Facile fabrication of chitosan/bone/bamboo biochar beads for simultaneous removal of co-existing Cr(VI) and bisphenol a from water.

Heavy metal Cr(VI) and organic BPA have posed harmful risks to human health, aquatic organisms and the ecosystem. In this work, Chitosan/bone/bamboo biochar beads (CS-AMCM) were synthesized by co-pyrolysis and in situ precipitation method. These microbeads featured a particle size of approximately 1 ± 0.2 mm and were rich in oxygen/nitrogen functional groups. CS-AMCM was characterized using XRD, Zeta potential, FTIR, etc. Experiments showed that adsorption processes of CS-AMCM on Cr(VI) and BPA fitted well to Langmuir model, with theoretical maximum capacities of 343.61 mg/g and 140.30 mg/g, respectively. Pore filling, electrostatic attraction, redox, complexation and ion exchange were the main mechanisms for Cr(VI), whereas for BPA, the intermolecular force (hydrogen bond) and pore filling were involved. CS-AMCM with adsorbed Cr(VI) demonstrated effective activation in producing ·OH and ·O2 from H2O2, which degraded BPA and Cr(VI) with the removal rates of 99.2% and 98.2%, respectively. CS-AMCM offers the advantages of low-cost, large adsorption capacity, high catalytic degradation efficiency, and favorable recycling in treating Cr(VI) and BPA mixed wastewater, which shows great potential in treating heavy metal and organic matter mixed pollution wastewater.

Synthesis of N-isonicotinic sulfonate chitosan and its antibiofilm activity against E. coli and S.aureus.

N-(sodium 2-hydroxypropylsulfonate) chitosan (HSCS), N-sulfonate chitosan (SCS) and N-isonicotinic sulfonate chitosan (ISCS) were prepared. The structures of the prepared chitosan derivatives were characterized by nuclear magnetic resonance (1H NMR) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, ultraviolet-visible (UV-vis) spectroscopy and elemental analysis (EA). Antibacterial and antibiofilm activities of these chitosan derivatives were evaluated in vitro. The minimum inhibitory concentration (MIC) of HSCS and SCS against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) were 0.625 mg/mL and 0.156 mg/mL, respectively. ISCS exhibited MIC values of 0.313 mg/mL and 0.078 mg/mL against E. coli and S. aureus, respectively. ISCS demonstrated superior antibacterial and antibiofilm properties compared to SCS and HSCS. These findings suggest that the incorporation of a pyridine structure into sulfonate chitosan enhances its antibacterial and antibiofilm activities, and the prepared ISCS has a promising application prospect for controlling the reproduction of microorganisms in the field of food packaging.

Pharmaceutical applications of chitosan in skin regeneration: A review.

Skin regeneration is the process that restores damaged tissues. When the body experiences trauma or surgical incisions, the skin and tissues on the wound surface become damaged. The body repairs this damage through complex physiological processes to restore the original structural and functional states of the affected tissues. Chitosan, a degradable natural bioactive polysaccharide, has attracted widespread attention partly owing to its excellent biocompatibility and antimicrobial properties; additionally, a modified form of this compound has been shown to promote skin regeneration. This review evaluates the recent research progress in the application of chitosan to promote skin regeneration. First, we discuss the basic principles of the extraction and preparation processes of chitosan from its source. Subsequently, we describe the functional properties of chitosan and the optimization of these properties through modification. We then focus on the existing chitosan-based biomaterials developed for clinical applications and their corresponding effects on skin regeneration, particularly in cases of diabetic and burn wounds. Finally, we explore the challenges and prospects associated with the use of chitosan in skin regeneration. Overall, this review provides a reference for related research and contributes to the further development of chitosan-based products in cutaneous skin regeneration.

Determination of bioactive flavonoids using ß-cyclodextrin combined with chitosan-modified magnetic nanoparticles.

To accurately determine flavonoids (rutin, quercetin or kaempferol), it is necessary to extract them from complex matrices. The ultrasound-assisted magnetic dispersion microsolid phase extraction technique has been predominantly used for separation and enrichment of the target analytes. The combination of magnetic chitosan nanoparticles and a deep eutectic supramolecular solvent (DESP) is likely to enhance the efficiency of flavonoid extraction from food. In this study, adsorbents were prepared by modifying chitosan with magnetic nanoparticles, and the eluent was a DESP derived from ß-cyclodextrin and an organic acid. The successful preparation of these materials was confirmed by FTIR, XRD, FE-SEM and 1H NMR. The extraction recovery rates exceeded 93 %, with limits of detection and quantitation ranging from 0.9 to 2.4 µg/L and 2.7 to 7.2 µg/L, respectively, and the flavonoid clearance rates for ABTS and DPPH radicals reached 100 %. Therefore, the integration of magnetic chitosan nanoparticles with the DESP provides a new and efficient method for the extraction of flavonoids while also presenting a potential application of the DESP in separations.

Synthesis and characterization of n-phosphonium chitosan and its virucidal activity evaluation against coronavirus.

Despite the worldwide vaccination effort against COVID-19, the demand for biocidal materials has increased. One promising solution is the chemical modification of polysaccharides, such as chitosan, which can provide antiviral activity through the insertion of cationic terminals. In this study, chitosan was modified with (4-carboxybutyl) triphenylphosphonium bromide to create N-phosphonium chitosan (NPCS), a quaternized derivative. The resulting NPCS samples with three degrees of substitution (15.6 %, 19.8 % and 24.2 %) were characterized and found to have improved solubility in water and alkaline solutions but reduced thermal stability. The particles zeta potential exhibits positive charges and is directly correlated with the degree of substitution of the derivative. In virucidal assays, all NPCS samples were able to inhibit 99.999 % of the MHV-3 coronavirus within 5 min at low concentrations of 0.1 mg/mL, while maintaining low cytotoxicity to L929 cells. In addition to its potential application against current coronavirus strains, NPCS could also be valuable in combating future pandemics caused by other viral pathogens. The antiviral properties of NPCS make it a promising material for use in coating surface and personal protective equipment to limit the spread of disease-causing viruses.

A pH-responsive chiral mesoporous silica nanoparticles for delivery of doxorubicin in tumor-targeted therapy.

The purpose of this study was to develop a nano-drug delivery system with intelligent stimuli-responsive drug delivery in tumor microenvironment (TME). Based on chiral mesoporous silica nanoparticles (CMSN) with a chiral recognition function in our previous research, a pH-responsive CMSN (CS-CMSN) was successfully prepared by chemical modification of chitosan (CS), and the related physicochemical properties, drug release performance, potential anti-tumor effect, and biological safety were studied. The results showed that the CS-CMSN were successfully modified by CS. Moreover, CS-CMSN displayed superior encapsulation ability for doxorubicin (DOX) and exhibited controllable pH-responsive drug release properties. In particular, in a physiological environment (pH 7.4/6.5), CS shielded the nanopores, prevented DOX release, and minimized side effects on normal cells. Once the CS-CMSN was exposed to the TME (pH 5.0), the pH-sensitive moiety of CS was cleaved in an acidic environment, along with the rapid release of DOX. In vitro cell experiments further proved that DOX@CS-CMSN was more strongly taken up by 4T1 cells and could enhance the toxicity to 4T1 tumor cells as well as promote cell apoptosis. More importantly, CS-CMSN were shown to have good biosafety in vitro and in vivo. Overall, the delivery of DOX by CS-CMSN nanocarriers is a promising strategy for tumor-targeted therapy.

Computational design of a chitosan derivative for improving the color stability of anthocyanins: Theoretical calculation and experimental verification.

The objective of this study was to design a chitosan (CS) derivative with good protective effect on the color stability of anthocyanins (ACNs) under accelerated storage. The binding affinities and interactions of 12 organic acids with cyanidin-3-O-glucoside (C3G) were evaluated using quantum mechanics method. Sinapic acid (SinA) showing the strongest interaction with C3G was selected for the synthesis of SinA-grafted-CS (SinA-g-CS), which was further characterized by FTIR and 1H NMR. Under accelerated storage conditions (40 °C), SinA-g-CS significantly improved the color stability of black rice anthocyanins (BRA) in the presence of l-ascorbic acid (pH 3.0), and showed a better protective effect than that of CS. Moreover, molecular dynamics simulation analysis showed SinA-g-CS formed more hydrogen bonds with C3G than CS. Our study demonstrated that SinA-g-CS designed by computational methods can effectively protect ACNs from degradation, and has the potential to be used in ACN-rich beverages as a replacement for CS.

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 environmental pollution protection. This review, in line with the focus of this special issue, provides the reader with (1) an overview on different sources of chitin, (2) advances in techniques used to extract chitin and converting it into chitosan, (3) the importance of the inherent characteristics of the chitosan from different sources that makes them suitable for specific applications and, finally, (4) briefly summarizes ways of tailoring chitosan for specific applications. The review also presents the influence of the degree of acetylation (DA) and degree of deacetylation (DDA), molecular weight (Mw) on the physicochemical and biological properties of chitosan, acid-base behavior, biodegradability, solubility, reactivity, among many other properties that determine processability and suitability for specific applications. This is intended to help guide researchers select the right chitosan raw material for their specific applications.

Preparation, characterization and antibacterial activity of new ionized chitosan.

In order to improve the solubility and antibacterial activity of chitosan and expand its application range, ionized chitosan (ICS) was successfully synthesized from chitosan through methylation and sulfonation reactions in this study. The chemical structures of the polymers were verified by Fourier transform infrared spectroscopy (FTIR) and 1H NMR, and a series of characterizations of the polymer were carried out by analytical methods such as element analysis (EA), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The results showed that the water solubility of the modified ICS was significantly improved. The introduction of propyl sulfonic acid groups with particle size decreasing and potential increasing greatly improved the antibacterial activity of chitosan, indicating that the ICS had the potential as a water-soluble antibacterial agent.

Efficient removal of Cd (II) from aqueous solution by chitosan modified kiwi branch biochar.

Production of cost-efficient composite materials from low-cost modified biochar for the removal of Cd (II) from wastewater is much needed to meet the growing needs of industrial wastewater treatments. A novel chitosan-modified kiwi branch biochar (CHKB) was fabricated as low-cost modified biochar for the removal of Cd (II) from aqueous solution. Batch adsorption and characterization experiments indicated that the modification of kiwi biochar (KB) by chitosan remarkably improved its adsorption performance. The results revealed that the adsorption isotherms can be best described by a Langmuir model and that a pseudo-second-order model fits the Cd (II) adsorption kinetics well, which indicates that it is a monolayer process controlled by chemisorption. CHKB exhibited a Langmuir maximum adsorption capacity of Cd (II) (126.58 mg g-1), whereas that of KB was only 4.26 mg g-1. The adsorption ability of CHKB was improved by increasing the surface area and an abundance of surface functional groups (-OH, -NH, CO, etc.). The cation exchange, electrostatic interaction, surface complexation, and precipitation were the main mechanisms in the sorption of Cd (II) on CHKB. Excellent adsorption performance, low cost, and environmental-friendliness made CHKB a fantastic adsorbent for the removal of Cd (II) in wastewater.

Fluorescent Chitosan Modified with Heterocyclic Aromatic Dyes.

Chitosan is a valuable, functional, and biodegradable polysaccharide that can be modified to expand its applications. This work aimed to obtain chitosan derivatives with fluorescent properties. Three heterocyclic aromatic dyes (based on benzimidazole, benzoxazole, and benzothiazole) were synthesized and used for the chemical modification of chitosan. Emission spectroscopy revealed the strong fluorescent properties of the obtained chitosan derivatives even at a low N-substitution degree of the dye. The effect of high-energy ultraviolet radiation (UV-C) on modified chitosan samples was studied in solution with UV-Vis spectroscopy and in the solid state with FTIR spectroscopy. Moreover, cytotoxicity towards three different cell types was evaluated to estimate the possibilities of biomedical applications of such fluorescent chitosan-based materials. It was found that the three new derivatives of chitosan were characterized by good resistance to UV-C, which suggests the possibility of using these materials in medicine and various industrial sectors.

A Complementary and Revised View on the N-Acylation of Chitosan with Hexanoyl Chloride.

The modification of the biobased polymer chitosan is a broad and widely studied field. Herein, an insight into the hydrophobization of low-molecular-weight chitosan by substitution of amino functionalities with hexanoyl chloride is reported. Thereby, the influence of the pH of the reaction media was investigated. Further, methods for the determination of the degree of substitution based on 1H-NMR, FTIR, and potentiometric titration were compared and discussed regarding their accuracy and precision. 1H-NMR was the most accurate method, while FTIR and the potentiometric titration, though precise and reproducible, underlie the influence of complete protonation and solubility issues. Additionally, the impact of the pH variation during the synthesis on the properties of the samples was investigated by Cd2+ sorption experiments. The adjusted pH values during the synthesis and, therefore, the obtained degrees of substitution possessed a strong impact on the adsorption properties of the final material.

Chemical and physical Chitosan modification for designing enzymatic industrial biocatalysts: How to choose the best strategy?

Chitosan is one of the most abundant natural polymer worldwide, and due to its inherent characteristics, its use in industrial processes has been extensively explored. Because it is biodegradable, biocompatible, non-toxic, hydrophilic, cheap, and has good physical-chemical stability, it is seen as an excellent alternative for the replacement of synthetic materials in the search for more sustainable production methodologies. Thus being, a possible biotechnological application of Chitosan is as a direct support for enzyme immobilization. However, its applicability is quite specific, and to overcome this issue, alternative pretreatments are required, such as chemical and physical modifications to its structure, enabling its use in a wider array of applications. This review aims to present the topic in detail, by exploring and discussing methods of employment of Chitosan in enzymatic immobilization processes with various enzymes, presenting its advantages and disadvantages, as well as listing possible chemical modifications and combinations with other compounds for formulating an ideal support for this purpose. First, we will present Chitosan emphasizing its characteristics that allow its use as enzyme support. Furthermore, we will discuss possible physicochemical modifications that can be made to Chitosan, mentioning the improvements obtained in each process. These discussions will enable a comprehensive comparison between, and an informed choice of, the best technologies concerning enzyme immobilization and the application conditions of the biocatalyst.

Pristine and modified chitosan as solid catalysts for catalysis and biodiesel production: A minireview.

Chitosan is one of the readily available polymers with relatively high abundance, biodegradable and sustainable materials with divergent functional groups that are employed in broad range of applications. Chitosan is widely used in many fields like adsorption, drug carrier for therapeutic activity, environmental remediation, drug formulation and among others. One of the unique features of chitosan is that it can be transformed to other forms like beads, films, flakes, sponges and fibres depending upon the applications. This review is aimed at showing the potential applications of chitosan and its modified solids in organic transformations. The number of existing articles is organized based on the nature of materials and subsequently with the types of reactions. After a brief description on the structural features of chitosan, properties, characterization methods including various analytical/microscopic techniques and some of the best practices to be followed in catalysis are also discussed. The next section of this review describes the catalytic activity of native chitosan without any modifications while the subsequent sections provide the catalytic activity of chitosan derivatives, chitosan covalently modified with metal complexes/salts through linkers and chitosan as support for metal nanoparticles (NPs). These sections discuss number of organic reactions that include Knoevenagel condensation, oxidation, reduction, heterocycles synthesis, cross-coupling reactions and pollutant degradation among others. A separate section provides the catalytic applications of chitosan and its modified forms for the production of fatty acid methyl esters (FAME) through esterification/transesterification reactions. The final section summarizes our views on the future directions of this field in the coming years.

A sandwich model of Cr(VI) adsorption and detoxification by Fenton modified chitosan.

The Fenton reaction has the advantages of short reaction time, low cost, no toxicity, and straightforward application and control. The Fenton reaction generates highly reactive HO•, which has been applied effectively. However, the effect of the generated Fe3+ has not been investigated widely. In this study, the Fenton reaction was used to improve the Cr(VI) adsorption and detoxification capacities of chitosan. After the Fenton modification, chitosan efficiently adsorbed Cr(VI) and transformed it into the less toxic Cr(III) in a wide pH range as a result of layer formation, which was described by a sandwich model. The adsorption of Cr(VI) onto the Fenton modified chitosan was in good agreement with the Freundlich adsorption model, and the adsorption capacity exceeded 120 mg/g. During the Fenton reaction, H2 O2 and HO• with high oxidative activity broke the hydrogen bonds in the chitosan structure, resulting in the release of free amine groups for Fe3+ to form metal-binding biopolymers. The distance between the chitosan polymers increased, and additional adsorption sites were created. HCrO4 - entered the gap between the chitosan polymer and was adsorbed on the newly created adsorption sites. The sandwich adsorption model indicated that the Fenton modified chitosan provided a high concentration of active sites for Cr(VI) capture and detoxification. PRACTITIONER POINTS: Fenton reaction was used to improve the adsorption ability of chitosan. The formed Fe3+ in Fenton reaction was utilized. HO· broke the hydrogen bonds and Fe3+ ions chelated with chitosan in modification. Cr(VI) could be adsorbed and reduced efficiently by Fenton modified chitosan. The Fenton modified chitosan provided a high concentration of active sites for Cr(VI) capture and detoxification.

Selective adsorption of Pb(II) and Hg(II) on melamine-grafted chitosan.

Amine groups can play significant roles in modified chitosans for adsorption of heavy metal ions. A novel chitosan modified adsorbent (GMCS) grafted with lots of amine groups was synthesized by using glutaraldehyde as a crosslinker between chitosan and melamine. The structure and morphology of GMCS was characterized using FT-IR, 13C NMR, elemental analysis, XRD, TGA, SEM, BET and zeta potential analysis. The adsorption of GMCS and chitosan for different heavy metal ions was compared. The results indicated that GMCS had higher selectivity and uptake for adsorption of Pb2+ and Hg2+ than chitosan. Effects of some variables for uptakes of Pb2+ and Hg2+ on GMCS were studied. The kinetic and isothermal results showed that the adsorption followed the pseudo-second-order kinetic and Langmuir isotherm models. The adsorbent had highest adsorption capacity of 618.2 mg/g and 490.7 mg/g at pH 5 and 6 for Pb2+ and Hg2+, respectively. The adsorption was an endothermic and spontaneous chemical process. Five cycled experiments of adsorption-desorption showed that the adsorbent could be efficiently regenerated.

Enhanced aqueous Cr(VI) removal using chitosan-modified magnetic biochars derived from bamboo residues.

The purpose of this study was to fabricate a chitosan modified magnetic bamboo biochar (CMBB) for Cr(VI) detoxification from aqueous solution. Results showed that chitosan modification provided more active adsorption sites on the surface of magnetic bamboo biochar (MBB), and hence enhanced Cr(VI) removal from aqueous solution. The maximum adsorption capacities of MBB and CMBB for Cr(VI) at 25 °C were 75.8 and 127 mg g-1, respectively. Increasing solution pH inbibited Cr(VI) adsorption by adsorbents. However, CMBB maintained a high Cr(VI) removal efficiencies over a broader pH range (2-10), and could attain 36% of the maximum adsorption (40 mg g-1) even at a high pH of 10.0. Rising temperature enhanced the Cr(VI) removal by two adsorbents. The escalating ionic strength and coexist substances, including Na+, Ca2+, Fe3+, Cl-, SO42-, PO43- and humate, inhibited the adsorption efficiency of Cr(VI) on adsorbents. After the fifth adsorption-desorption cycle, the adsorption efficiencies of CMBB and MBB for Cr(VI) remained above 90% and less than 50%, respectively. All these results indicated that CMBB could be a practical adsorbent that can be utilized for the detoxification of Cr(VI) ions from wastewater.

Chitosan and Its Derivatives - Biomaterials with Diverse Biological Activity for Manifold Applications.

Derived from chitin, chitosan is a natural polycationic linear polysaccharide being the second most abundant polymer next to cellulose. The main obstacle in the wide use of chitosan is its almost complete lack of solubility in water and alkaline solutions. To break this obstacle, the structure of chitosan is subjected to modification, improving its physic-chemical properties and facilitating application as components of composites or hydrogels. Derivatives of chitosan are biomaterials useful for different purposes because of their lack of toxicity, low allergenicity, biocompatibility and biodegradability. This review presents the methods of chemical modifications of chitosan which allow to obtain tailor- made properties required for a variety of biomedical applications. Selected pharmaceutical and biomedical applications of chitosan derivatives are also highlighted. Possibility to manage waste from arthropod and crab processing is also emphasized.

Synthesis, optimization and structural characterization of a chitosan-glucose derivative obtained by the Maillard reaction.

Chitosan (Chit) was submitted to the Maillard reaction (MR) by co-heating a solution with glucose (Glc). Different reaction conditions as temperature (40, 60 and 80 °C), Glc concentration (0.5%, 1%, and 2%, w/v), and reaction time (72, 52 and 24h) were evaluated. Assessment of the reaction extent was monitored by measuring changes in UV absorbance, browning and fluorescence. Under the best conditions, 2% (w/v) of Chit, 2% (w/v) of Glc at 60°C and 32 h of reaction time, a chitosan-glucose (Chit-Glc) derivative was purified and submitted to structural characterization to confirm its formation. Analysis of its molecular weight (MW) and the degree of substitution (DS) was carried out by HPLC-Size Exclusion Chromatography (SEC) and a colloid titration method, respectively. FT-IR and (1)H NMR were also used to analyze the functional groups and evaluate the introduction of Glc into the Chit molecule. According to our objectives, the results obtained in this work allowed to better understand the key parameters influencing the MR with Chit as well as to confirm the successful introduction of Glc into the Chit molecule obtaining a Chit-Glc derivative with a DS of 64.76 ± 4.40% and a MW of 210.37 kDa.