in the aquatic biosphere, chitin has great potential to be used as eco-friendly fertilizer to partially replace ammonia produced by the Haber–Bosch process (150 mmt per year) 48 . Chitin-derived nitrogen-containing platform chemicals, especially 3-acetamido-5-acetylfuran, have great potential for addressing SDG-13. Besides nitrogen fixation, the catalytic conversion of crustacean shells into some platform chemicals such as levulinic acid 49 , acetic acid and pyrrole 50 could be a sustainable route for reducing the carbon footprints of commodity products. Chitosan is also an advantageous biopolymer for controlled-release formulations for agricultural purposes, especially in the case of pest control. The electrostatic interaction of the amine groups of chitosan with other polymers provides the possibility of obtaining stable hydrogel beads for controlled-release formulations of pesticides, such as pH-responsive chitosan-modified cenosphere/alginate composite hydrogel encapsulating Imidacloprid 51 , an important role played by chitosan in realizing SDG-2 (zero hunger) environmental target 2.4.

About one third of the current global chitosan market is devoted to its application in water and wastewater treatment. Chitosan-based flocculants are commercially available, but chitosan-based adsorbents for water treatment (especially for removing micropollutants) are still under development. Owing to their hydroxyl, amine and amide functional groups, chitin and chitosan are efficient adsorbents for heavy metals and organic micropollutants 52 . In this context, chitosan has been evaluated in the forms of wet chitosan microspheres with immobilized laccase 53 , cross-linked chitosan/zeolite 54 , trifunctional chitosan-EDTA-β-cyclodextrin polymer 55 and ethylene diamine tetra acetic acid-functionalized β-cyclodextrin-chitosan 56 . The challenge of cost-effective removal of a wide range of micropollutants may therefore be addressed by developing specific chitin- or chitosan-based adsorbents, which would be in line with the ambitions of SDG-6.

Chitin’s potential

Future research is required to expand the role of chitin in achieving the SDGs. The environmental impacts of the large-scale utilization of crustacean waste for bulk products, especially packaging and agrochemical materials, can be quantified on the basis of its effects on carbon and nitrogen cycles. Chemically derived chitin or chitosan (second-generation) is still the only commercially available source used in bulk products 57 . The industrial bottlenecks of using waste-derived chitin nanocrystals, known as chitin-nanofibrils, for producing food packaging have been assessed in a European Union project (the n-CHITOPACK project was funded for approximately €1 million), which reported that replacing non-renewable materials used in food packaging with chitin-based films could lead to a 12 mmt CO 2 emission reduction per year 4 . Such a reduction can satisfy nearly 2% of the decarbonization rate (0.6 Gt CO 2 yr −1 ) required to achieve the ambitious mitigation scenario that would limit 2100 warming to 1.5 °C (RCP 2.6—2017 scenario) 58 . Chitin has the potential to provide a nitrogen-containing agrochemical that can be used instead of petrochemically derived ammonia to address concerns about the effects of fossil-fuel-derived ammonia on global nitrogen cycles. Crustacean waste with an annual production rate of 8 mmt could provide about 0.7 mmt of nitrogen that could replace 0.85 mmt of ammonia, nearly 0.5% of the global ammonia demand. Nevertheless, its role in reducing carbon and nitrogen footprints does not represent the totality of chitin’s beneficial sustainable value or its sustainable impact, especially when economic, environmental and social (health) issues are considered together.

While allergenicity concerns would need to be addressed, the shift from polypropylene- to chitin-based films in the food packaging industry would exert a positive effect on the ‘carcinogens’ impact category, even with the current ‘non-environmentally-optimized’ extraction methods 59 . The carcinogenic impacts of chitin-based films (defined as the annual number of deaths caused by the substance) are stated as being 72% lower than those of polypropylene films 59 . Moreover, a considerable amount of toxic pesticides, 1,000 times the amount reaching target pests, are currently released into the ecosystem, threatening human health on a global scale 60 , which could be largely prevented through commercializing chitosan-based formulations to enhance the targeted and controlled release of pesticides.

Conclusions and future directions

It has been predicted that global seafood consumption will increase during the next 30 years by 36–74% 61 . Despite there being eight years remaining to address the SDGs, only 15% of the intended progress has been made on target 12.3 regarding food loss and waste 62 . Given the levels of research funding highlighted in this paper, crustacean waste valorization should see accelerated progression in the near future.

Current technologies for chitosan production suffer from delivering a lack of quality in terms of achievable purity and reproducibility, sustainability issues through emitting heavy pollution during the production process, or high production and storage costs. The biological properties of extracted chitin and its derivatives already form important components of advanced biomaterials. This area merits further investments in developing technologies based on protein engineering and cell factories to harness the full potential of this waste stream. The production of third-generation chitin or chitosan polymers may address these challenges in the future. The ambition of producing a homogeneous and application-specific chitosan structure with a predetermined acetylation pattern could pave the way for the highly sophisticated use of chitosan, particularly as a biodegradable cationic polyelectrolyte in advanced biomaterials. Knowledge creation on the relationships between the acetylation pattern and different properties of chitosan at the molecular level is thus an important aspect for future studies in the field.

If industry and public awareness were increased, the demand for chitin-derived products such as smart food packaging materials would expand, acting as a driver for technological developments in crustacean waste valorization. However, life sciences researchers need to explore mitigation options for products of animal origin and address challenges such as allergenic or viral contaminations of waste-derived chitosan. Without these advances, the ability to fabricate highly sophisticated biomaterials for special applications in the pharmaceutical and medical industries will be limited.

It is time to reimagine the value of crustacean-waste-based products to support future food systems through shell biorefineries, not only from an economic resilience perspective but also to mitigate sustainability and human health concerns. Such attention will ensure that this important food system waste product can become a resource that is utilized in line with the ambitions of the United Nations SDGs.

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Acknowledgements

This work was supported by the Ministry of Higher Education, Malaysia, under the Higher Institution Centre of Excellence (HICoE), Institute of Tropical Aquaculture and Fisheries (AKUATROP) programme (vot. no. 56052, UMT/CRIM/2-2/5 Jilid 2 (11)). V.K.G. acknowledges the institutional research funding supported by Scotland’s Rural College (SRUC). M.T. and V.K.G. acknowledge that this work has been done under the umbrella of the MoU between Scotland’s Rural College and Universiti Malaysia Terengganu.

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H.A. conceptualized the project, analysed the data and wrote the original draft. M.S., L.M. and J.F.K. analysed the data and reviewed and edited the original draft. J.G. collected and analysed the industrial data. S.M.M.B. studied the applications of chitosan and developed the illustrations. M.A., V.K.G. and M.T. contributed to this work throughout its conceptualization, including obtaining resources and funding, supervision, writing and editing.

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Amiri, H., Aghbashlo, M., Sharma, M. et al. Chitin and chitosan derived from crustacean waste valorization streams can support food systems and the UN Sustainable Development Goals. Nat Food 3 , 822–828 (2022). https://doi.org/10.1038/s43016-022-00591-y

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Chitosan: Derivatives, Properties and Applications

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Vineet Kumar Rathore 7 &
Jigisha K. Parikh 7

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Chitosan is biomaterial-derived chitin that is found in abundance in nature. It is one of the main constituents in the shells of crustaceans, insect cuticles, mushrooms, and cell walls of fungi and green algae. The method of synthesis and precursors used to play important role in determining major properties of chitosan like molecular weight, viscosity, and solubility in water. Due to its natural origin, it is having a variety of applications in modern health science, food industry, cosmetics industry, water treatment, etc. In the present work, a review of the derivatives, their properties, and applications of chitosan in several areas like health science, food industry, cosmetics, and water treatment has been carried out. In medical science, it is of particular interest due to its biocompatibility and its possible applications in bone and tissue engineering and dentistry. In the food industry, chitosan can be used as a possible supplement for protein-rich food and also as an alternative for plastic-based packing material. In cosmetics, chitosan-based lotions, creams, and other personal care products are gaining popularity due to their excellent moisture-retaining ability and biocompatibility. In the water treatment industry, chitosan is studied by many research groups as an effective bio-coagulant and bio-flocculent to remove various types of contaminants.

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Fundamentals and Applications of Chitosan

Applications of chitosan in food, pharmaceuticals, medicine, cosmetics, agriculture, textiles, pulp and paper, biotechnology, and environmental chemistry

A Comprehensive Review Based on Chitin and Chitosan Composites

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Rathore, V.K., Parikh, J.K. (2022). Chitosan: Derivatives, Properties and Applications. In: Ratan, J.K., Sahu, D., Pandhare, N.N., Bhavanam, A. (eds) Advances in Chemical, Bio and Environmental Engineering. CHEMBIOEN 2021. Environmental Science and Engineering. Springer, Cham. https://doi.org/10.1007/978-3-030-96554-9_50

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Chitin and Chitosan: Production and Application of Versatile Biomedical Nanomaterials

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1 Tabriz Medical University, East Azerbaijan, Tabriz, Iran.
2 Wellman Center for Photomedicine, Massachusetts General Hospital, Boston, Massachusetts, USA; Department of Dermatology, Harvard Medical School, Boston, Massachusetts, USA; Harvard-MIT Division of Health Sciences and Technology, Cambridge, Massachusetts, USA.
PMID: 27819009
PMCID: PMC5094803

Chitin is the most abundant aminopolysaccharide polymer occurring in nature, and is the building material that gives strength to the exoskeletons of crustaceans, insects, and the cell walls of fungi. Through enzymatic or chemical deacetylation, chitin can be converted to its most well-known derivative, chitosan. The main natural sources of chitin are shrimp and crab shells, which are an abundant byproduct of the food-processing industry, that provides large quantities of this biopolymer to be used in biomedical applications. In living chitin-synthesizing organisms, the synthesis and degradation of chitin require strict enzymatic control to maintain homeostasis. Chitin synthase, the pivotal enzyme in the chitin synthesis pathway, uses UDP-N-acetylglucosamine (UDPGlcNAc), produce the chitin polymer, whereas, chitinase enzymes degrade chitin. Bacteria are considered as the major mediators of chitin degradation in nature. Chitin and chitosan, owing to their unique biochemical properties such as biocompatibility, biodegradability, non-toxicity, ability to form films, etc, have found many promising biomedical applications. Nanotechnology has also increasingly applied chitin and chitosan-based materials in its most recent achievements. Chitin and chitosan have been widely employed to fabricate polymer scaffolds. Moreover, the use of chitosan to produce designed-nanocarriers and to enable microencapsulation techniques is under increasing investigation for the delivery of drugs, biologics and vaccines. Each application is likely to require uniquely designed chitosan-based nano/micro-particles with specific dimensions and cargo-release characteristics. The ability to reproducibly manufacture chitosan nano/microparticles that can encapsulate protein cargos with high loading efficiencies remains a challenge. Chitosan can be successfully used in solution, as hydrogels and/or nano/microparticles, and (with different degrees of deacetylation) an endless array of derivatives with customized biochemical properties can be prepared. As a result, chitosan is one of the most well-studied biomaterials. The purpose of this review is to survey the biosynthesis and isolation, and summarize nanotechnology applications of chitin and chitosan ranging from tissue engineering, wound dressings, antimicrobial agents, antiaging cosmetics, and vaccine adjuvants.

Keywords: Chitin; biomedical nanotechnology; chitosan; drug delivery; nanoparticle; synthetic nanofiber; vaccine adjuvant.

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Home > Books > Concepts, Compounds and the Alternatives of Antibacterials

Chitosan as a Biomaterial — Structure, Properties, and Electrospun Nanofibers

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Chitosan is a polysaccharide derived from chitin; chitin is the second most abundant polysaccharide in the world, after cellulose. Chitosan is biocompatible, biodegradable and non-toxic, so that it can be usedin medicalapplications such as antimicrobial and wound healing biomaterials. It also used as chelating agent due to its ability to bind with cholesterol, fats, proteins and metal ions.

Biocompatibility
Biodegradability
Antimicrobial activity
Functionality
Elecrtrospinning

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H. m. ibrahim *.

National Research Center, Textile Research Division, Dokki, Cairo, Egypt

E.M.R. El- Zairy

Faculty of Applied Arts, Printing, Dyeing and Finishing Dept., Helwan Univ., Cairo, Egypt

*Address all correspondence to: [email protected]

1. Introduction

Chitosan is a polysaccharide derived from chitin; chitin is the second most abundant polysaccharide in the world, after cellulose. The presence of amino groups in the chitosan structure might be protonated-providing solubility in diluted acidic aqueous solutions, several remarkable properties of chitosan offered unique opportunities to the development of biomedical applications. The elucidation of their mechanism will lead to a better understanding of chitosan medical and pharmaceutical interest. The haemostatic activity of chitosan can also be related to the presence of positive charges on chitosan backbone. Due to its positive charges, chitosan can also interact with the negative part of cells membrane, which can lead to reorganization and an opening of the tight junction proteins, explaining the permeation enhancing property of this polysaccharide.

The polycationic nature of chitosan also allows explaining chitosan analgesic effects. Now, to explain chitosan biodegradability, it is important to remember that chitosan is not only a polymer bearing amino groups, but also a polysaccharide, which consequently contains breakable glycosidic bonds. Chitosan is actually degraded in vivo by several proteases, and mainly lysozyme.

Chitosan is biocompatible, biodegradable and non-toxic, so that it can be used as medical applications as antimicrobial and wound healing biomaterials. It used as chelating agent due to its ability to bind with cholesterol, fats, proteins and metal ions [ 1 ]

Due to chitosan’s many attractive properties such as biodegradability, natural origin, abundance, reactivity, etc., it has many areas of application including medical, agricultural, food processing, nutritional enhancement, cosmetics, and waste and water treatment.

Chitosan is difficult to electrospun into a fibrous structure because it has a polycationic character in an acidic aqueous solution due to the many amino groups in its backbone. Fibrous structures were successfully formed by electrospinning chitosan solutions in 90 wt. % aqueous acetic acid solution or by using trifluoroacetic acid (TFA) or TFA/dichloromethane (DCM).

Since the electrospinning of chitosan itself proved to be difficult, chitosan was mixed with other synthetic or natural polymers, such as PEO or PVA.

Chitin and chitosan nanofibers with (50-500nm diameter) are biocompatible and biodegradable, so they can used as hemostatic and wound healing materials [ 2 ].

2. Chitosan

Chitosan is a polysaccharide derived from chitin. Its molecular weight is typically between 300-1000 kDa depending on the source of chitin. After cellulose, chitin is the second abounant natural polymer in the world. It is found in crustacean such as shrimps and crab [ 1 , 3 ]

The main Sources of Chitin and Chitosan are : Insects (e.g. Cuticle, Ovipositors and Beetle cocoon), Crustaceans e.g. (Crab shell and Shrimp shell), Squid e.g. ( Ommastrephes pen and Loligo stomach wall), Centric Diatoms e.g. ( Thalassiosira fluviatilis and Algae) and Fungi e.g. ( Mucor rouxi and Aspergillis nidulans) .

Chemical structure of chitin made up of 1-4 linked 2-acetamido-2-deoxy-β-D-glucopyranose ( Figure 1 ).

Chemical structure of chitin [ 4 ].

Although chitin is found naturally in large amounts through many sources, chitosan is only found in nature in limited quantities, such as in some fungi. The chitosan used in industrial or research applications is typically derived from chitin through the use of chemical or enzymatic treatments [ 4 ].

Chitosan is a copolymer of N-acetyl-D-glucose amine and D-glucose amine as shown in figure 2 .It is a linear and semicrystals polymer [ 5 , 6 ] chitosan has de acetylation degree at least 60% of glucose amine residue.(which corresponds to a deacetylation degree of 60). The deacetylation of chitin is conducted by chemical hydrolysis under severe alkaline conditions or by enzymatic hydrolysis in the presence of particular enzymes, among of chitin deacetylase [ 7 , 8 ].

After cellulose, chitin is the second most abundant biopolymer [ 6 ] and is commonly found in invertebrates as crustacean shells or insect cuticles but also in some mushrooms envelopes, green algae cell walls, and yeasts [ 9 - 11 ]. At industrial scale, the two main sources of chitosan are crustaceans and fungal mycelia; the animal source shows however some drawbacks as seasonal, of limited supplies and with product variability which can lead to inconsistent physicochemical characteristics [ 12 ]. The mushroom source offers the advantage of a controlled production environment all year round that insures a better reproducibility of the resulting chitosan [ 13 ], chitosan is safe for both healthcare and biomedical application [ 5 , 14 ]. The mushroom-extracted chitosan typically presents a narrower molecular mass distribution than the chitosan produced from seafood [ 14 ], and may also differ in terms of molecular mass, DD and distribution of deacetylated groups [ 13 , 15 ]. Chitosan DD greatly varies between 60 and 100% while its molecular weight typically ranges from 300 to 1000 kDA [ 16 ], depending on the source and preparation. Chitosan oligomers can be prepared by degradation of chitosan using specific enzyme [ 5 ] or reagent as hydrogen peroxide [ 17 ].

After production, many different tools such as pH-potentiometric titration, IR-spectroscopy, viscosimetry, 1H NMR spectroscopy, UV-spectroscopy, and enzymatic degradation can determine chitosan properties [ 5 , 6 , 18 ].

2.1. The relationship between structure and properties

Chitosan differ from chitin by the presence of amino groups which appears in its solubility in dilute acids (pH < 6), and forming complexes with metal ions so that it can be used for waste water treatment and purification. [ 5 , 6 ]. In contrast, practical applications of chitin are extremely limited due to its poor solubility, if any [ 19 ]. Interestingly, the aqueous solubility of chitosan is pH dependent allowing processability under mild conditions [ 20 ].

Chitosan with protonated amino groups becomes a polycation that can subsequently form ionic complexes with a wide variety of natural or synthetic anionic species [ 20 ], such as lipids, proteins, DNA and some negatively charged synthetic polymers as poly (acrylic acid) [ 19 - 22 ]. As a matter of fact, chitosan is the only positively charged, naturally occurring polysaccharide [ 19 ].

Chitosan molecules have both amino and hydroxyl groups so that it can form stable covalent bonds via several reactions such as etherification, esterification and reductive amination reactions [ 5 , 6 ].

Chitosan have remarkable antibacterial activity [ 5 , 23 , 24 ], along with antifungal [ 11 ], mucoadhesive [ 25 ], analgesic [ 11 ] and haemostatic properties [ 26 ]. It can be biodegraded into non-toxic residues [ 27 , 28 ] the rate of its degradation being highly related to the molecular mass of the polymer and its deacetylation degree – and has proved to some extent biocompatibility with physiological medium [ 29 , 30 ]. All these singular features make chitosan an outstanding candidate for biomedical applications.

Chitosan, deacetylated form of chitin to at least 50% of the free amine form, has a heterogeneous chemical structure made up of both 1-4 linked 2-acetamido-2-deoxy-β-D-glucopyranose as well as 2-amino-2-deoxy-β-D-glucopyranose ( Figure 2 ).

Chemical structure chitosan [ 4 ].

2.2. Chitin and chitosan production

Chitosan produced from crustacean shell such as crab and shrimp. These shells contains 30-40% proteins, 30-50% calcium carbonate and 20-30% chitin (etd.lsu.edu).

Production of chitosan involves four steps: demineralization, (DM), deproteinization (DP), decolorization (DC), and deacetylation (DA), as shown in Figure 3 ( etd.lsu.edu ).

The process for the deacetylation of chitin, obtained from crab or shrimp shells, to form chitosan is described in Figure 5 and generally produces a chitosan with 70% to 95% deacetylation [ 4 ].

Chitosan production flow scheme [ 4 , 31 ].

3. Chitosan as biomaterial

Chitosan have several properties to be used in biomedical applications. It has positive charges in acidic medium, due to protonation of amino groups, and it can bind with negative residues in the mucin, that lead to improve mucoadhesive properties [ 5 , 15 ].

Also positive charges on chitosan can bind to negative charges on red blood cells (RBC) so that chitosan used as haemostatic agent [ 5 , 32 , 33 ].

Chitosan has two mechanisms to explain its antimicrobial activity. The first mechanism proposed that positive charges on chitosan could bind with negative charges at the bacterial cell surface, which alter permeability and leaks solutes outside the cells. The second one proposed that it could bind with bacterial DNA cell, which inhibit RNA synthesis [ 5 ].

The polycationic nature of chitosan also allows explaining chitosan analgesic effects. Indeed, the amino groups of the D-glucosamine residues can protonate in the presence of proton ions that are released in the inflammatory area, resulting in an analgesic effect [ 34 ].

Now, to explain chitosan biodegradability, it is important to remember that chitosan is not only a polymer bearing amino groups, but also a polysaccharide, which consequently contains breakable glycosidic bonds. Chitosan is actually degraded in vivo by several proteases, and mainly lysozyme [ 11 , 35 , 36 ]. Till now, eight human chitinases have been identified, three of them possessing enzymatic activity on chitosan [ 37 ]. The biodegradation of chitosan leads to the formation of non-toxic oligosaccharides of variable length. These oligosaccharides can be incorporated in metabolic pathways or be further excreted [ 38 ]. The degradation rate of chitosan is mainly related to its degree of deacetylation, but also to the distribution of N-acetyl D-glucosamine residues and the molecular mass of chitosan [ 39 - 41 ].

Chitosan shows biocompatibility in biomedical applications such as sutures and artificial skins [ 5 , 6 , 10 , 34 ] and was notably approved by the Food and Drug Administration (FDA) for use in wound dressings [ 42 ]. However, the compatibility of chitosan with physiological medium depends on the preparation method (residual proteins could indeed cause allergic reactions) and on the DD – biocompatibility increases with DD increase. Chitosan actually proved to be more cytocompatible in vitro than chitin. Indeed, while the number of positive charges increases the interaction between cells and chitosan increases as well, which tends to improve biocompatibility [ 43 ].

Besides, some chemical modifications of chitosan structure could induce toxicity [ 35 ].

Production process of chitosan has great effect on chitosan properties because these processes control the degree of acetylation of chitosan, i.e. free amino groups that allow it to bind with negatively charged molecules [ 1 , 4 , 44 ].

Chitosan has several biological properties that make it an attractive material for use in medical applications. These properties include: biodegradability, lack of toxicity, anti-fungal effects, wound healing acceleration and immune system stimulation [ 4 , 44 - 46 ].

4. Applications of chitosan and chitosan derivatives

Due to chitosan’s many attractive properties such as biodegradability, natural origin, abundance, reactivity, etc., it has many areas of application including: medical, agricultural, food processing, nutritional enhancement, cosmetics, and waste and water treatment [ 4 , 44 ].

4.1. Agricultural applications

The abundance, biodegradability, nontoxic, and natural origin of chitosan allow it to be safely used in agricultural applications because it can be used without concerns of pollution, disposal, or harm to consumers if ingested. Seed coating, leaf coating, fertilizer, and time released drug or fertilizer responses are some of the applications within agricultural where chitosan is utilized. The use of chitosan in these areas has shown to increase the amount of crops produced by improving germination, rooting, leaf growth, seed yield, and soil moisture retention, while reducing the occurrence of fungal infections and diseases [ 47 ].

4.2. Wastewater treatment applications

Chitosan’s functional groups and natural chelating properties make chitosan useful in wastewater treatment by allowing for the binding and removal of metal ions such as copper, lead, mercury, and uranium from wastewater [ 4 ]. It can also be utilized to breakdown food particles that contain protein and remove dyes and other negatively charged solids from wastewater streams and processing outlets [ 47 ].

4.3. Food industry applications

Chitosan’s chelating properties and high functionality make it valuable in several applications within the food industry such as binding with and removing certain elements, particles, and materials such as dyes and fats from foods. The antibacterial and antifungal properties found in chitosan can also be used during the storage and preservation of food [ 4 , 46 , 47 ].

4.4. Medical applications

Due to chitosan’s ability to function in many forms it has many areas of interest within the medical industry including orthopedic and Periodontal Applications [ 44 , 46 ]. Tissue engineering [ 44 , 45 , 47 - 49 ], Wound Healing [ 44 , 45 , 50 , 51 ] and Drug Delivery [ 52 , 53 ].

Some examples of biomedical applications of are artificial skin, surgical sutures, artificial blood vessels, controlled drug release, contact lens, eye humor fluid, bandages, sponges, burn dressings, blood cholesterol control, anti-inflammatory, tumor inhibition, anti-viral, dental plaque inhibition, bone healing treatment, wound healing accelerator, hemostatic agent, antibacterial agent, antifungal agent, weight loss effect [ 44 ].

5. Electrospinning of chitosan

Electrospinning is a process that utilizes a strong electrostatic field to obtain ultrafine fibers from a polymer solution accelerated towards the grounded collector due to the motion of charge carriers present in the solution in order to complete the electrical circuit. Electrospun fibers with their high surface area to volume ratio and small pores, are drawing interest in vast variety of applications, some being, filtration products, scaffolds for tissue engineering, wound dressings, drug release materials, fiber reinforcement composites, protective clothing [ 54 - 56 ].

5.1. History of electrospinning

In 1700s, influence of electrostatics was observed on water behavior and an electric charge influenced the excitation of dielectric liquid. This probably led to the invention of electrospinning to produce fibers in the early 1900s by Cooley and Morton. Cooley added rotatory electrode to the electrospinning jet. Formhals, in 1930, produce yarns by using electrospinning without spinneret [ 57 ] and patented his invention relating to the process and the apparatus. In 1940, Formhals patented another method for producing composite fiber webs from multiple polymer substrates by electrostatically spinning polymer fibers on a moving base substrate. In 1969, Taylor studied the shape of the polymer droplet produced at the tip of the needle when an electric field was applied and showed that it was a cone and the jets ejected from the vortices of the cone. This cone was later referred to as the ‘Taylor cone’. The effects of electric field, experimental conditions and the factors affecting the atomization and fiber stability were studied [ 58 ]. For the fiber industries, one important consideration is the rate of fiber production. Electrospinning, compared to the popular industrial fiber spinning processes, has very low production rates [ 57 ]. Industrial dry spinning has a yarn take-up rate of 200– 1500 m min−1 while yarn fabricated from electrospinning has a take-up speed of 30 m min−1. Thus, before 1990, there was very little industrially oriented research interest found on electrospinning. Melt spinning being the preferred method for producing synthetic fibers, efforts were made to electrospin fibers using polymer melts, but difficulties were encountered in fabricating fibers with nanometer diameters and, therefore, little progress was made in this specific approach. Nevertheless, Dalton et al [ 59 ] recently succeeded in depositing electrospun polymer melt fibers directly on to cells to form layered tissue constructs for tissue engineering. This eliminated the introduction of cytotoxic solvents into the cell culture when the fibers were deposited. While there have been patents filed for various electrospinning set-ups since the 1900s, it is only in the last decade that academia got heavily involved in using electrospinning to fabricate various nano-fibrous assemblies for a range of potential applications.

Figure 4 shows a comparison of diameters between nanofibers, proteins, viruses and bacterial cells [ 60 ].

Comparison of the Diameters of Electrospun Fibers to those of Biological and Technological Objects [ 60 ].

5.2. Electrospinning process

Electrospinning as the production of fine fibers (either nano or micro) from polymer solutions by using high voltage electric field (kV) at room temperature and atmospheric conditions There are two electrospinning setups, vertical and horizontal [ 1 , 61 , 62 ].

Electrospinning devices, Figure 5 , consists of three main componenet: high voltage electric field, spinneret and collecting electrode.[ 1 , 63 , 64 ].

Through electrospinning process, polymer solutions subjected to high voltage electric field that induce electric charge on its surface. At critical electric field, the repulsive electrical forces can overcome the surface tension and eject unstable charge jet from Taylor cone tip, which evaporate the solvent and leave the polymer [ 1 , 65 - 68 ]. The jet is only stable at the tip of the spinneret and after that, instability starts. Thus, the electrospinning process offers a simplified technique for fiber formation.

Due to the critical voltage, applied potential reaches a critical value and the repulsive force within the charged solution exceeds surface tension and a jet erupts from the tip of the cone. These charged ions in the polymer jet move in response to the applied electric field towards the electrode of opposite polarity, thereby transferring tensile forces to the polymer jet making the latter undergo a chaotic motion or bending instability with whipping action. The jet moves towards the opposite charged collector, which collects the charged fibers. The jet ejected from the apex of the cone continues to thin down along the path of its travel towards the collector. As the jet travels through the atmosphere, the solvent evaporates, leaving behind a dry fiber on the collecting device. The structure formation happens on a millisecond scale[ 69 ]. An important step within production of the fibers is the elongation taking place within the jet with a strain rate as high as 10 4 sec -1 [ 55 , 58 , 70 , 71 ].

Schematic illustration of electrospinning setup [ 56 ].

A typical electrospinning setup only requires a high voltage power supply, a syringe, a flat tip needle and a conducting collector as shown in Figure 7 . Electrospinning is able to produce continuous nanofibers from a wide range of materials. Nevertheless, there are many parameters, which affect the fiber morphology and properties in electrospinning. The main parameters are polymer parameters and processing conditions [ 54 , 56 , 72 ].

5.3. Effects of various parameters on electrospinning

There are several parameters affect the electrospinning process. These parameters are solution, process and ambient parameters [ 1 , 56 , 73 ]. In Table 1 , there are summary of various parameters and their effects on fiber morphology[ 1 ].



Viscosity (η)	Low (η) generate beads, high (η) causes increase in fibre diameter and disappearance of beads
concentration	Fibre diameter increase with increasing of polymer concentration.
Molecular weight of polymer	The number of beads decrease, with increasing of molecular weight.
Conductivity	Decrease in fiber diameter with increase in conductivity.
Surface tension	Jets. Instability appears with high surface tension

Applied voltage	Decrease in fiber diameter with increase in voltage.
Distance between tip and collector	Generation of beads with too small and too large distance, minimum distance required for uniform fibers.
Feed rate/Flow rate	Decrease in fiber diameter with decrease in flow rate, generation of beads with too high flow rate.

Humidity	High humidity results in circular pores on the fibers.
Temperature	Increase in temperature results in decrease in fiber diameter.

Electrospinning Parameters (Solution, Processing and Ambient) and their Effects on Fiber Morphology [ 1 ].

5.4. Solvents used for electrospinning

Solvents play an important role in electrospinning to the dissolution of polymer in soluble solvent is the first step in the electrospinning process. These solvents should be volatile and have low boiling point such as chloroform, ethanol, dimethylformamide (DMF), trifluoroacetic acid (TEA), dichloromethane (DCM) [ 1 , 74 - 76 ].

Solution properties such as viscosity and surface tension have great effect on the morphology of nanofibers [ 1 , 77 ].

Basically, a solvent performs two crucial roles in electrospinning: Firstly, to dissolve the polymer molecules for forming the electrified jet. Secondly to carry the dissolved polymer molecules towards the collector [ 78 ], e.g. dimethylformamide, a dipolar aprotic solvent, has been successfully used as a solvent for electrospinning of poly (acrylonitrile) and its addition enhances the solution conductivity which is a prerequisite for the formation of bead free uniform fibers [ 79 ]. It was found that by increasing the concentration, there was a gradual decrease in surface tension of the solution, which favoured production of thinner fibers [ 80 ].

6. Electrospinning of chitosan solutions

Chitosan cannot form nanofibers through electrospinning process because its poly cationic nature due to the presence of many amino groups in its structure which increase solution surface tension [ 2 , 81 ].

Fibrous structures were successfully formed by electrospinning chitosan solutions in 90wt% aqueous acetic acid solution [ 80 ] or by using trifluoroacetic acid (TFA) or TFA/dichloromethane (DCM) [ 78 ]. However, electrospinning conditions are relatively limited in terms of concentration, molecular weight, and degree of deacetylation [ 82 ]. The resultant chitosan fibers need to be cross-linked to maintain their structural integrity, as they can readily swell in aqueous solution [ 83 ].

Since the electrospinning of chitosan itself proved to be difficult. Chitosan was mixed with other synthetic or natural polymers, such as PEO in aqueous acid, PVA, aqueous acetic acid solution or aqueous acrylic acid solution, poly (lactic acid) (PLA) in trifluoroacetic acid/ methylene chloride mixture solvents or its copolymers in aqueous acetic acid solution, silk fibroin (SF) in formic acid, and collagen in 1,1,1,3,3,3,-hexafluoro-2-propanol/trifluoroacetic acid mixture solvent [ 2 ]. Several chitosan derivatives such as hexanoyl chitosan in Chloroform as a solvent, quaternized chitosan aqueous acetic acid solution or Water, N-carboxyethylchitosan in aqueous acrylic acid solution or water as solvent, and chitosan grafts with L-lactide or PEG oligomer in dimethylformamide/tetrahydrofuran solvent [ 2 ] were synthesized and electrospun with or without polymer additives, to improve the solubility and electrospinnability of chitosan

Chitin and chitosan nanofibers are biocompatible, biodegradable and nono-toxic so that it is used in biomedical applications such as antithrombogenic, hemostatic, and wound healing. The use of nanofibrous chitosan matrices is thus expected to mimic the natural ECM, in which cells attach, proliferate, and differentiate [ 2 , 84 , 85 ]. The use of nanofibrous chitosan matrices is thus expected to mimic the natural ECM, in which cells attach, proliferate, and differentiate.

An organic/inorganic composite scaffold of hydroxyapatite (HAp) and electrospun nanofibrous matrix was prepared by using chitosan/poly(vinyl alcohol) (CS/PVA) and N-carboxyethylchitosan/PVA (CECS/PVA) electrospun membranes, and HAp was formed in supersaturated CaCl 2 and KH 2 PO 4 solution [ 86 ].

Xu et al was successful to prepare chitosan nanofibers used for enzyme immobilization by mixing its solution with polyvinyl alcohol (PVA) then added to sodium hydroxide solution for remaining the PVA and stabilizing chitosan nanofibers [ 87 ].

Chitosan nanofibers used for wound healing because it shows antibacterial activity against Staphylococcus aureus and Escherichia coli [ 87 , 88 ]. In addition, chitosan nanofibers with (40-290 nm diameters) were prepared by electrospinning of its solution with polyethylene oxide (PEO) blended solution [ 89 ].

Quaternized chitosan (QCS) form nanofibers in the presence of polyvinyl alcohol (PVA) and poly vinyl pyrrolidone (PVP) as fiber aiding materials [ 90 , 91 ].

Ultrafine fibers could be generated by controlling the addition of PEO in 2:1 or 1:1 mass ratios of CS to PEO from 4–6 wt% CS/PEO solutions to be used for cartilage tissue repair [ 92 , 93 ].

Chitosan electrospun nanofibers are cellular biocompatible. Chitosan molecular and solvent used control the beads formation such as hexanoyl chitosan/poly lactide nanofibers in chloroform formed without beads. Also in chitosan/PVA nanofibers, beads formation decreased by increased the content of PVA repair [ 92 , 94 ].

PVA are non-toxic, non-ionogenic and water-soluble polymer. Therefore, the nanofibrous materials prepared by electrospinning of CECS/PVA aqueous solutions, dissolved when put in contact with water. CECS / PVA mats stabilized by heating at 100 o C. it is used in tissue schafolds applications [ 92 , 94 ]. FTIR, XRD, and DSC studies demonstrated that there were strong intermolecular hydrogen bonds between the molecules of CS and PVA in the PVA/CS blend nanofibrous membranes [ 95 ]. SEM images showed that the morphology and diameter of the nanofibers were mainly affected by concentration of the blend solution (weight ratio of the blend) respectively [ 95 ]. It appears that electrospinning may emerge as a versatile method to manufacture CS fibers.

7. Nanofibers produced by electrospinning

7.1. nanofiber morphology.

Nanofibers produced by electrospinning have gained popularity in research in part due to their morphological characteristics. These nano-diameter fibers have high surface areas, small pore sizes and are able to be produced in three dimensional forms ( Figure 6 ). Because the above mentioned characteristics can be modified through process parameters to suit individual applications and needs, electrospinning has become a growing topic among researchers [ 71 ].

Scanning electron microscopy (SEM) image of electrospun poly (vinyl alcohol) produced on laboratory electrospinning setup.

7.2. Nanofiber properties

The properties associated with nanofibers can be traced back to both process parameters and morphological characteristics. For example electrospun fibers have small pores that are a result of the evaporation of the solvent used during the electrospinning process and these pores affect mechanical properties of the fibers such as tensile strength and Young’s modulus [ 58 ]. Other studies have found that the physical properties of nanofibers tend to be somewhat inferior to that of their film and resin counterparts of a similar thickness. [ 65 , 71 ] This is believed to be a result of lower crystallinity due to rapid evaporation of the solvent followed by rapid cooling, which occurs in the final stages of the electrospinning process [ 58 ].

7.3. Nanofiber applications

Characteristics such as large surface areas and the ability to be engineered in various forms have allowed nanofibers to be used in applications including: filtration [ 51 ], composite reinforcement [ 96 ], multifunctional membranes [ 51 ], tissue engineering scaffolds [ 3 , 45 , 51 , 97 , 98 ], wound dressings [ 50 , 65 , 99 , 100 ], drug delivery [ 100 - 102 ], artificial organs [ 65 , 103 ], and vascular grafts [ 65 , 102 - 104 ]. Although all of these areas of interest are, still studied, biomedical applications for polymeric nanofibers have made up a majority of the new growth in the field of nanofiber research ( Figure 7 ). [ 65 ] This growth is in part due to increased understanding of the human body, cellular structure, and the body’s reaction to foreign materials.

An estimation of the targeted nanofiber research fields based on the number of patent applications for electrospun nanofibers [ 65 ].

Researchers in the past have made attempts to electrospin chitosan in order to further utilize this material [ 33 , 48 , 49 , 78 , 80 , 81 , 84 , 89 , 93 , 105 ]. Chitosan produces many challenges in being electrospun largely due to its high solution viscosity. Chitosan’s rigid D-glucosamine structures, high crystallinity and ability to hydrogen bond lead to poor solubility in common organic solvents [ 105 ]. The smallest diameter fibers were reported using a poly(vinyl alcohol)/chitosan blend which resulted in nanofibers with average diameters between 20 and 100 nm [ 105 ]. Other studies have reported nearly defect free nanofibers, with slightly larger fiber diameters using a poly (ethylene oxide) (PEO)/chitosan blend [ 49 , 89 , 93 , 105 ]. The successful electrospinning of pure chitosan has only been reported using a solvent system of 90 % acetic acid and a 7 wt.% concentration of chitosan [ 80 ].

The first successful reports of PEO/chitosan electrospun blends reported the electrospinning of nanofibers with diameters ranging from 40 to 290 nm, but that the most consistent and defect free fibers had an average diameter ranging from 200 to 250 nm (Spasova et al, 2004) Another study using a PEO/chitosan blend reported defect free nanofibers with diameters that ranged from 80 to 180 nm, but found that that the samples did not have consistent diameters. Using Fourier transform infrared spectroscopy and differential scanning calorimeter it was discovered that the two polymers had separated and the larger fibers largely consisted of PEO and the smaller fibers were predominately chitosan [ 93 ]. To further reduce the diameter of the electrospun PEO/chitosan blend fibers another research group introduced Triton X-100™ as a nonionic surfactant as well as dimethylsulphoxide as an additional solvent. These additions greatly improved the ability to electrospin PEO/chitosan blends with a high polymer concentration and produced fibers with diameters that ranged from 40 to 110 nm [ 49 ]. The same group also tested this nanomesh for cellular attachment and viability and found that cells more readily attached and were able to be sustained more efficiently than on a cast film of the same materials [ 49 ]. Another study was able to successfully electrospin PEO/chitosan blends with no additional additives, which resulted in fibers with an average diameter of 300 nm [ 48 ]. This group’s main objective was to test the cellular viability of a chitosan blend in the electrospun nanomesh form. They concluded that chondrocyte cells showed good cell adhesion, proliferation and viability on the chitosan-based electrospun material. It also concluded that the electrospun material had a higher modulus compared to the control film made by solvent casting. [ 48 ]

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Chitosan: Are the Health Claims True for This Popular Supplement?

What Is Chitosan
Side Effects

Interactions

Sources & Where to Look

Frequently Asked Questions

Chitosan is a polysaccharide derived from chitin , an abundant substance found in the exoskeleton of crustaceans (a type of shellfish) and insects, and in the cell walls of certain fungi.

Chitosan is widely popular, with the global market value surpassing $6 billion in 2019. This is because it has been used in water treatment agents and in the pharmaceutical, biomedical, cosmetic, and food industries.

But while chitosan is also believed to offer health benefits, research results regarding its efficacy appear mixed. It's most commonly used for weight loss, high blood pressure , high blood sugar, and dyslipidemia .

This article will provide in-depth information on chitosan, including what it is and how it works. The article will also discuss the potential uses, safety risks, dosage, drug interactions, and sources of chitosan in foods and supplements.

Getty Images / dheeraj11

What Is Chitosan, and How Does It Work?

After cellulose, chitin is the second most abundant polysaccharide in the world. Polysaccharides are complex carbohydrates that may include dietary fiber .

Chitin provides structure to the exoskeletons of crustaceans (e.g., lobster, shrimp, crab), certain insects, and fungi cell walls. Chitosan results from a chemical reaction in which chitin is broken down.

Aside from dietary supplements, chitosan is also used in the pharmaceutical, biomedical, cosmetic, and food industries. Various aspects of chitosan, such as its solubility and viscosity, make it of special interest to these industries.

When consumed, chitosan reacts with the acidic environment in your stomach to form a gel. This gel is thought to bond with fatty compounds and block them from absorption in the gastrointestinal tract. Ultimately, the mixture of chitosan and fat is excreted through feces.

This process may benefit those with certain health conditions, which will be explored next.

Potential Uses of Chitosan Supplements

Supplement use should be individualized and vetted by a healthcare professional, such as a registered dietitian, pharmacist, or healthcare provider. No supplement is intended to treat, cure, or prevent disease.

Through scientific research, chitosan has been found to possess antimicrobial, antioxidant, anti-inflammatory, and other properties. These biological properties may be useful for a variety of health conditions.

Studies continue to emerge as researchers learn more about the polysaccharide and its potential applications. Some of the possible uses of chitosan are outlined below.

May Decrease High Blood Sugar

Chitosan has been proposed as a complementary treatment for high blood sugar, a common symptom of both metabolic syndrome (a group of conditions that together can lead to heart disease, diabetes, and stroke) and type 2 diabetes .

Animal and laboratory studies have found a link between chitosan and improved blood sugar regulation through decreased insulin resistance (when muscle, liver, and fat cells do not respond well to insulin and cannot take up glucose from the blood, creating the need for the pancreas to make more insulin) and increased blood sugar uptake by tissues. These benefits have been tested in various clinical trials.

A meta-analysis of 10 clinical trials found somewhat conflicting results regarding the effectiveness of chitosan in lowering blood sugar . While chitosan appeared to decrease fasting blood sugar and hemoglobin A1c ( HbA1c ), a blood test to check the average blood sugar levels over three months, it did not have a significant effect on insulin levels.

Researchers pointed out that the best results were seen when chitosan was used at a dose of 1.6 to 3 grams (g) per day and for at least 13 weeks.

One study found that chitosan may also play a role in diabetes prevention. In the study, participants with prediabetes (when blood glucose levels are high but not high enough to be considered diabetes) were randomized to take either a placebo (a substance of no benefit) or chitosan supplement for 12 weeks. Compared to the placebo, chitosan improved inflammation, HbA1c, and blood sugar levels.

Overall, human trials on chitosan for blood sugar control are lacking in study size and design. Additional research is needed in this area.

May Decrease High Blood Pressure

A limited number of clinical trials have shown a relationship between chitosan and blood pressure . More specifically, chitosan has been found to reduce high blood pressure in some small-scale human studies. However, some research results have been mixed.

Chitosan is thought to reduce blood pressure by binding with fats and carrying them through the digestive tract to be made into feces. Increased fat excretion would lead to reduced levels of fats in the blood, a risk factor for high blood pressure.

A review of eight studies concluded that chitosan may lower blood pressure but not significantly. The best results came when chitosan was used in high doses but for shorter periods. Diastolic blood pressure (but not systolic blood pressure) decreased significantly when chitosan was taken for less than 12 weeks at doses greater than or equal to 2.4 g per day.

Although these results may appear convincing, they are not definitive proof that chitosan supplementation lowers blood pressure. More research is necessary to further explore the relationship between chitosan and blood pressure.

May Help With Weight Loss

Probably the most popular health claim of chitosan is that it may help with weight loss. While there is some evidence to support this claim, it's important to remember that using dietary supplements as a sole measure for weight loss is not recommended.

Chitosan derived from fungi was used in one clinical trial involving 96 adult participants who were classified as overweight or having obesity . Participants were given capsules that contained either a placebo or 500 mg of chitosan and were asked to take them five times per day for 90 days.

Compared to the placebo, results showed that chitosan significantly reduced body weight, body mass index (BMI) , and anthropometric measurements (blood, muscle, and fat measurements) in the study participants.

In a different study, chitosan was compared to a placebo in 61 kids classified as overweight or having obesity. After 12 weeks, chitosan use resulted in decreased body weight, waist circumference, BMI, total lipids, and fasting blood sugar in the young participants. These results are thought to be due to chitosan's ability to remove fat from the digestive tract for excretion.

Despite these results, larger human trials should be conducted before chitosan can be safely recommended for weight loss.

May Promote Wound Healing

Due to its antimicrobial and structural properties, there is interest in using topical chitosan for wound healing.

Research shows that chitosan aids in the wound healing process. Chitosan has been found to have antibacterial effects, which are vital to wound healing. It has also been found to increase the rate of skin proliferation (the making of new skin).

Recently, researchers have looked at chitosan hydrogels, which contain water and can be used similarly to bandages. Chitosan hydrogels may decrease the risk of infection that can affect some wounds.

A recent trial tested a chitosan wound dressing on people with second-degree burns . The chitosan dressing decreased both pain and the time it took for the wounds to heal. Chitosan was also found to reduce incidents of wound infection.

In another small study, chitosan dressings were used on diabetic wounds and compared to another wound dressing made from nanosilver particles. The effectiveness of the chitosan dressing was found to be similar compared to the nanosilver dressing. Both dressings led to gradual healing in the diabetic wounds and also prevented infections .

Safety Risks & Side Effects

Supplements typically come with a risk of side effects, and chitosan is no exception.

At this time, very few side effects have been reported for chitosan. The most common side effects associated with chitosan affect the digestive system. These may include nausea and/or constipation . However, these were only reported in a small percentage of people.

Chitosan is generally recognized as safe (GRAS) by the Food and Drug Administration (FDA) as a food additive. However, there is concern that some chitosan supplements could contain contaminants if not properly manufactured.

It's unknown how long chitosan can safely be used. In various studies, chitosan has been safely used for up to 12 to 13 weeks.

Aside from possible side effects, chitosan may not be right for everyone.

Because one of the main sources of chitosan is crustaceans, people with a shellfish allergy should avoid using it. Anyone with a mushroom allergy should also avoid chitosan sourced from fungi.

It's recommended that people who are pregnant or breastfeeding avoid using chitosan. This is due to the lack of safety information regarding chitosan use in these populations.

More information is needed to determine the full safety profile of chitosan supplements.

Dosage: How Much Chitosan Should I Take?

Dietary supplements are not regulated like prescription medications in the United States. Therefore, some may be safer than others. When choosing a supplement , consider factors such as third-party testing, potential drug interactions, and other safety concerns. Talk to a healthcare provider or a registered dietitian nutritionist (RD or RDN) about supplement quality and safety.

Currently, there are no dosage guidelines for chitosan supplements.

In clinical trials, chitosan dosing ranged from 0.3 g per day to 3.4 g per day in adults. Chitosan was also commonly used for 12 to 13 weeks in the trials.

It's recommended that you follow dosage directions as indicated on the supplement label. You can also obtain dosage recommendations from a healthcare provider.

Chitosan may negatively interact with certain medications, supplements, or nutrients. These interactions may block the absorption or proper use of chitosan or the medications, supplements, or nutrients it is taken with.

There is concern that chitosan interacts with medications and supplements that may have similar uses. These medications and supplements include:

Medications or supplements that act as blood thinners
Antiviral medications or supplements
Medications or supplements used to treat diabetes

Chitosan may also reduce the absorption of fat-soluble vitamins . However, this was only seen in animal studies. This may occur when chitosan binds to fatty substances in the digestive tract before being absorbed into the bloodstream.

It should be noted that there isn't solid evidence or clear documentation of these or other interactions for chitosan. However, it's best to be cautious and talk with a healthcare provider before using chitosan to discuss potential interactions, especially if you use any medications or supplements.

It is also important to carefully read the ingredients list and nutrition facts panel of a supplement to know which ingredients and how much of each ingredient is included. Please review supplement labels with a healthcare provider to discuss any potential interactions with foods, other supplements, and medications.

Sources of Chitosan & Where to Look

Various foods and supplements contain chitosan. Compared to chitosan-containing foods, supplements may be easier to access and appear to be a more popular method for consuming the polysaccharide.

Food Sources of Chitosan

The main food sources of chitosan include crustaceans and certain types of mushrooms. Chitosan may also come from the exoskeleton of insects.

In crustaceans and mushrooms, chitosan is found in its original form of chitin (recall that chitosan is a derivative of chitin). Specifically, chitin is a part of the exoskeleton of crustaceans and the cell walls of some mushrooms and other fungi.

The only way to consume chitin that comes from crustaceans is through dietary supplements. This is because the exoskeletons of shrimp, crabs, lobsters, and other crustaceans are not commonly eaten.

Chitin has been found in both edible and nonedible mushrooms . However, an enzymatic reaction has to occur for chitin to be converted to chitosan. Chitosan is considered to be more easily digested than chitin.

Supplements tend to be a better option for getting chitosan.

Supplement Sources of Chitosan

Due to their popularity, chitosan supplements are not difficult to find. There are a number of websites that sell chitosan supplements. You can also find chitosan supplements in certain retail stores, grocery stores, or specialty nutrition shops.

Chitosan supplements come in many forms, including capsules, powders, and tablets. There are also topical chitosan options, like gels.

Some chitosan supplements may be mixed with other nutrients, herbs, or ingredients. Be sure to read the full list of ingredients to understand the product you purchase.

Many chitosan supplements are sourced from crustaceans. If you are vegan or vegetarian, look for chitosan that has been sourced from mushrooms instead.

Of course, you shouldn't use chitosan products if you're allergic to any of the ingredients. For example, if you have a shellfish allergy, then you should avoid using chitosan supplements that come from crustaceans.

Several chitosan supplements on the market can fit other diets, like a gluten-free diet or an organic diet. This information should be listed on the label or packaging of the supplement.

Chitosan is a derivative of chitin, a polysaccharide present in the exoskeletons of crustaceans, certain insects, and the cell walls of fungi.

Chitosan contains nutrients and bioactive compounds that may be useful for high blood sugar, high blood pressure, wounds, and other conditions. In general, more research is needed on chitosan to prove its benefits.

Side effects are possible when taking chitosan, so talk with a healthcare provider to make sure it's the right supplement choice for you.

Some people should avoid using chitosan.

Some chitosan products contain common allergens , like shellfish. Other chitosan products are made from mushrooms. Avoid using chitosan if you're allergic to shellfish, mushrooms, or any other substance in the ingredients list.

You should talk with a healthcare provider about using chitosan if you're pregnant or breastfeeding. There isn't much research on the use of chitosan in these populations, so it may be best to avoid it.

To get chitosan naturally, you'd need to eat foods that contain chitin. Chitin-containing foods include mushrooms and crustaceans. However, chitin is only available in the exoskeletons of crustaceans, a part of the animal that isn't typically eaten.

Chitosan is most commonly found in supplements. This is because a chemical reaction is needed to transform chitin from foods into chitosan.

When using chitosan supplements, you can take them daily. However, little is known about the safety of using chitosan for more than 12 weeks. Therefore, it might not be safe to take chitosan for more than 12 weeks.

Talk with a healthcare provider about the proper way to use chitosan supplements.

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By Brittany Lubeck, MS, RDN Lubeck is a registered dietitian and freelance nutrition writer with a master's degree in clinical nutrition.

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Chitosan: sources, processing and modification techniques.

Graphical Abstract

1. Introduction

2. biosynthesis of chitin, 3. chitin extraction techniques, 4. chitin deacetylation techniques, 5. structure-function properties of chitosan, 5.1. influence of dda and molecular weight (m w ) on chitosan properties and applications, 5.2. influence of origin of chitosan, 6. tailoring chitosan for specific applications, 7. conclusions and future perspectives, author contributions, institutional review board statement, informed consent statement, conflicts of interest.

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Field of Application	Applications	References
Biomedical and Pharmaceutical applications	Antioxidant: free radical scavenger/quencher Antimicrobial agent: positively charged chitosan-NH groups interact with negatively charged microbial cell membrane creating pores Drug delivery: mucoadhesive properties increase drug permeation of intestinal, nasal, and buccal epithelial cells, Gene therapy: Delivering various genes and siRNA Chitosan based drugs. For example, lowering effect of cholesterol for obesity treatment Regenerative technology/tissue engineering: bone, neural, cornea, cardiac and skin regenerative technology. Provides a three-dimensional tissue growth matrix, activate macrophage activity and stimulate cell proliferation Wound management: homeostatic agent, participate in repair, replacement, activation of humor immunity, complement system, and CD4+ cells, enhances granulation as well as the organization of the repaired tissues. It slowly degrades into N-acetyl-β-d-glucosamine that stimulates fibroblast proliferation, regular collagen deposition in addition to stimulating hyaluronic acid synthesis at the wound site.	[ , , , , , , , , , , , , , , , , , , , , , , ]
Health care products	Cosmetics formulations: Antimicrobial, antifungal, UV absorbing abilities exploited in various cosmetics formulations including in shampoos, rinses, colorants, hair lotions, spray, toothpaste formulations and tonics. Sunscreens, moisturizer foundation, eyeshadow, lipstick, cleansing materials, and bath agent, toothpaste, mouthwashes, and chewing gum as a dental filler.	[ , , , ]
Food Industry	Packaging, edible coatings, body filling, emulsifying agent, natural flavor extender, texture controlling, thickening and stabilizing agent, food preservation (antimicrobial agent), antioxidant agent. Flocculation/Clarification and deacilification of fruits and beverages	[ , , , , , , , ]
Agriculture	Antimicrobial activities against various plant pathogens. Fruit preservative. controlled delivery of fertilizers, pesticides, and insecticides. Increase in the auxin concentration and urea release in the soil, germination capacity, root length and activity, and seedling height	[ , , ]
Industrial application	Functional materials: Graphitic carbon nanocapsules/composites, tungsten carbide chitin whiskers, etc. are used in the production of micro-electrochemical systems and 3D networks	[ , , ]
	Electrolyte: Sulfuric acid and chitosan combination has the ability to discharge high voltage Chitosan provides ionic conductivity and can be used in the production of solid-state batteries Photography: fixing agent for color prints	[ , , , , , , , ]
	Paper manufacture: Production of filter papers, water-resistant papers, biodegrading packages, water-resistant papers	[ , , , , ]
	Enzyme carrier: immobilizing enzymes on solid materials	[ , , ]
Construction industry	wood adhesive, fungicide, wood quality enhancer, and preservative	[ , , ]
Waste treatment	Flocculating, and negative charge (chelating agent), for dye, heavy metal ions removal and decontamination. Used for various processing plants such as whey, dairy, poultry, and seafood processing plants	[ , , , , , ]

Extraction Techniques	Process Conditions	Advantages	Disadvantages	References
Chemical methods	Deproteinization conditions: NaOH, KOH, Na SO , Na CO Temp: 25–100 °C, 30 min–72 h Demineralization: HCL, HNO , CH COOH, HCOOH Temp: 25–100 °C, 30 min–48 h Decolorization: organic solvents such as acetone, ethyl alcohol, diethyl ether Bleaching: KMnO , NaCIO/H O ; Temp: 20–60 °C, 25 min–12 h Recovery: precipitation with 5–10%NaOH Deacetylation: NaOH/KOH 30–50% w/v, Temp: 80–150 °C, Time 1–8 h	Short processing time Produces chitin with high DA% Accompanied by deacetylation Process used at industrial scale	Multistep process Deacetylation unavoidable Environmentally unfriendly generate large quantities of waste that cannot be used as human and animal nutrients. Calcium carbonate lost to waste stream	[ , , ]
Biological and enzyme based methods	Demineralization: fermentation using lactic acid producing bacteria or lactic acid Deproteinization using enzymes (cellulases, pectinases, chitinases, lipases, papain, hemicellulases, pepsin and lysozyme produces chitooligosaccharides, lysozyme Protease deproteinization and demineralization: in (10% HCl solution at 20 °C for 30 min) at 55 °C and pH of 8.5 Combined deproteinization and demineralization: microorganisms producing proteases or proteases Protease demineralization at 25 °C for 20 min in the presence of lactic acid ratio of 1:1.1 w/w and acetic acid ratio of 1:1.2 w/w) Deproteinized with chitinase at 45 °C and a pH of 6.0 with shaking at 150 rpm Alcalase, esperase and neutrase in deproteinization, followed by deacetylation by alkaline treatment, reached the highest degrees of deacetylation with 61.0–63.7% NaOH for 14.9–16.4 h Combination of species, including Serratia marcescens and L. plantarum, increased deproteinization and demineralization activity Decoloration: acetone or organic solvent, Deacetylation: chitin deacetylase producing by bacteria Lactic acid ratio of 1:1.1 w/w and shells: acetic acid ratio of 1:1.2 w/w) had a maximum demineralization	High quality of final product Sustainable process Environmentally safe; specific, fast in action, reduces the use of energy, chemicals and/or water compared to conventional processes Regular deacetylation and MW	Long processing time (days) Process still under development enzymatic method had a higher degree of acetylation (19.4%) and viscosity than that prepared by chemical method (17.2%).	[ , , , , , , , , , , , , , , ]
Ionic liquids	Complete dissolution followed by the selective precipitation of chitin. Treatment with [C2C1im] [CH3COO] [ ]. causes swelling swell Ionic liquids 1-ethyl-3-methylimidazolium acetate [C2mim] [OAc], 1-butyl-3-methylimidazolium chloride [C4mim]Cl, [C2mim]Cl, [C2mim] [OAc], and 1-allyl-3-methylimidazolium acetate [Amim] [OAc], are effective against chitin from shrimp shells, crab shell waste, and squid pens. Combination of steam explosion and ionic liquid pretreatments for efficient utilization of fungal chitin	Scaling-up the process were successful leading to the establishment of a company 525 Solutions at industrial scale [ ]. Dissolution and coagulation of the polymer combined with enzymatic hydrolysis, reduces its crystallinity, making the polymer more accessible to the enzyme	Harsh totally dissolves chitin Toxicity and nonbiodegradability DESs are the ability to perform a three-step process in single step, including demineralization, deproteinization and chitin dissolution	[ , , , , , , , ]
Deep eutectic solvents	Demineralization, deproteinization and chitin dissolution perform a three-step process in single step Mixture of hydrogen bond acceptor (HBA) and a hydrogen bond donor (HBD), choline chloride (ChCl) is commonly used as an HBA, while HBDs include lactic acid, malonic acid, and citric acid 150 °C Incubating different ratio mixtures of DESs (ChCl/citric acid, ChCl/L-lactic acid, and ChCl/malic acid) with chitin sources at temperatures between 50–150 °C for 2–6 h DES plus Microwave: DES ratios of 1:5, 1:10, and 1:20. Next, the mixture was heated under 700 W microwave irradiation (Haier MZC-2070M1) for different durations of time (1, 3, 7, and 9 min) Demineralization was carried out by the malic acids. When choline chloride–malic acid was applied to the shrimp shells, minerals, which are mostly in the form of crystalline CaCO , were removed by the malic acid, leaving the proteins and chitin. The spacing between the chitin–protein fibers was filled with proteins and minerals; thus, the removal of minerals resulted in a weakening of the linkages within the inner structural organization of the shrimp shells. Since the minerals are removed by the malic acids, in order to conduct demineralization, one component of the DESs used in the chitin extraction should be an acid.	Single step for simultaneous removal of protein and minerals Demineralization, deproteinization and chitin dissolution perform a three-step process in single step Low melting temperature, non-flammability, highly chemical and thermal stability and superior biodegradability. No deacetylation Solvent recycling possible	High solvent viscosity causes difficulty at large scale DESs are a new class of ionic liquid analogues derived from inexpensive commercially available raw materials with a melting point lower than that of each individual component. DESs are biodegradable, cheap and easy to produce	[ , , , , , ]
Ultrasound extraction	Ultrasound’s cavitation effect solubilizes protein associated with chitin, dissociates covalent bonds in polymer chains and disperses aggregates Uses high-intensity Ultrasound signals at 750 W power and 20 kHz ± 50 Hz operating frequency to enhance the efficiency of extraction of chitin,	Reduces the extraction time and avoids the requirement of high temperatures.		[ , , ]
Microwave-assisted extraction	Microwave heating involves two main mechanisms: (i) dipolar polarization and (ii) ionic conduction Increasing the microwave irradiation to 130 watts of power for 15 min resulted in high deproteinization (11.46%) and a low ash content (5.4%) at 700 °C for 2 h using 50% of NaOH solution in a power range of 500–650 W resulted in a low DDA, and the deacetylation reaction was more than 80% completed after 10 min. MAE allowed the production of chitosan with medium and high MW (300–360 kDa).	Fast deacetylation of chitosan in 24 min, compared to conventional heating method that requires 6–7 h Upscaling possibility		[ , , , , ]

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Pellis, A.; Guebitz, G.M.; Nyanhongo, G.S. Chitosan: Sources, Processing and Modification Techniques. Gels 2022 , 8 , 393. https://doi.org/10.3390/gels8070393

Pellis A, Guebitz GM, Nyanhongo GS. Chitosan: Sources, Processing and Modification Techniques. Gels . 2022; 8(7):393. https://doi.org/10.3390/gels8070393

Pellis, Alessandro, Georg M. Guebitz, and Gibson Stephen Nyanhongo. 2022. "Chitosan: Sources, Processing and Modification Techniques" Gels 8, no. 7: 393. https://doi.org/10.3390/gels8070393

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Dyson takes its next step into the world of beauty with its first ever wet line styling products - the Dyson Chitosan™ formulations range

PR Newswire

NEW YORK, Aug. 15, 2024

The brand pioneering technological beauty also introduces their first connected hair tool, the Airwrap i.d.™ multi-styler and dryer

NEW YORK, Aug. 15, 2024 /PRNewswire/ -- Dyson is setting a new standard in beauty technology with the launch of two groundbreaking products: the Dyson Chitosan™ formulations range and the Dyson Airwrap i.d.™ multi-styler and dryer, both introducing first-ever technology for the brand.

Dyson Chitosan™ Formulations Range

Expanding its beauty portfolio, Dyson launches its first-ever wet line styling products, the Dyson Chitosan™ Pre-Style Cream and the Dyson Chitosan™ Post-Style Serum . Powered by chitosan— a complex macromolecule derived from oyster mushrooms— and engineered with Dyson Triodetic™ technology, this range promises flexible, all-day hold with natural movement and shine.

The move into formulations represents a new frontier for Dyson, with a move into ingredient research.

Chitosan is a molecule those in the beauty community may not be familiar with. Those who are familiar are likely to have heard of the shellfish derivative, used as a supplement or in some packaging solutions. Through research, Dyson sourced a version of chitosan from oyster mushrooms. Chitosan is a complex macromolecule that is found in the cell walls of the mushroom. Delicate yet strong, it's what gives the fungi its shape and provides the basis of Dyson's flexible hold. It's this hero ingredient that gives the Dyson Chitosan™ range its name.

Kathleen Pierce, President of Beauty at Dyson , "Our engineers have rigorously tested to find the optimum percentage of chitosan for all-day, flexible hold, while maintaining natural movement."

Dyson's new styling products are designed to work seamlessly with Dyson's hair tools. The pre-style cream primes and conditions hair, reducing frizz and enhancing shine, while the post-style serum locks in styles with hydration and a protective shield against humidity.

With four varieties, each formulation is tailored for different hair types, incorporating specific ingredients such as grape seed oil and argan oil to meet various conditioning needs. The packaging is engineered with a precision applicator that dispenses a consistent amount of product, minimizing waste and ensuring accurate application. The product offers refillable bottles and recyclable refill cartridges that underscore Dyson's commitment to sustainability.
Consists of four variations: Straight to Wavy (Light and Rich Conditioning) and Curly to Coily (Light and Rich Conditioning)
Enriched with Chitosan, premium oils such as grapeseed, castor and argan oil, beeswax, and heat protectant properties, it fights frizz & enhances shine
Rich formula transforms from a cream to a sheer serum in the hand, for even application
Wash hair and towel dry
Pump to dispense product
Sheer between palms
Smooth through mid-lengths and ends
Dry and style
This lightweight serum repairs surface damage with amino acids, providing weightless, flexible hold.
Enhanced with Hyaluronic Acid to fight humidity-induced frizz, for softness and shine, and is suitable for all hair types

Dyson Airwrap i.d.™ Multi-Styler and Dryer

Dyson introduces its first connected beauty device, the Dyson Airwrap i.d.™ multi-styler and dryer, which integrates Bluetooth® technology for a more personalized styling experience. This globally acclaimed device now features i.d. curl™, a personalized curling sequence that automates the curling process based on user profile data such as hair type, length, and skill level. With just one push of a button, i.d. curl™ wraps, styles, and sets curls flawlessly while controlling heat and airflow for optimal results. Dyson Airwrap i.d.™ is available in two options based on hair type: Dyson Airwrap ID™ Multi-styler for Curly to Coily Hair T3-4 and Dyson Airwrap ID™ Multi-styler for Straight to Wavy Hair T1-2.

With the launch of Airwrap i.d.™, Dyson introduces three new attachments: the Conical Barrel for tighter, defined curls; the Wave+Curl Diffuser for improved natural curl patterns; and the Blade Concentrator for a smoother finish. With these additions, the multi-styler now offers 19 attachments, making it versatile enough to cater to all hair types without the risk of heat damage. The device uses intelligent heat control to ensure temperatures stay below 302°F, protecting hair from damage and preserving shine.

The Dyson Airwrap i.d.™ will come in several color options including Ceramic Patina and Topaz, Vinca Blue and Topaz, and the special Strawberry Bronze/Blush Pink edition for the 2024 gifting period.

Looking Forward

Dyson's foray into ingredient science with the Chitosan™ range and its advanced styling technology with the Airwrap i.d.™ multi-styler highlight the brand's ongoing commitment to innovation in beauty. With a focus on both technological advancement and sustainable practices, Dyson continues to push boundaries and deliver products that enhance both performance and user experience.

The Dyson Chitosan™ formulations range will be available starting August 15, 2024, with full-size bottles priced at $59.99 and refills at $54.99. Purchase directly from Dyson.com.

The Dyson Airwrap i.d.™ multi-styler and dryer will be available from August 26, 2024, priced at $599.99 and consumers can sign up on Dyson's website to be notified when the product is available.

To buy, learn more and experience the products, visit your local Dyson Demo Store. For more information, visit Dyson.com.

Media Contacts:

For more information, please contact: Sue Chan, [email protected]

About Dyson

Dyson is a global technology company with engineering, research, development, manufacturing and testing operations in Singapore, the UK, Malaysia, Mexico, China and the Philippines. Having started in a coach house in the UK, Dyson has consistently grown since it was established in 1993. Today, it has global headquarters in Singapore and two technology campuses in the UK spanning over 700 acres in Malmesbury and Hullavington. Since 1993, Dyson has invested more than £1bn in its Wiltshire offices and laboratories that house the early-stage research, design and development of future Dyson technology. Dyson remains family-owned and employs 14,000 people globally including a 6,000 strong engineering team. It sells products in 85 markets in over 250 Dyson Demo stores around the world, including a Dyson Virtual Reality Demo Store too.

Dyson is investing £2.75bn in the business to conceive revolutionary products and technologies, and has global teams of engineers, scientists and software developers focused on the development of solid-state battery cells, high-speed digital motors, sensing and vision systems, robotics, machine learning technologies and A.I. investment.

Dyson is also investing half a billion GBP to expand and accelerate its research and technology development across its beauty portfolio, with plans to launch 20 new beauty products in the next four years. Developing technology for all hair types remains a crucial focus for the research and development teams. This investment will create new lab spaces to both sharpen Dyson's understanding of global hair types and damage, while also support the continued diversification of Dyson's beauty technology.

SOURCE Dyson

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Journal of Materials Chemistry B

Injectable and biodegradable collagen–chitosan microspheres for enhanced skin regeneration.

* Corresponding authors

a State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, P. R. China E-mail: [email protected]

b Gansu Engineering Research Center of Medical Collagen, P. R. China

c Cuiying Honors College, Lanzhou University, Lanzhou, P. R. China

Skin aging is influenced by both external environmental factors and intrinsic biological mechanisms. Traditional microsphere implants aim to rejuvenate aging skin through collagen regeneration, yet their non-biodegradability and risk of granuloma formation often limit their effectiveness. In this study, we developed novel, injectable, highly bioactive, and degradable collagen–chitosan double-crosslinked composite microspheres for skin rejuvenation. The microspheres demonstrated excellent injectability, requiring an injection force of only 0.9 N, and significant biodegradability, effectively degraded in solutions containing phosphate buffer, type I collagenase, and pepsin. In addition, the microspheres exhibited excellent biocompatibility and bioactivity, significantly promoting the proliferation, adhesion, and migration of human foreskin fibroblast-1 (HFF-1) cells. In a photoaged mouse skin model, the implantation of microspheres significantly enhanced dermal density and skin elasticity while reducing transepidermal water loss. Importantly, the implant promoted the regeneration of collagen fibers. This study suggests that collagen–chitosan double-crosslinked composite microspheres hold significant potential for skin rejuvenation treatments.

Graphical abstract: Injectable and biodegradable collagen–chitosan microspheres for enhanced skin regeneration

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H. Yan, Q. Wang, W. Li, N. Li, P. Huang and J. Xiao, J. Mater. Chem. B , 2024, Advance Article , DOI: 10.1039/D4TB00537F

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Recent advances of chitosan-based polymers in biomedical applications and environmental protection

Sevda fatullayeva.

Department of Nanostructured Metal-Polymer Catalysts, Institute of Catalysis & Inorganic Chemistry named after academician M.F. Nagiyev, Azerbaijan National Academy of Sciences, AZ1143, H.Javid Ave, 113, Baku, Azerbaijan

Dilgam Tagiyev

Nizami zeynalov, samira mammadova, elmira aliyeva, associated data.

The datasets analysed during the current study are available from the corresponding author on reasonable request.

Interest in polymer-based biomaterials such as chitosan and its modifications and also the methods of their application in various fields of science is uninterruptedly growing. Owing to unique physicochemical, biological, ecological, physiological properties, such as biocompatibility, biodegradability, stability in the natural environment, non-toxicity, high biological activity, economic affordability, chelating of metal ions, high sorption properties, chitosan is used in various biomedical and industrial processes. The reactivity of the amino and hydroxyl groups in the structure makes it more interesting for diverse applications in drug delivery, tissue engineering, wound healing, regenerative medicine, blood anticoagulation and bone, tendon or blood vessel engineering, dentistry, biotechnology, biosensing, cosmetics, water treatment, agriculture. Taking into account the current situation in the world with COVID-19 and other viruses, chitosan is also active in the form of a vaccine system, it can deliver antibodies to the nasal mucosa and load gene drugs that prevent or disrupt the replication of viral DNA/RNA, and deliver them to infected cells. The presented article is an overview of the nowaday state of the application of chitosan, based on literature of recent years, showing importance of fundamental and applied studies aimed to expand application of chitosan-based polymers in many fields of science.

Introduction

Biopolymers, having unique properties, ease of using and processing, variety in combination with economy and environmental friendliness, differ from other classes of materials. These are high molecular weight natural materials that constitute the structural basis of all living organisms and play a significant role in vital processes [ 1 ]. They can be obtained both from living organisms (plants, animals, bacteria, fungi) and by synthesis method. New developments in the production of biopolymers are aimed at using these biomaterials as medical materials, food additives, adsorbents, packaging, cosmetics, fabrics for clothes, chemicals for water purification, industrial plastics, biosensors, etc. [ 2 ].

Production of biodegradable carbohydrate biopolymers, which are both a structural material (cellulose, chitin), an energy reserve (starch, glycogen), and also perform numerous biological functions, shows a special interest [ 3 , 4 ]. Thus, the role of biomaterials synthesized on the basis of carbohydrate biopolymers has been studied in intercellular interactions, cell differentiation, the formation of multicellular systems, the development of malignant neoplasms, etc. [ 5 ]. Cellulose-, chitin-, and chitosan-based materials in the form of fibers, membranes, hydrogels, sponges have been developed and implemented in such important areas as pharmaceuticals, biomedicine, the food industry, etc. [ 6 – 12 ]. The combination of properties such as solubility, viscosity, gelation, mechanical, surface and interfacial properties, composition, degree of polymerization, types of bonds and structure allows to create biomaterials that are promising compounds which meet the requirements of environmental friendliness and economic sustainability for a variety of applications [ 13 ].

The aim of some modern studies is to obtain highly effective drugs with sorption activity towards toxic metals, which are dangerous environmental pollutants that can be accumulated and negatively affect the vital functions of the human organism, leading to various pathologies. From the literature data it is known that enterosorbents (drugs of various structures that bind exo- and endogenous substances in the gastrointestinal tract by adsorption) based on polysaccharides and used for purification and binding of various toxins in the internal medium of the organism are very promising for these purposes [ 14 ]. In addition, these compounds possess a wide range of pharmacological properties. Removal of toxic metals from the organism is one of the important directions of modern science as well. In this regard, our research carried out on synthesis and application of enterosorbents obtained on the base of chitosan and poly-N-vinylpyrrolidone, with the aim of removal of toxic metals from the human organism is very topical and practical; we are going to present the obtained results in our further publications.

The aim of this review is to present the recent scientific advances in properties and applications of various chitosan-based polymers. Synthesis, study and practical application of chitosan-based polymers in many biomedical fields and as the important environmental treatment materials for removal of toxic metals from different media are one of the achievements of scientific progress in the search of new promising materials in recent years.

Production and structure of chitosan

Source and production of chitosan.

Chitosan is produced from chitin, which is present in the bodies of crustacean, molluscs, insects, fungi, etc., by the chemical or enzymatic partial N -deacetylation process [ 15 , 16 ]. Production process of chitosan (Fig. 1 ) consists of deproteinization (heat at 60–100 °C for 1–72 h in the presence of 0.125–2.5 M of NaOH, Na 2 CO 3 , KOH, K 2 CO 3 , Ca(OH) 2 , Na 2 SO 3 ); demineralization (HCl, HNO 3 , H 2 SO 4 , CH 3 COOH and HCOOH at 100 °C for 1–48 h); decolouration (dissolve in organic solvents, bleach with KMnO 4 , heat at 20–60 °C for 0.25–12 h); and deacetylation (30–50% solution of NaOH) [ 17 – 20 ].

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Scheme of chitosan production from chitin [ 21 ]

Structure of chitosan

Chitosan is a natural linear polysaccharide composed of randomly distributed β -(1–4)-linked D -glucosamine and N -acetyl- D -glucosamine (Fig. 2 a), namely it is consisted of two monosaccharide units: 2-amino-2-deoxy- β - D -glucopyranose and 2-acetamido-2-deoxy- β - D -glucopyranose linked by β -(1–4) glycosidic bonds, in which about 50% of the acetyl groups will be removed from the chitin by a hydration process or enzyme hydrolysis [ 22 , 23 ].When the deacetylation degree is higher than 50%, the polymer is called chitosan (in case of less than 50% it is called chitin) [ 24 – 26 ]. To avoid depolymerization and the formation of reactive particles under the influence of oxygen, sodium borohydride is added or the system is purged with nitrogen [ 27 ]. Jang et al. [ 28 ] found that chitosan has α , β and γ crystal structures (Fig. 2 b).

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Structure ( a ) and polymeric forms ( b ) of chitosan

α -Chitosan (main form) has a tight structure with strong intermolecular forces and is formed by two parallel and inversely arranged polysaccharide chains [ 29 ]. β -Chitosan is formed by two parallel and aligned polysaccharide chains with poor intermolecular hydrogen bonds [ 30 ]. γ -Chitosan is composed of three parallel polysaccharide chains, two of which were aligned in the same direction and the other was arranged in the opposite direction [ 31 ]. The sources of α -chitosan are crabs and shrimps, β -chitosan are squids, and γ -chitosan are loligos [ 32 ].

Properties and modifications of chitosan biopolymers

Properties of chitosan biopolymers.

Chitosan is white odourless powder (or flakes) with different molecular weight (MW), degree of deacetylation (DD), insoluble in water and organic solvents, soluble in dilute hydrochloric, formic and acetic acids. Melting point is approximately 290 °C [ 33 , 34 ]. Thus, the reason for the dissolution of chitosan in dilute hydrochloric acid is explained by the interaction of amino groups with hydrogen cations and converting it into a positively charged polyelectrolyte [ 35 , 36 ].

Cations in the composition damage hydrogen bonds among the chitosan molecules, and it leads to dissolving them in water. The solubility of chitosan depends on MW and DD. The higher the DD of chitosan, the higher the degree of protonation of amino groups in the molecule, and the easier it dissolves. The larger MW of chitosan, the large number of hydrogen bonds formed in its polymer chain, and more difficult it dissolves [ 37 , 38 ]. Solubility in water increases, biodegradability and biocompatibility enhance at partial removal of the acetyl groups [ 39 ]. DD and MW greatly determine many properties of chitosan, in particular, antimicrobial and anti-biofilm activities, DD determines chitosan solubility and viscosity [ 40 ]. Therefore, at the application of chitosan biopolymers in practice (for example, as biomaterials, biopesticides, in drug delivery, immunology, etc.), it is necessary to have information about the main characteristics and control some parameters, such as the content of heavy metals, radionuclides, residual protein content, the presence of endotoxins, allergens bacteria and yeast, and other impurities [ 41 ].

Unlike other representatives of polysaccharides (cellulose, pectin, agar, dextran, etc.) chitosan possesses many important properties (Fig. 3 ), including non-toxicity, chelating activities, biocompatibility, biodegradability, adsorption capacities, film-forming ability, bacteriostatic action [ 42 ].

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Various physical and chemical properties of chitosan [ 47 ]

The antiviral, antibacterial activity of chitosan has been proven, the immunostimulating, adjuvant, adaptogenic, antihypoxic, cholestric, radioprotective, hemostatic effects of chitosan and its derivatives have been confirmed [ 43 – 45 ]. The antibacterial effect of chitosan is explained by the interaction of its positively charged amino groups with negatively charged phosphoryl groups of phospholipids of the bacterial cell wall, changes in metabolism, which leads to cell death [ 46 ].

It is known that chitosan is capable of interacting with nucleic acids, which, in turn, leads to the disturbance of synthesis of vital proteins and enzymes, and damaging the structure and function of the bacterial cell [ 48 ]. The fungicidal properties of chitosan are described by identical mechanisms [ 49 ]. The analgesic effect of chitosan has been established due to its ability to absorb bradykinin [ 50 ]. Chitosan sulfate, the structural analogue of chitosan, is similar in structure to the heparin—natural blood anticoagulant [ 51 , 52 ]; the possibility of a synergistic effect of chitosan allows to create the drugs with anticoagulant and anti-sclerotic action [ 53 ]. Furthermore, sulfated chitosan is a natural antioxidant, which absorbs hydroxyl and superoxide anion radicals, and can be a substrate for creating drugs and biologically active additives as well [ 51 , 54 ]. Chitosan can be used for treatment of diabetes because it increases insulin levels [ 55 ]. Possibility of using as a polymer matrix for the delivery and dosage release of drugs and anti-allergic properties of chitosan are proven [ 56 ]. Application of chitosan in immunotherapy is proposed as an antitumor agent that suppresses the growth of tumor cells, pathogens, stimulates humoral and cellular immunity, for gene therapy with the aim of targeted delivery of genetic material [ 45 ]. Chitosan has wound healing properties, stimulates the formation of granulation tissue and the activity of fibroblast proliferation [ 57 , 58 ] and suppresses fibrosis [ 44 ]. Chitosan and its derivatives can be used to create biodegradable carriers of pharmaceuticals in the form of films, which provides the prolonging effect of their action [ 53 , 59 , 60 ].

Modifications of chitosan biopolymers

In order to improve the solubility, rheological properties, thermal stability, and oxidation resistance, chitosan is subjected to chemical modifications (Fig. 4 ) [ 61 ].

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Different modifications of chitosan biopolymers [ 62 ]. Modifications can be used to attach different functional groups and to regulate hydrophobic, cationic and anionic properties of the obtained derivatives of chitosan demonstrating unlimited potential for application in various fields of science

Amino groups, hydroxyl groups at C 3 and C 6 positions are the active groups in the chemical structure of chitosan. As a rule, the NH 2 -amino group is more reactive than the C 6 -OH primary hydroxyl group (due to the free rotation), and the primary hydroxyl group is more reactive than the C 3 -OH secondary hydroxyl group. Chemical modification of chitosan could be carried out on amino, hydroxyl, or both amino and hydroxyl groups to form N -, O - or N,O -modified chitosan derivatives [ 63 , 64 ]. Etherification, esterification, crosslinking, graft copolymerization and O-acetylation are reactions carried out on hydroxyl groups, while acetylation, quaternization, Schiff's base reaction and grafting are carried out on amino groups [ 65 ].

Schiff bases formation reactions

Modifications of chitosan biopolymers via reactions of Schiff bases formation are well-known. Chitosan reacts readily with most aliphatic and aromatic aldehydes to produce Schiff bases—imines. The Schiff base formed after the reaction of aldehyde and chitosan could be reduced by sodium borohydride to synthesize N -derivatives of chitosan [ 66 , 67 ]. They could chelate transition metal ions in aqueous solution to form insoluble metal chelates, which could be separated. This reaction is very useful for the application of chitosan for removal of toxic metals.

Quaternization reactions

Modifications of chitosan biopolymers via quaternization reaction are carried out by means of a free amino group on the chitosan. It includes introduction of quaternary ammonium groups or small molecule quaternary ammonium salts on the amino group of chitosan. These groups have strong hydration ability and large steric hindrance. The quaternized chitosan has increased solubility in water and good antibacterial properties [ 68 – 70 ].

Alkylation and acylation reactions

Modifications of chitosan biopolymers via alkylation and acylation reactions are carried out with halogenated hydrocarbons, anhydrides, acid halides as acylating agents in a certain reaction medium. Synthesized compounds destroy the hydrogen bonds among chitosan molecules, change the original crystal structure, greatly improving the solubility and widening application range of chitosan [ 71 – 74 ].

Carboxylation and carboxymethylation reactions

Modifications of chitosan biopolymers via carboxylation and carboxymethylation reactions involve the introduction of acid groups into the main chain of chitosan in order to improve the solubility, moisturizing and film-forming properties of the compound [ 75 , 76 ]. Carboxymethylation can occur both at the hydroxyl and amino groups of chitosan with the formation of O-carboxymethyl and N-carboxymethyl derivatives, respectively. Carboxymethyl chitosan, a water-soluble anionic polymer was selectively modified to prepare antitumour drug conjugates [ 77 , 78 ], also was reported as a potential vehicle for targeted drug delivery to the liver due to its preferentially located and long retainment in the liver and spleen after intravenous injection [ 79 ]. The modification of chitosan with sugars on amino groups allows to introduce cell-specific sugars recognized by cells, viruses and bacteria into carriers of specific drugs, DNA and antibodies [ 80 , 81 ].

Graft copolymerization reactions

Modifications of chitosan biopolymers via graft copolymerization reaction improve the solubility and biological activity of the polymer [ 82 ] and are used for medical and pharmaceutical applications as orthopedic/periodontal, wound-dressing materials, tissue engineering and controlled drug/gene delivery [ 83 – 86 ]. Based on this modification and a molecular imprinting technique, chitosan could be used for special absorption of template molecules mimicking natural recognition materials such as antibodies for diagnostics [ 87 ]. Recently composites of chitosan with various polymers (polyethylene glycol, polylactic acid, polypyrrole, collagen, starch) and with inorganic materials (bioactive glass, ceramics) have been intensively studied for drug delivery systems, tissue engineering, and other medical applications [ 88 – 91 ]. Hyaluronic acid, alginate, chondroitin sulfate, hydroxyapatite are used with chitosan for preparation of multilayer-structured biomaterials based on the layer-by-layer technique for applications in tissue engineering [ 92 – 96 ].

Cross-linking reactions

Modifications of chitosan biopolymers via cross-linking allow to obtain chitosan derivatives with stable chemical properties, insoluble in acids and bases and which are used as a carrier for the adsorption of drugs, immobilized enzymes, heavy metal adsorbents, etc. Researchers have compared the composition of metal complexes formed by the coordination of chitosan with some heavy metal ions before and after cross-linking. The ability of chitosan to adsorb metal ions was as follows: Hg > Cu > Pb > Zn > Cd > Mn [ 97 ].

Other chemical modifications of chitosan such as esterification, hydroxyalkylation, sulfonation, etc. are known and studied [ 98 – 101 ]. At present, chitosan is also physically modified through mechanical grinding , ionizing radiation and ultrasonic treatment to prepare biomaterials for the various applications [ 102 ].

Recent researches of chitosan biopolymers

The presence of amino and hydroxyl groups in chitosan opens the great opportunities for many industrial and biomedical applications. Use of chitosan biopolymers is uninterruptedly growing in such fields as medicine, pharmaceutical research, paper, textile, agriculture and food industries, cosmetology, tissue engineering, ecology, biotechnology, wastewater treatment (Fig. 5 ). Chitosan-based materials have also found application in veterinary medicine, medical nutrition, production of dietary supplements, biopesticides, biosensors, chromatographic materials [ 103 – 112 ]. The use of chitosan has been described in direct tablet compression, as tablet disintegrant, for the production of controlled release dosage form or for the improvement of drug dissolution [ 113 ].

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Application potential of chitosan. Unique properties of chitosan and its derivatives find the application in various fields of human activity

Application of chitosan biopolymers in biomedical practice

Recent applications are in ophthalmic, nasal, sublingual, buccal, periodontal, gastrointestinal, colon-specific, vaginal, mucosal-vaccine and gene carrier fields. Chitosan, being an adsorbable and nontoxic polymer, is favored in drug delivery because of antiulcer and antacid properties, which help in preventing drug irritation [ 114 , 115 ]. During the last years the use of chitosan composite-based scaffolds as a biomaterial has been reported for tissue engineering [ 116 , 117 ] due to the cationic nature and ability to form interconnected porous structures. Chitosan with other biomaterials such as hydroxyapatite, bioactive glass ceramic are used for bone repair and reconstruction to form a carbonated apatite layer to enhance the mechanical properties [ 118 – 122 ]. Owing to unique properties (toughness, biocompatibility, oxygen permeability) chitosan-based biomaterials in the form of fibers, mats, sponges have been used for burn treatment and wound dressings [ 123 ]. Influence of chitosan biomaterials on the synthesis of collagen for wound healing was studied [ 124 ]. Chitosan has been modified by authors [ 125 ] for using as a dressing material for treatment of wounds and burns. It was found that dressing materials based on chitosan and its modified forms, having haemostatic and analgesic properties, and also possessing properties of high strength, non-toxicity, good water absorption capacity and biocompatibility, together with other polymers (both synthetic and natural) accelerate the process of wound contraction and healing [ 126 ].

Researches carried out in the field of infectious diseases show the effectiveness of the use of chitosan in this area. Systems developed on the base of chitosan with different properties have been proposed [ 127 ]. It has been shown that these systems reduce the side effects of drugs and increase the effectiveness of treatment. Taking account the current situation in the world with COVID-19 and other viruses, chitosan is also active in the form of a vaccine system, for example, it can deliver antibodies to the nasal mucosa and load gene drugs that prevent or disrupt the replication of viral DNA/RNA, and deliver them to infected cells. Further work on the development of systems is proposed that will be widely used in clinical practice, in particular, for the treatment of infectious diseases (Fig. 6 ).

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Applications of chitosan-based biomaterials in infection diseases [ 127 ]. Chitosan biomaterials having good biocompatibility, bioactivity and biosafety, demonstrate great potential in the field of infection control

From year to year, the spread of dangerous pathogenic bacteria is very serious for all mankind and that requires the creation of new materials for the treatment of bacterial infections. Thus, antibacterial and antibiotic properties of the chitosan biomaterial with grafted ferulic acid (CFA) against Listeria monocytogenes (LM), Pseudomonas aeruginosa (PA), and Staphylococcus aureus (SA) were studied [ 128 ]. It was found that CFA exhibits bactericidal action against LM and SA and bacteriostatic action against PA within 24 h of incubation. In dependence on the concentration it suppresses the viability of pathogenic bacteria, which was associated with a change in membrane properties.

Silver nanoparticles functionalized with chitosan (CS-AgNP) using ethanolic buds extract of Sygyzium aromaticum have been studied by authors of the given research [ 129 ]. Decrease in the level of fibrinogen was observed, platelet aggregation was decreased at relatively high concentrations of CS-AgNP. It has been shown, that due to the stable nature, antibacterial, anticoagulant, antiplatelet and thrombolytic activity, CS-AgNP can be used as effective antibacterial agents and anticoagulants with low toxicity in the biomedical field.

The antibacterial efficacy of chitosan has been confirmed as a drug for pulpectomy of infectious teeth [ 130 ]. Chitosan can play an important role in preventive dentistry as an agent to prevent dental diseases (caries, periodontitis), an ingredient in dentifrices (toothpaste, chewing gum) having antibacterial effects, increasing salivary secretion, dental adhesives, etc. [ 131 ]. Blend hydrogels based on poly(vinyl alcohol) and carboxymethylated chitosan were prepared by electron beam irradiation at room temperature. The antibacterial activity of the hydrogels was studied by optical density method. It was found that the hydrogels exhibited satisfying antibacterial activity against E.coli. and can be widely used in the field of biomedicine and pharmacy [ 132 ].

A new antifungal denture base material was proposed by modifying polymethyl methacrylate (PMMA) with chitosan salt (chitosan hydrochloride (CS-HCl) or chitosan glutamate (CS-G)) [ 133 ]. When studying its properties in vitro, the analyses carried out showed that, despite the antifungal effect of CS salts in solution, modification of the PMMA polymer with these CS salts does not improve the antifungal, antibiofilm and antiadhesive properties of the base material of PMMA dentures.

Possible applications of biomaterials based on chitosan, antibiotics and antifungal drugs, considering the factors and mechanisms of the antimicrobial and antifungal action of chitosan, and also clarifying the question of the genetic response of microorganisms to chitosan are described [ 134 , 135 ]. It was established that there are electrostatic interactions between positively charged chitosan and negatively charged cell surface of the microorganism (teichoic acid in gram-positive bacteria, lipopolysaccharide (LPS) in gram-negative bacteria and phosphorylated mannosyl in fungi). In addition, chitosan chelates environmental ions and nutrients which are necessary for the survival of bacteria. It was found that low-molecular-weight chitosan and oligo-chitosan exhibit an extracellular antifungal action, inhibit mitochondrial activity and ATP production, and are also able to penetrate the cell wall, inhibiting DNA/RNA and protein synthesis. The research indicates that despite the fact that chitosan exhibits a high antimicrobial effect, its use on a large scale is limited by some of its properties, such as low solubility in water, lack of a certain molecular weight and purity.

Nanoparticles based on chitosan and its modified forms are widely tested as drug carriers in ophthalmology for the treatment of bacterial and viral infections, glaucoma, age-related macular degeneration and diabetic retinopathy. Authors summarize recent advances in chitosan-based nanotherapy for drug delivery to the eye and the problems that arise during this process [ 136 ]. It has been shown that a high degree of cross-linking in chitosan nanoparticles allows to increase drug retention and facilitates penetration into the eyes.

The following research describes in detail the recent developments of chitosan blends with an emphasis on electrospun nanofibers, which represent a new class of biomaterials, in the field of biomedical applications (drug delivery, wound healing, tissue engineering, biosensing, regenerative medicine) (Fig. 7 ) [ 137 ].

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Electrospun nanofibers [ 137 ] as a novel class of materials that can be used in various biomedical applications

A new method (electrospinning) for the production of chitosan nanofibers with a large surface area and porosity was considered [ 138 ]. Specialists working with this material can optimize the properties of these fibers and expand their range of applications. Thus, it is indicated that the development of complex organ structures will be achieved by the method of electrospinning in combination with 3D printing technology, three-dimensional scaffolds will be designed, integrated with growth factors and cells with high viability. It is noted that despite the fact that specialists were able to simulate the structure and morphology of natural tissue, these studies need further clinical trials until they can be reliably applied in medical practice.

Chitosan-g-poly(acrylic acid)/attapulgite/sodium alginate composites were synthesized as drug delivery matrices [ 139 ]. It was found that the composite hydrogels displayed high pH-sensitivity. The cumulative release ratios of diclofenac sodium from the hydrogel were 3.76% at pH = 2.1 and 100% at pH = 6.8 within 24 h, respectively. It has been noted that such pH-sensitive polymeric materials can be offered for the development of new controlled drug delivery systems.

Hydrogels based on different ratios of chitosan and sodium alginate were synthesized by gamma irradiation in the presence of glutaraldehyde, as a cross-linking agent. It was found that these blend hydrogels exhibited high water swelling and showed high thermal stability. Also, pH responsive release character of ketoprofen drug was studied in this research [ 140 ].

The recent developments in chitosan delivery systems for the treatment of brain tumors and neurodegenerative diseases are presented [ 141 ]. It has been found that chitosan nanoparticles improve therapeutic efficacy in various brain diseases due to their biocompatibility, biodegradability, low toxicity, controlled release, mucoadhesiveness and effective absorption by nasal mucosa and tumor cells. Chitosan nanoparticles are also often used as carriers for the delivery of therapeutic agents, successfully increasing their concentration in the brain, and when administered intranasally chitosan nanoparticles are commonly used to deliver drugs to the brain and can increase nasal residence time and absorption by the nasal mucosa.

It is known that chitosan composites are widely used in medical practice (treatment of burns, artificial kidneys, blood anticoagulation and bone, tendon or blood vessel engineering), and also developed for use in biosensors, packaging, separation processes, food or agricultural industries, and catalytic processes. It is planned to create modulated three-dimensional structures of chitosan using cross-linking processes that improve its use in various fields of medicine, as well as the development of porous catalysts based on chitosan in order to increase the efficiency of catalytic processes by increasing the number of available active sites [ 142 ].

The presence of electron-donating amino and hydroxyl groups allows to use chitosan biopolymers in the separation and purification of biologically active compounds (nucleic acids and products of their hydrolysis, steroids, amino acids). Recent studies have indicated usage of chitosan-based compounds as effective materials to inhibit biofilm formation and attenuate of virulence properties by various pathogenic bacteria [ 143 ].

Application of chitosan biopolymers in environmental protection

Environmental pollution with heavy toxic metals is dangerous for all living organisms. Currently, methods (such as bioadsorption, solvent extraction, remediation by plants and microbial communities, green separation by hydrogel polymers, immobilization, and others) are being developed for the extraction of heavy metals from soil and wastewater. Taking into account the ingestion of heavy metals by humans with food and to prevent serious risks to human health, development of effective methods for removal of heavy toxic metals and to eliminate the toxicity of these metals in air, soil, and water is of great importance. The food chain of the adsorption process of heavy toxic metals by humans is shown in Fig. 8 [ 144 , 145 ].

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Adsorption process of heavy metals from water, soil, air to food chain and finally to human [ 146 ]

In work [ 147 ] it was shown that chitosan hydrolysates obtained by hydrolysis of high-molecular-weight chitosan by the fenton reaction can be used as potent agents that block or form tight complexes with fine dust in the air, containing some solid particles and unknown species of microorganisms. This data can be used in the future for the production of various dust-proof masks and filters for the purpose of human healthcare.

Nanomaterials prepared on the basis of chitosan and its modified forms together with carbon nanotubes have been used as bacterial disinfectors of various pollutants in the field of water purification [ 148 ]. The use of these materials compared to ozonation, chlorination and other disinfection methods has demonstrated the absence of treatment by-products. In the future, the authors plan to develop materials with increased stability and low toxicity, and pay special attention to the design of nanomaterials, which affects the properties and efficiency of the material, in order to eliminate undesired adsorption of biomolecules and increase antibacterial activity.

A promising direction for application of chitosan biopolymers is the sphere of environmental protection, for development of drugs with radioprotective properties, sorbents for the isolation of radionuclides [ 149 ]. Chitosan can also be used as a flocculant for water treatment, surfactants and membranes in ultrafiltration, reverse osmosis and evaporation, purification of industrial effluents containing heavy metal ions [ 150 – 154 ]. Chitosan is capable of forming complexes with transition metals [ 155 , 156 ]. The heavy metal complexes are formed as a result of donation of a nonbonding pair of nitrogen or oxygen electrons on the -NH 2 and/or -OH groups, respectively, to a heavy metal ion. Chitosan granules obtained by cross-linking chitosan with tripolyphosphate have significant adsorption properties towards the metal ions and could be effectively used in wastewater treatment [ 157 – 159 ]. The nature of the cation is very important in the mechanism of interaction; the affinity of chitosan for cations absorbed on film shows selectivity in the following order [ 160 ]:

One of the important applications of chitosan biopolymers is connected with their ability to bind heavy and toxic metal ions. The adsorption capacity values of modified chitosans (MChs) for metal ions removal were reported by Zhang et al. [ 161 ]. It has been noted that adsorption process depends not only on adsorbent structure (modifications of chitosan) but also on conditions of the process (pH, temperature, adsorbent dosage, contact time, co-existing ions). The following results for Cu(II) ions adsorption were observed on various MChs (Table (Table1 1 ).

Experimental conditions and adsorption capacities of MChs for the removal of Cu(II) ions from aqueous solutions [ 161 ]

Modified chitosan	Characterization methods	Amount of Cu(II) mg/g	Optimum conditions
Modified chitosan	Characterization methods	Amount of Cu(II) mg/g	pH	T(K)	contact time(min)
Chitosan/sulfydryl-functionalized grapheme oxide composite	FTIR, TG, SEM, XRD	425.00	2.0	293	30
Carbonaceous sulfur-containing chitosan–Fe(III)	FTIR, SEM, NEXAFS	413.20	6.0	298	15
Chitosan/poly(vinyl amine) composite beads	FTIR	192.57	4.5	298	500
Epichlorohydrin o-crosslinked maleic acyl chitosan adsorbent	FTIR, XRD	132.50	5.0	303	90
Chitosan–epichlorohydrin–triphosphate adsorbent	FTIR, EDS, TGA, DSC	130.72	6.0	298	1800
Grafted chitosan beads	FTIR, SEM	126.00	6.0	303	300
Cross-linked magnetic chitosan-2-aminopyridine glyoxal Schiff's base resin	SEM, FTIR, TGA, XRD	124.00	5.0	303	120
8-Hydroxyquinioline-2-carboxaldehyde chitosan	FTIR, 13C-NMR, DSC, SEM	88.07	5.0	303	360
Chitosan-modified MnFe O nanoparticles	XRD, TEM, FTIR, zeta potential	65.10	6.5	298	500
Epichlorohydrin cross-linked xanthate chitosan	FTIR, 13C-NMR, XPS	43.47	5.0	323	1440
Chitosan/poly(vinyl) alcohol thin adsorptive membranes modified with amino functionalized multiwalled carbon nanotubes	FTIR, SEM, permeability	20.10	5.5	313	240
Chitosan/sporopollenin microcapsules	SEM, FTIR, TGA	1.34	5.5	298	120

Authors of research [ 162 ] developed monodisperse microspheres of chitosan by the microfluidic method and carried out experiments to study the adsorption characteristics to remove copper ions from waste water. The adsorption mechanism was developed based on various adsorption kinetics and isotherms models. The research results showed a high adsorption capacity (75.52 mg/g) and a readsorption efficiency of 74% after 5 cycles. The adsorption capacity in the presence of other competing ions was also studied by the density functional theory (DFT) analysis. It was shown that the most energetically favorable structure of the studied metal complexes is the central model, where metal ions are coordinatedly bound to several amino groups (Fig. 9 ).

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Structures of investigated divalent metal-CS complexes [ 162 ]

Pb(II) imprinted magnetic biosorbent was prepared by means of lead ion imprinting technology and cross-linking reactions between chitosan, Fe 3 O 4 and Serratia marcescens in order to remove of Pb 2+ ions. The influence of solution pH, adsorbent dosage, selectivity of sorption and desorption processes were studied on the adsorption of lead ion. Kinetics and thermodynamics of adsorption process were investigated and adsorbent was studied by XRD, VSM, SEM, EDS, FTIR, XPS and BET analyses. It has been established that nitrogen of amino group and oxygen of hydroxyl group in Pb(II) imprinted magnetic biosorbent were coordination atoms [ 163 ].

A method of heavy metal ions removal by bioadsorption with hybrid 3D printing technology was proposed [ 164 ]. For this purpose, 3D chitosan composite of a monolithic structure of reusable application was prepared, which showed high efficiency in contrast to conventional biosorbents. The adsorption capacity of this material was about 13.7 mg/g at T = 25 °C and pH = 5.5. The analyses performed showed that the –NH 2 and –OH functional groups of chitosan are actively involved in the adsorption process, which indicates the possibility of this sorbent using to remove numerous metal ions from different solutions.

In work [ 165 , 166 ] recent data on removal of lead (Pb), cadmium (Cd), mercury (Hg) and arsenic (As) by chitosan-based magnetic adsorbents from various aqueous solutions are presented. It has been shown that these adsorbents have a high adsorptive capacity towards toxic metals and can be reused in consecutive adsorption–desorption cycles. Langmuir isotherm model confirms good monolayer capacity values of 341.7 mg/g for lead, 152 mg/g for mercury, 321.9 mg/g for cadmium and 65.5 mg/g for arsenic (Fig. 10 ).

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Mechanism of monolayer chemical adsorption of toxic metal ions on the surface of chitosan-based magnetic adsorbent [ 165 ]. Metal ions, marked by red circles, are gradually adsorbed on the surface of the magnetic adsorbent

Removal of cadmium ions from waste water was studied using polypropylene/sisal fiber/banana fiber (PP/SF/BF) and chitosan/sisal fiber/banana fiber (CS/SF/BF) composite materials as adsorbents. It has been established that sorption capacity of CS/SF/BF composite (419 mg/g) is higher than PP/SF/BF composite (304 mg/g), and permits multilayer adsorption. The carried out tests have shown that adsorption process was best satisfied with the Freundlich isotherm [ 167 ].

Modified chitosan-based nanocomposites (MCS/GO-PEI) were prepared for removal toxic heavy metals and organic compounds from environmental water. The results of research showed that sorption process was characterized by pseudo-second-order kinetic and Langmuir isotherm model. High adsorptive capacities of these samples for arsenic, mercury ions, congo red, amaranth (220.26, 124.84, 162.07, 93.81 mg/g, respectively) were presented and the possibility of re-using these nanocomposites as promising adsorbents was shown [ 168 ]. Preparation of graphene oxide/chitosan (GO/CS) composites as new promising sorbent materials for removal of heavy metal ions, dyes and other organic molecules from aquatic environment is presented in paper [ 169 , 170 ]. Sorption of copper (II), cobalt (II) and iron (III) ions, using chitosan composite sponges prepared by ice-segregation procedure, was studied for purification of waste water [ 171 ]. It has been determined that iron (III) ions were mainly adsorbed from two-component mixtures with cobalt (II) ions at pH = 4, whereas copper (II) ions were removed from two-component mixtures with cobalt (II) ions at pH = 6. Carried out experiments showed high chemical stability and reusability of these sponges in sorption–desorption processes.

Nitrogen-enriched chitosan-based activated carbon biosorbent was prepared for separation of Cr(VI) and Pb(II) ions from contaminated water. Thermodynamic parameters have been studied, and kinetics of adsorption of these metal ions is well-fitted by a pseudo-second-order model. High efficiency, availability, recyclability, and cost effectiveness make it possible to use this biosorbent for wastewater treatment [ 172 , 173 ].

Magnetic phosphorylated chitosan composite (P-MCS) as an adsorbent for Co(II) ions was prepared by authors [ 174 ]. Adsorption capacity for Co(II) was equal to 46.1 mg/g. Adsorption isotherms and kinetic models of these ions well fitted the Langmuir model and the pseudo-second-order model, respectively. The carried out experiments have shown dependence of Co(II) adsorption process on surface chelation between functional groups and metal ions, and possibility of use P-MCS for treatment of wastewater.

In order to eliminate the limitations in the use of chitosan as an adsorbent for the removal of heavy metals, such modifications as cross-linking, grafting, and the use of magnetic chitosan (modified with Fe 3 O 4 ) were carried out [ 175 ]. It was suggested in further studies to focus attention on: issues of regeneration and desorption; replacing glutaraldehyde and epichlorohydrin as crosslinking agents with less toxic ones; the use of an adsorbent that does not depend on pH; the use of various optimization tools (for example, the response surface methodology) and other issues in order to use chitosan on an industrial scale.

New class of crystalline porous composite consisting of metal ions and multidentate organic ligands is metal organic framework (MOF), which showed an appreciable capability in wastewater treatment for the removal of heavy metal ions. Functionalization of chitosan with ionic liquids (new class of salts with combination of organic and inorganic ions and with very unique and novel properties) was found to have increased adsorption capacity. They are immobilized on a solid support or they chemically react due to their high reactivity in adsorption process. Analyses carried out in work [ 176 ] showed that introduction of ionic liquids in chitosan improves thermal stability and heavy metal uptake properties.

Chitosan conjugated magnetite nanoparticle (CH-MNP) as an effective adsorbent was synthesized for the removal of Pb(II) ions by means of controlled co-precipitation technique and studied by response surface methodology (RSM) for optimization of process parameters [ 177 ]. Optimum value of pH, adsorbent concentration and contact time were obtained as 5.1, 1.04 g/L, and 59.9 min, respectively. Adsorption isotherm data were correlated well with the Langmuir adsorption isotherm model, and the equilibrium data followed the pseudo-second-order kinetics and intraparticle diffusion kinetic model.

New EDTA modified γ-MnO 2 /chitosan/Fe 3 O 4 nanocomposite was produced for the removal of heavy ions from aqueous solutions. Experiments data have been shown high adsorption capacities for Pb(II) and Zn(II) (310.4 and 136 mg/g, respectively). Results of thermodynamic tests (ΔG° < 0, ΔH° > 0, and ΔS° > 0) showed that the nature of adsorption by this nanocomposite for Pb(II) and Zn(II) ions is spontaneous and endothermic, and is favored at higher temperatures [ 178 ].

Adsorption and removal of chromium (VI) ions from aqueous solutions, using chitosan hydrogel cross-linked with polyacrylic acid and N, N'-methylenebisacrylamide, has been studied in paper [ 173 ]. Evaluation of adsorption mechanism was carried out using Langmuir, Freundlich, Redlich-Peterson, and Sips nonlinear isotherms. The removal of chromium (VI) at pH 4.5 and an initial metal concentration of 100 mg/L was 94.72%. It was proposed to use chitosan hydrogel as an economical and environmentally friendly adsorbent of heavy metal ions for water and wastewater treatment.

A new efficient method of adsorption and removal of heavy metal ions with electric field-driven from wastewater has been proposed [ 179 ]. A composite adsorbent based on chitosan (CS) and sodium phytate (SP) deposited on a polyethylene glycol terephthalate (PET) material was used and placed near the cathode in a pair of titanium plate electrodes. Experiments have shown that the rate of copper ions removal adsorbed on the CS-SP/PET adsorbent increased from 56 to 88% for 10 mg Cu (II) solution per liter when the applied voltage was from 0 to 1.2 V (energy consumption was economical). The adsorption mechanism was correlated to the Langmuir isotherm model and the kinetic equation of the pseudo-second order.

Chitosan and silica gel-based composite was prepared with the purpose to study the adsorption of heavy metal ions in various solutions [ 180 ]. This composite was studied by FTIR and SEM–EDS methods in order to obtain information about the presence of active sites and surface morphology. The study of the adsorption process by this material showed the maximum percentage of removal of Cu (89.78%), Pb (96.9%) and Ni (69.33%) at pH = 5, Hg (92.78%) at pH = 6 with adsorbent mass of 1.5 g, temperature 30 °C and 120 min contact time. Adsorption of Pb is best satisfied to pseudo-first order, whereas pseudo-second order is best fitted to the adsorption of Cu, Ni and Hg. Obtained values of change in enthalpy testify to the effect that both physical and chemical adsorption occur in this process.

A highly adsorptive cross-linked carboxymethyl chitosan (CMC)/2,3-dimethoxybenzaldehyde Schiff base complex was synthesized for removal of heavy metals such as lead (II) and cadmium (II) ions from aqueous solutions and characterized using FTIR, XRD and SEM analysis [ 181 ]. It was confirmed that adsorption follows the Freundlich model and the pseudo-second order kinetic model. The cross-linked Schiff base has been found to be an effective, environmentally friendly and inexpensive adsorbent.

Development of a new economical and environmentally friendly chitosan nanoadsorbent has been proposed for water purification [ 182 ]. Use of inorganic nanomaterials, agricultural waste, adsorbents based on polymer nanocomposites for removing of heavy metal ions such as Hg (II), Cu (II), Cr (VI), Zn (II), Co (II), Cd (II), Pb (II) from wastewater has been studied. Experiments have shown that polymer-based materials have a strong chelating ability towards heavy metal ions, fast adsorption kinetics, and are well regenerated due to the synergistic effect of polymers and various nanofillers present in nanocomposites.

Hydrogels based on different ratios of carboxymethyl cellulose (CMC) and carboxymethyl chitosan (CMCh) and prepared by γ-irradiation showed high adsorption capacities for Pb and Au ions. It has been established that the effective sorption of these metal ions occurred with amino groups of the hydrogel with (CMC/CMCh) composition of 75/25 or 50/50. Properties of the obtained hydrogels (gel fraction, swelling ratio, gel strength) were also studied [ 183 ].

Carboxymethylated chitosan hydrogels were obtained by γ-ray irradiation crosslinking method. Kinetic studies of sorption process were carried out with a purpose to determine favourable conditions for the adsorption of Fe(III) ions on these hydrogels and showed that maximum uptake of Fe(III) ions was equal to 18.5 mg/g at pH = 4.7 [ 184 ]. Favorable adsorption behavior was explained due to the coordination of Fe(III) ions with amino, hydroxyl and carboxyl groups in the structures of the proposed hydrogels.

Application of chitosan biopolymers in other spheres

Chitosan is widely used in cosmetology as a moisturizer, emulsifier, antistatic, emollient for hair and skin care. Chitosan biopolymers are polycation hydrocolloids that become viscous at interaction with acid and can act as abrasive film formers interacting with integuments and hair. Its use as an antioxidant agent and gelling agent in the food industry has also been proven [ 185 , 186 ]. This biopolymer is used as a food wrap owing to its ability to form semipermeable tough, long-lasting, flexible films, thus extending the shelf life of food [ 187 , 188 ], inhibiting microbial growth [ 189 , 190 ]. Chitosan has been used in agriculture as antifungal agents and also to accelerate the growth of plant and decelerate root knot worm infestations [ 191 ].

In the paper and textile industry, chitosan is applied to cellulose fiber during the formation of paper, while the strength of the paper sheet is significantly increased, the resistance to bursting, tearing, and image stability are improved. Chitosan is used to improve the dyeing quality of fabrics made from various fibers. There are known data on the use of this biopolymer for the preparation of antistatic, stain-resistant, printing and finishing materials, for the removal of dyes and the manufacture of textile seams, threads and fibers as well [ 192 ].

Commercial chitosan products

Chitosan can be produced from different sources and the most traditional source of chitosan is from waste crustaceans’ shells from the seafood processing industry, such as crab or shrimp shells. While research has indicated the availability of other sources, these are currently the most sources actively explored on a commercial scale. Chitosan market volume is expected to reach 2.55 × 10 9 US dollar by 2022. Although many articles have been published during the last twenty years, chitosan applications in the biomedical field are still limited, mainly due to the difficulty of obtaining of the biopolymer with high purity and reliability at its source. Furthermore, production of new chitosan-based materials is quite limited, mainly due to their cost, which remains higher than that of petroleum-based polymers with similar properties [ 131 ]. It is required to develop more economical and environmentally friendly methods in order to obtain chitosan and convert it into useful products. On the other hand, the production cost of crustaceans based chitosan is cheap compared with fungal based chitosan. Crustaceans raw materials are readily available and cheap whereas the cost of raw materials is the main bottleneck for fungal chitosan production. Crustaceans chitosan can be found from 10 US dollar per kg to 1000 US dollar per kg. It also depends on product quality and application [ 193 ].

It should be noted that some commercial products of chitosan are known in the world market. Different forms of chitosan-based materials are used as wound dressing (HemCon® Bandage, ChitoGauze® PRO, ChitoFlex® PRO, ChitoSam™, Syvek-Patch®, Chitopack C® and Chitopack S®, Chitodine®, ChitosanSkin®, TraumaStat®, TraumaDEX®, Celox™), as hemostatic sealants (ChitoSeat™) in biomedical practice. Reaxon® (Medovent, Germany) is a chitosan-based nerve conduit which is resistant to destruction, prevents irritation, inflammation and infection, inhibits scar tissue and neuroma formation. Chitosan-based nutritional supplements (Epakitin™, Nutri + Gen®) are commercially available for use in chronic kidney disease in pets. Various chitosan-based products (ChitoClear®, Chitoseen™-F, MicroChitosan NutriCology®, etc.) are for sale as safe weight loss supplement, cholesterol-reducing agents, and also as antioxidant agents.

Many chitosan-containing products (Curasan™, Hydamer™, Zenvivo™, Ritachitosan®, Chitosan MM222, Chitoseen™-K, ChitoCure®, ChitoClear®, etc.) are also commercially available for cosmetic and hygienic usage. [ 131 ].

At present, chitosan due to the availability, renewability of raw material and the unique properties is a subject of researches and is widely used in various fields of biotechnology, medicine, pharmacy and industry.

In the coming years, demand for polymer-based biomaterials with better performance will be unquestionably the highest. Distribution of chitosan-based biomaterials at the larger scale can contribute as a sustainable and renewable material for the scientific developments in future. Furthermore, in the past decade in various fields of researches significant advancement has submitted but is still incomplete and applications of chitosan in the biomedical area are still limited. There are still many unresolved issues and challenges. Bioactivity of chitosan-based polymers has been studied for many years, however, the structure activity relationship and the mechanism of activity needs further investigation. This might be connected with poor bioavailability, and lacked of human clinical trials, and all these factors required further analysis.

At present time, there is not enough literature information on the application of polymer-based enterosorbents in medical practice, which is considered as one of the promising directions in the treatment and prevention of diseases of various etiologies [ 194 , 195 ]. Preparation and application of enterosorbents reduces the intensity of antibiotic and hormone therapy. The development of this direction depends on both technological possibilities and the state of the environment.

Author contribution

All authors contributed to the study conception and design. Material preparation and analysis were performed by [Sevda Fatullayeva], data collection by [Samira Mammadova] and [Elmira Aliyeva], review and editing by [Nizami Zeynalov] and [Dilgam Tagiyev]. The first draft of the manuscript was written by [Sevda Fatullayeva] and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

The authors declare that no funds, grants, or other support were received during the preparation of this manuscript.

Data availability

Declarations.

The authors have no relevant financial or non-financial interests to disclose.

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Contributor Information

Sevda Fatullayeva, Email: moc.liamtoh@aveyallutafaves .

Dilgam Tagiyev, Email: ur.relbmar@veyigatd .

Nizami Zeynalov, Email: moc.liamg@3imazinvolanyez .

Samira Mammadova, Email: ur.liam@m_arimas .

Elmira Aliyeva, Email: ur.tsil@48aveyilaarimle .

IMAGES

Chitosan: A Potential Biopolymer in Drug Delivery and Biomedical Applications
An Overview, Properties and Biomedical Applications of Chitosan
Chitin and Chitosan Production from Mushrooms
Chitosan application as a material dedicated to medicine.
Molecular weight of different types of chitosan.
Chitosan and Chitosan Modified by Functionalization

COMMENTS

Chitosan: An Overview of Its Properties and Applications
However, chitosan potentiality is somehow hindered by the inconsistency in the research data and the lack of knowledge in the ultimate mechanism underlying the properties of chitosan. Between 2011-2020, the number of publications on chitosan has displayed a steady growth.
Chitosan: A review on properties, biological activities and recent
Chitosan is a naturally occurring amino polysaccharide obtained by deacetylation of chitin and is second most commonly used natural polymer. Its non-toxic, biocompatibility and biodegradability properties have prompted extensive research into several applications.
Chitosan: An Update on Potential Biomedical and Pharmaceutical
Chitosan is a biodegradable and inexpensive polymer which has numerous applications in biomedical as well as pharmaceutical industries. A large amount of research work has been done on chitosan and its derivatives for the purpose of tissue engineering, drug delivery, wound healing, water treatment, antitumor and antimicrobial effects.
Chitosan: A Natural Biopolymer with a Wide and Varied Range of
In another research, chitosan was cross-linked with glutaraldehyde to the immobilization of Pd 2+-species in its structure, reaching yields very close to 100% (Figure 15) . Other authors also synthesized proline-loaded chitosan beads and gelatin chitosan beads by cross-linking with similar results in couplings reactions of iodo- and bromoarenes ...
Chitosan: An Overview of Its Properties and Applications
Abstract. Chitosan has garnered much interest due to its properties and possible applications. Every year the number of publications and patents based on this polymer increase. Chitosan exhibits poor solubility in neutral and basic media, limiting its use in such conditions. Another serious obstacle is directly related to its natural origin.
A comprehensive review of chitosan applications in paper science and
Chitosan is a linear biodegradable natural carbohydrate polymer that is comprised of β (1→4)-linked 2-amino-2-deoxy-β-d-glucose units.The presence of amino groups in the chemical structure of chitosan makes it soluble in acidic solutions with pH values below about 6 (Fig. 1).Such conditions lead to protonation of the amino groups, which consequently gives chitosan its cationic characteristics.
Antimicrobial properties of chitosan from different ...
This is the first research that investigated the antibacterial activity of chitosan produced from the three developmental stages of H. illucens through qualitative and quantitative analysis, agar ...
Antimicrobial Chitosan and Chitosan Derivatives: A Review of the
This review gives an updated overview of the current state-of-the-art for antimicrobial chitosan and chitosan derivatives and the effects of structural modifications on activity and toxicity. The various synthetic routes introduced for chemical modification of chitosan are discussed, and the most common functional groups are highlighted. Different analytical techniques used for structural ...
Artificial intelligence-based optimization for chitosan ...
The ζ-potential of the chitosan nanoparticles was quantified utilizing a Malvern 3000 Zetasizer Nano ZS, UK at "Central Laboratories, City of Scientific Research and Technological Applications ...
Chitosan: A review of sources and preparation methods
DD is a critical parameter of chitosan, as prior research has reported that chitosan with a higher DD demonstrates stronger biological effects as well as increased water solubility [3].This is because a higher DD indicates a higher concentration of amino groups in the molecule, and the protonation of the -NH 2 functional group is vital for manifesting chitosan's biological effects and water ...
Chitin and Chitosan: Structure, Properties and Applications in
Chitin and chitosan have some special properties that make them suitable for versatile applications. But the use of chitin and chitosan in medical and pharmaceutical sector has grown rapidly and currently received a great deal of interest from the researchers throughout the globe due to their interesting properties such as strong antibacterial effect, biocompatibility, biodegradability, non ...
Chitin and chitosan derived from crustacean waste valorization ...
Fig. 2: Growth in chitin and chitosan research projects, publications and patents from 2000 to 2022. a, The global landscape of chitin- and chitosan-based publications ...
Chitosan: Derivatives, Properties and Applications
In cosmetics, chitosan-based lotions, creams, and other personal care products are gaining popularity due to their excellent moisture-retaining ability and biocompatibility. In the water treatment industry, chitosan is studied by many research groups as an effective bio-coagulant and bio-flocculent to remove various types of contaminants.
Chitosan: Sources, Processing and Modification Techniques
Chitosan is a copolymer composed of glucosamine and N-acetyl glucosamine derived from chitin. ... Given chitosan's rapidly increasing industrial importance and ongoing intensive research, this review summarizes ongoing research in exploiting different sources of chitosan, extraction techniques and highlights some of the exploited functional ...
Chitosan: An Overview of Its Properties and Applications
Chitosan has garnered much interest due to its properties and possible applications. Every year the number of publications and patents based on this polymer increase.
Chitin and Chitosan: Production and Application of Versatile Biomedical
Chitin, which occurs in nature as ordered macrofibrils, is the major structural component in the exoskeletons of the crustaceans, crabs and shrimps, as well as the cell walls of fungi. For biomedical applications chitin is usually converted to its deacetylated derivative, chitosan ( 1 ). Chitin and chitosan are both biocompatible, biodegradable ...
Chitosan
Chitosan / ˈ k aɪ t ə s æ n / is a linear polysaccharide composed of randomly distributed β-(1→4)-linked D-glucosamine (deacetylated unit) and N-acetyl-D-glucosamine (acetylated unit). It is made by treating the chitin shells of shrimp and other crustaceans with an alkaline substance, such as sodium hydroxide. [1] [2]Chitosan has a number of commercial and possible biomedical uses.
Chitin and Chitosan: Production and Application of Versatile ...
Chitosan can be successfully used in solution, as hydrogels and/or nano/microparticles, and (with different degrees of deacetylation) an endless array of derivatives with customized biochemical properties can be prepared. As a result, chitosan is one of the most well-studied biomaterials. The purpose of this review is to survey the biosynthesis ...
(PDF) Chitosan
Chitin is the most abundant natural amino polysaccharide and is next to cellulose in abundance on. the planet. Chitosan is obtained by deacetylation of chitin. Chitosan is being researched by ...
Chitosan as a Biomaterial
The chitosan used in industrial or research applications is typically derived from chitin through the use of chemical or enzymatic treatments . Chitosan is a copolymer of N-acetyl-D-glucose amine and D-glucose amine as shown in figure 2 .It is a linear and semicrystals polymer [ 5 , 6 ] chitosan has de acetylation degree at least 60% of glucose ...
Chitosan: Are the Health Claims True for This Popular Supplement?
Avoid using chitosan if you're allergic to shellfish, mushrooms, or any other substance in the ingredients list. You should talk with a healthcare provider about using chitosan if you're pregnant or breastfeeding. There isn't much research on the use of chitosan in these populations, so it may be best to avoid it.
Chitosan as a bioactive polymer: Processing, properties and
Chitosan is a bioactive polymer with a wide variety of applications due to its functional properties such as antibacterial activity, non-toxicity, ease of modification, and biodegradability. ... further research is needed in order to analyze the feasibility of other manufacture processes to scale-up the production of CS films [30].
Encapsulation of Pomelo Peel Essential oil (Citrus maxima) Using the
Research results on the effect of concentration and pH of chitosan solution were consistent with the report by Bastos et al (2018), with the appropriate pH range of chitosan used in the microencapsulation process being pH 4 ‒ 5. 37 Therefore, a chitosan solution with a concentration of 2% (w/v based on the volume of mixture) and a pH value of ...
Dyson launches its first-ever hair-care range, Dyson Chitosan
A new frontier for the brand, which has never touched the world of formulation before, Dyson Chitosan draws on 10 years of research into hair health and the science behind lasting styles.
Chitosan: An Overview of Its Properties and Applications
Chitosan has garnered much interest due to its properties and possible applications. Every year the number of publications and patents based on this polymer increase. Chitosan exhibits poor solubility in neutral and basic media, limiting its use in such conditions. Another serious obstacle is directly related to its natural origin. Chitosan is not a single polymer with a defined structure but ...
Chitosan: Sources, Processing and Modification Techniques
Chitosan, a copolymer of glucosamine and N-acetyl glucosamine, is derived from chitin. Chitin is found in cell walls of crustaceans, fungi, insects and in some algae, microorganisms, and some invertebrate animals. Chitosan is emerging as a very important raw material for the synthesis of a wide range of products used for food, medical, pharmaceutical, health care, agriculture, industry, and ...
Chitosan: An overview of biological activities, derivatives, properties
There are various past research on chitosan's cell death, notably regarding the link between cell death and molecular size. 2.1.3. PPC (physicochemical properties of chitosan) under LMWC. The PPC of the original chitosan and low molecular weight chitosan are largely same. It is a high-nitrogen linear amino polysaccharide [40]. The base has a ...
Dyson takes its next step into the world of beauty with its first ever
Through research, Dyson sourced a version of chitosan from oyster mushrooms. Chitosan is a complex macromolecule that is found in the cell walls of the mushroom. Delicate yet strong, it's what ...
Injectable and biodegradable collagen-chitosan microspheres for
b Gansu Engineering Research Center of Medical Collagen, ... In this study, we developed novel, injectable, highly bioactive, and degradable collagen-chitosan double-crosslinked composite microspheres for skin rejuvenation. The microspheres demonstrated excellent injectability, requiring an injection force of only 0.9 N, and significant ...
Recent advances of chitosan-based polymers in biomedical applications
The following research describes in detail the recent developments of chitosan blends with an emphasis on electrospun nanofibers, which represent a new class of biomaterials, in the field of biomedical applications (drug delivery, wound healing, tissue engineering, biosensing, regenerative medicine) (Fig. 7) .

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Chitosan as a Biomaterial — Structure, Properties, and Electrospun Nanofibers

Concepts, Compounds and the Alternatives of Antibacterials

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E.M.R. El- Zairy

1. Introduction

2. Chitosan

2.1. The relationship between structure and properties

2.2. Chitin and chitosan production

3. Chitosan as biomaterial

4. Applications of chitosan and chitosan derivatives

4.1. Agricultural applications

4.2. Wastewater treatment applications

4.3. Food industry applications

4.4. Medical applications

5. Electrospinning of chitosan

5.1. History of electrospinning

5.2. Electrospinning process

5.3. Effects of various parameters on electrospinning

5.4. Solvents used for electrospinning

6. Electrospinning of chitosan solutions

7. Nanofibers produced by electrospinning

7.2. Nanofiber properties

7.3. Nanofiber applications

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