Chitin and Chitosan as Multipurpose Natural Polymers for Groundwater Arsenic Removal and As2O3 Delivery in Tumor Therapy

Chitin and chitosan are natural polysaccharide polymers. These polymers have been used in several agricultural, food protection and nutraceutical applications. Moreover, chitin and chitosan have been also used in biomedical and biotechnological applications as drug delivery systems or in pharmaceutical formulations. So far, there are only few studies dealing with arsenic (As) removal from groundwater using chitin or chitosan and no evidence of the use of these natural polymers for arsenic trioxide (As₂O₃) delivery in tumor therapy. Here we suggest that chitin and/or chitosan might have the right properties to be employed as efficient polymers for such applications. Besides, nanotechnology offers suitable tools for the fabrication of novel nanostructured materials of natural origin. Since different nanostructured materials have already been employed successfully in various multidisciplinary fields, we expect that the integration of nanotechnology and natural polymer chemistry will further lead to innovative applications for environment and medicine.     

Chitin Research Revisited

Two centuries after the discovery of chitin, it is widely accepted that this biopolymer is an important biomaterial in many aspects. Numerous studies on chitin have focused on its biomedical applications. In this review, various aspects of chitin research including sources, structure, biosynthesis, chitinolytic enzyme, chitin binding protein, genetic engineering approach to produce chitin, chitin and evolution, and a wide range of applications in bio- and nanotechnology will be dealt with.     

Chitosan: An Update on Potential Biomedical and Pharmaceutical Applications

Chitosan is a natural polycationic linear polysaccharide derived from chitin. The low solubility of chitosan in neutral and alkaline solution limits its application. Nevertheless, chemical modification into composites or hydrogels brings to it new functional properties for different applications. Chitosans are recognized as versatile biomaterials because of their non-toxicity, low allergenicity, biocompatibility and biodegradability. This review presents the recent research, trends and prospects in chitosan. Some special pharmaceutical and biomedical applications are also highlighted.     

Chitosan composites for bone tissue engineering--an overview

Bone contains considerable amounts of minerals and proteins. Hydroxyapatite [Ca₁₀(PO₄)₆(OH)₂] is one of the most stable forms of calcium phosphate and it occurs in bones as major component (60 to 65%), along with other materials including collagen, chondroitin sulfate, keratin sulfate and lipids. In recent years, significant progress has been made in organ transplantation, surgical reconstruction and the use of artificial protheses to treat the loss or failure of an organ or bone tissue. Chitosan has played a major role in bone tissue engineering over the last two decades, being a natural polymer obtained from chitin, which forms a major component of crustacean exoskeleton. In recent years, considerable attention has been given to chitosan composite materials and their applications in the field of bone tissue engineering due to its minimal foreign body reactions, an intrinsic antibacterial nature, biocompatibility, biodegradability, and the ability to be molded into various geometries and forms such as porous structures, suitable for cell ingrowth and osteoconduction. The composite of chitosan including hydroxyapatite is very popular because of the biodegradability and biocompatibility in nature. Recently, grafted chitosan natural polymer with carbon nanotubes has been incorporated to increase the mechanical strength of these composites. Chitosan composites are thus emerging as potential materials for artificial bone and bone regeneration in tissue engineering. Herein, the preparation, mechanical properties, chemical interactions and in vitro activity of chitosan composites for bone tissue engineering will be discussed.     

Chitosan Modification and Pharmaceutical/Biomedical Applications

Chitosan has received much attention as a functional biopolymer for diverse applications, especially in pharmaceutics and medicine. Our recent efforts focused on the chemical and biological modification of chitosan in order to increase its solubility in aqueous solutions and absorbability in the in vivo system, thus for a better use of chitosan. This review summarizes chitosan modification and its pharmaceutical/biomedical applications based on our achievements as well as the domestic and overseas developments: (1) enzymatic preparation of low molecular weight chitosans/chitooligosaccharides with their hypocholesterolemic and immuno-modulating effects; (2) the effects of chitin, chitosan and their derivatives on blood hemostasis; and (3) synthesis of a non-toxic ion ligand—D-Glucosaminic acid from Oxidation of D-Glucosamine for cancer and diabetes therapy.     

Synthesis and Characterization of 2-Decenoic Acid Modified Chitosan for Infection Prevention and Tissue Engineering

Chitosan nanofiber membranes are recognized as functional antimicrobial materials, as they can effectively provide a barrier that guides tissue growth and supports healing. Methods to stabilize nanofibers in aqueous solutions include acylation with fatty acids. Modification with fatty acids that also have antimicrobial and biofilm-resistant properties may be particularly beneficial in tissue regeneration applications. This study investigated the ability to customize the fatty acid attachment by acyl chlorides to include antimicrobial 2-decenoic acid. Synthesis of 2-decenoyl chloride was followed by acylation of electrospun chitosan membranes in pyridine. Physicochemical properties were characterized through scanning electron microscopy, FTIR, contact angle, and thermogravimetric analysis. The ability of membranes to resist biofilm formation by S. aureus and P. aeruginosa was evaluated by direct inoculation. Cytocompatibility was evaluated by adding membranes to cultures of NIH3T3 fibroblast cells. Acylation with chlorides stabilized nanofibers in aqueous media without significant swelling of fibers and increased hydrophobicity of the membranes. Acyl-modified membranes reduced both S. aureus and P. aeruginosa bacterial biofilm formation on membrane while also supporting fibroblast growth. Acylated chitosan membranes may be useful as wound dressings, guided regeneration scaffolds, local drug delivery, or filtration.     

Antimicrobial properties of chitosan nanoparticles: Mode of action and factors affecting activity

The present investigation describes the synthesis and characterization of novel biodegradable nanoparticles based on chitosan for biomedical applications. The presence of primary amine groups in repeating units of chitosan grants it several properties like antibacterial activity, antitumor activity and so on. Chitosan forms nanoparticles spontaneously on the addition of polyanion tripolyphosphate which has greater antimicrobial activity than parent chitosan. In the present study, chitosan nanoparticles (ChNP) were prepared by the ionic gelation method. The physiochemical characteristics of nanoparticles were analyzed using XRD, SEM, FTIR. The antibacterial activity of chitosan nanoparticles against medical pathogens Klebsiella pneumoniae, Escherichia coli, Staphylococcus aureus and Pseudomonas aeruginosa was evaluated by calculation of minimum inhibitory concentration (MIC) and compared with chitosan and chitin activity. The mode of action and factors affecting antibacterial activity were also analyzed. ChNP compounds exhibited superior antimicrobial activity against all microorganisms in comparison with chitosan and chitin. The antibiofilm activity was studied using crystal violet assay and growth on congo red agar. The study is thus a good demonstration of the applicability of chitosan nanoparticles as an effective antimicrobial agent with antibiofilm activity as well.     

Biomedical exploitation of chitin and chitosan via mechano-chemical disassembly, electrospinning, dissolution in imidazolium ionic liquids, and supercritical drying

Recently developed technology permits to optimize simultaneously surface area, porosity, density, rigidity and surface morphology of chitin-derived materials of biomedical interest. Safe and ecofriendly disassembly of chitin has superseded the dangerous acid hydrolysis and provides higher yields and scaling-up possibilities: the chitosan nanofibrils are finding applications in reinforced bone scaffolds and composite dressings for dermal wounds. Electrospun chitosan nanofibers, in the form of biocompatible thin mats and non-wovens, are being actively studied: composites of gelatin + chitosan + polyurethane have been proposed for cardiac valves and for nerve conduits; fibers are also manufactured from electrospun particles that self-assemble during subsequent freeze-drying. Ionic liquids (salts of alkylated imidazolium) are suitable as non-aqueous solvents that permit desirable reactions to occur for drug delivery purposes. Gel drying with supercritical CO(2) leads to structures most similar to the extracellular matrix, even when the chitosan is crosslinked, or in combination with metal oxides of interest in orthopedics.     

Biomedical and Clinical Importance of Mussel-Inspired Polymers and Materials

The substance secreted by mussels, also known as nature’s glue, is a type of liquid protein that hardens rapidly into a solid water-resistant adhesive material. While in seawater or saline conditions, mussels can adhere to all types of surfaces, sustaining its bonds via mussel adhesive proteins (MAPs), a group of proteins containing 3,4-dihydroxyphenylalanine (DOPA) and catecholic amino acid. Several aspects of this adhesion process have inspired the development of various types of synthetic materials for biomedical applications. Further, there is an urgent need to utilize biologically inspired strategies to develop new biocompatible materials for medical applications. Consequently, many researchers have recently reported bio-inspired techniques and materials that show results similar to or better than those shown by MAPs for a range of medical applications. However, the susceptibility to oxidation of 3,4-dihydroxyphenylalanine poses major challenges with regard to the practical translation of mussel adhesion. In this review, various strategies are discussed to provide an option for DOPA/metal ion chelation and to compensate for the limitations imposed by facile 3,4-dihydroxyphenylalanine autoxidation. We discuss the anti-proliferative, anti-inflammatory, anti-microbial activity, and adhesive behaviors of mussel bio-products and mussel-inspired materials (MIMs) that make them attractive for synthetic adaptation. The development of biologically inspired adhesive interfaces, bioactive mussel products, MIMs, and arising areas of research leading to biomedical applications are considered in this review.     

Chitin Deacetylases: Properties and Applications

Chitin deacetylases, occurring in marine bacteria, several fungi and a few insects, catalyze the deacetylation of chitin, a structural biopolymer found in countless forms of marine life, fungal cell and spore walls as well as insect cuticle and peritrophic matrices. The deacetylases recognize a sequence of four GlcNAc units in the substrate, one of which undergoes deacetylation: the resulting chitosan has a more regular deacetylation pattern than a chitosan treated with hot NaOH. Nevertheless plain chitin is a poor substrate, but glycolated, reprecipitated or depolymerized chitins are good ones. The marine Vibrio sp. colonize the chitin particles and decompose the chitin thanks to the concerted action of chitinases and deacetylases, otherwise they could not tolerate chitosan, a recognized antibacterial biopolymer. In fact, chitosan is used to prevent infections in fishes and crustaceans. Considering that chitin deacetylases play very important roles in the biological attack and defense systems, they may find applications for the biological control of fungal plant pathogens or insect pests in agriculture and for the biocontrol of opportunistic fungal human pathogens.     

Fish Bone Derived Bi-Phasic Calcium Phosphate Coatings Fabricated by Pulsed Laser Deposition for Biomedical Applications

We report on new biomaterials with promising bone and cartilage regeneration potential, from sustainable, cheap resources of fish origin. Thin films were fabricated from fish bone-derived bi-phasic calcium phosphate targets via pulsed laser deposition with a KrF * excimer laser source (λ = 248 nm, τ_FWHM ≤ 25 ns). Targets and deposited nanostructures were characterized by SEM and XRD, as well as by Energy Dispersive X-ray (EDX) and FTIR spectroscopy. Films were next assessed in vitro by dedicated cytocompatibility and antimicrobial assays. Films were Ca-deficient and contained a significant fraction of β-tricalcium phosphate apart from hydroxyapatite, which could contribute to an increased solubility and an improved biocompatibility for bone regeneration applications. The deposited structures were biocompatible as confirmed by the lack of cytotoxicity on human gingival fibroblast cells, making them promising for fast osseointegration implants. Pulsed laser deposition (PLD) coatings inhibited the microbial adhesion and/or the subsequent biofilm development. A persistent protection against bacterial colonization (Escherichia coli) was demonstrated for at least 72 h, probably due to the release of the native trace elements (i.e., Na, Mg, Si, and/or S) from fish bones. Progress is therefore expected in the realm of multifunctional thin film biomaterials, combining antimicrobial, anti-inflammatory, and regenerative properties for advanced implant coatings and nosocomial infections prevention applications.     

Spray drift: impact of requirements to protect the environment

Spray drift studies in the US have evaluated the effects of application, meteorological and tank mix variables on spray drift. The data have been incorporated into models to predict drift from aerial applications, and to evaluate worst-case drift from ground rig (boom) and orchard airblast applications. An atomisation model has also been developed to predict droplet size for applications of tank mixes with user-defined or reasonable worst-case physical properties through a wide range of hydraulic nozzles applicable to aerial applications. The database and models help provide the exposure risk input to risk assessments for developing appropriate labelling based on exposure and toxicity risk to non-target sensitive areas. This needs to be balanced with allowing crop protection using careful risk/benefit assessments. Buffers or no spray zones may be based on spray quality, release height and other variables such as wind speed where necessary for protecting specific sensitive areas. The impact of protection measures aimed at minimising the incidence and impact of spray drift is discussed in the present paper.     

Marine Biopolymers as Bioactive Functional Ingredients of Electrospun Nanofibrous Scaffolds for Biomedical Applications

Marine biopolymers, abundantly present in seaweeds and marine animals, feature diverse structures and functionalities, and possess a wide range of beneficial biological activities. Characterized by high biocompatibility and biodegradability, as well as unique physicochemical properties, marine biopolymers are attracting a constantly increasing interest for the development of advanced systems for applications in the biomedical field. The development of electrospinning offers an innovative technological platform for the production of nonwoven nanofibrous scaffolds with increased surface area, high encapsulation efficacy, intrinsic interconnectivity, and structural analogy to the natural extracellular matrix. Marine biopolymer-based electrospun nanofibrous scaffolds with multifunctional characteristics and tunable mechanical properties now attract significant attention for biomedical applications, such as tissue engineering, drug delivery, and wound healing. The present review, covering the literature up to the end of 2021, highlights the advancements in the development of marine biopolymer-based electrospun nanofibers for their utilization as cell proliferation scaffolds, bioadhesives, release modifiers, and wound dressings.     

Influence of Poly(lactic acid) Layer on the Physical and Antibacterial Properties of Dry Bacterial Cellulose Sheet for Potential Acute Wound Healing Materials

Dry bacterial cellulose nanofiber (BC) sheet coated with poly(lactic acid) (PLA) was developed and characterized towards acute wound healing applications. This new approach of PLA coating on BC revealed enhanced physical and antibacterial properties. Commercial BC sheets originated from the manufacturing of nata de coco jelly were dried and coated with the PLA at various concentrations of 2, 4, 6, 8, 10 and 12 % w/v for the purpose of improving the mechanical properties and followed by loading of antiseptic such as benzalkonium chloride (BAC). PLA has been proposed for the use of coating materials at a concentration of 8 %, the biocomposite sheet started exhibiting a low moisture uptake, prolonged swelling in simulated wound fluid solution and high tear (9.17 Nm²/kg) and burst indices (32.5 kPa·m²/g). The 8 % PLA coating revealed porous fiber-like morphology as observed under scanning electron microscope. Therapeutic loading capacity of the BC/8 PLA was substantially higher than the pristine BC. Furthermore strong antimicrobial activities against Staphylococcus aureaus and Escherichia coli were observed for the BC/8PLA biocomposite film. These reports were clearly suggestive of the fact that synthetic biodegradable polymers, such as PLA, may be exploited for the synergistic combination with BC for antimicrobial and acute wound management. This new and modified fiber source material could reduce the dependency on plant based cellulose for more demanding biomedical applications such as wound healing materials, vascular graft, cartilage replacement, drug delivery and tissue engineering.     

Chitin Synthesis and Degradation in Crustaceans: A Genomic View and Application

Chitin is among the most important components of the crustacean cuticular exoskeleton and intestinal peritrophic matrix. With the progress of genomics and sequencing technology, a large number of gene sequences related to chitin metabolism have been deposited in the GenBank database in recent years. Here, we summarized the genes and pathways associated with the biosynthesis and degradation of chitins in crustaceans based on genomic analyses. We found that chitin biosynthesis genes typically occur in single or two copies, whereas chitin degradation genes are all multiple copies. Moreover, the chitinase genes are significantly expanded in most crustacean genomes. The gene structure and expression pattern of these genes are similar to those of insects, albeit with some specific characteristics. Additionally, the potential applications of the chitin metabolism genes in molting regulation and immune defense, as well as industrial chitin degradation and production, are also summarized in this review.     

Marine Polysaccharides as a Versatile Biomass for the Construction of Nano Drug Delivery Systems

Marine biomass is a treasure trove of materials. Marine polysaccharides have the characteristics of biocompatibility, biodegradability, non-toxicity, low cost, and abundance. An enormous variety of polysaccharides can be extracted from marine organisms such as algae, crustaceans, and microorganisms. The most studied marine polysaccharides include chitin, chitosan, alginates, hyaluronic acid, fucoidan, carrageenan, agarose, and Ulva. Marine polysaccharides have a wide range of applications in the field of biomedical materials, such as drug delivery, tissue engineering, wound dressings, and sensors. The drug delivery system (DDS) can comprehensively control the distribution of drugs in the organism in space, time, and dosage, thereby increasing the utilization efficiency of drugs, reducing costs, and reducing toxic side effects. The nano-drug delivery system (NDDS), due to its small size, can function at the subcellular level in vivo. The marine polysaccharide-based DDS combines the advantages of polysaccharide materials and nanotechnology, and is suitable as a carrier for different pharmaceutical preparations. This review summarizes the advantages and drawbacks of using marine polysaccharides to construct the NDDS and describes the preparation methods and modification strategies of marine polysaccharide-based nanocarriers.     

我国特有孑遗植物水松濒危原因及其保护对策

通过对水松各分布区实地调查,从生殖生物学、生态因子胁迫、人为干扰和遗传多样性等方面探讨水松濒危的主要原因。研究表明：水松原始的生物学特性制约了其生存规模,对生境的高要求影响了其持续繁衍,人为干扰引起的生境破碎化和过度砍伐所导致的个体数量下降是其濒危的直接因素,较低的遗传多样性水平是其濒危的内在因素。针对水松濒危的原因和现状,提出在种群规模大、遗传多样性高的分布地设立保护点,对生境退化、规模较小的种群采取迁地保护措施,并通过人工繁育幼苗扩大种群规模。     

Conductive 3D structure nanofibrous scaffolds for spinal cord regeneration

The complex nature of spinal cord injuries has provided much inspiration for the design of novel biomaterials and scaffolds which are capable of stimulating neural tissue repair strategies. Recently, conductive polymers have gained much attention for improving the nerve regeneration. In our previous study, a three-dimensional (3D) structure with reliable performance was achieved for electrospun scaffolds. The main purpose in the current study is formation of electrical excitable 3D scaffolds by appending polyaniline (PANI) to biocompatible polymers. In this paper, an attempt was made to develop conductive nanofibrous scaffolds, which can simultaneously present both electrical and topographical cues to cells. By using a proper 3D structure, two kinds of conductive scaffolds are compared with a non-conductive scaffold. The 3D nanofibrous core-sheath scaffolds, which are conductive, were prepared with nanorough sheath and aligned core. Two different sheath polymers, including poly(lactic-co-glycolic acid) PLGA and PLGA/PANI, with identical PCL/PANI cores were fabricated. Nanofibers of PCL and PLGA blends with PANI have fiber diameters of 234±60.8 nm and 770±166.6 nm, and conductivity of 3.17×10^-5 S/cm and 4.29×10^-5 S/cm, respectively. The cell proliferation evaluation of nerve cells on these two conductive scaffolds and previous non-conductive scaffolds (PLGA) indicate that the first conductive scaffold (PCL/ PANI-PLGA) could be more effective for nerve tissue regeneration. Locomotor scores of grafted animals by developed scaffolds showed significant performance of non-conductive 3D scaffolds. Moreover, the animal studies indicated the ability of two new types of conductive scaffolds as spinal cord regeneration candidates.