The Adsorption Effect of Quaternized Chitosan Derivatives on Bile Acid

Three quatemized chitosan derivatives were synthesized and their adsorption performance of bile acid from aqueous solution was studied. The adsorption capacities and rates of bile acid onto quatemized chitosan derivatives were evaluated. The kinetic experimental data properly correlated with the second-order kinetic model, which indicated that the chemical sorption is the rate-limiting step. The results showed that the quatemized chitosan derivatives are favorable adsorbents for bile acid.

Pb(Ⅱ) biosorption using chitosan and chitosan derivatives beads: Equilibrium, ion exchange and mechanism studies

The study examined the adsorption of Pb（II） ions from aqueous solution onto chitosan, chitosan-GLA and chitosan-alginate beads. Several important parameters influencing the adsorption of Pb（II） ions such as initial pH, adsorbent dosage and different initial concentration of Pb（II） ions were evaluated. The mechanism involved during the adsorption process was explored based on ion exchange study and using spectroscopic techniques. The adsorption capacities obtained based on non–linear Langmuir isotherm for chitosan, chitosan-GLA and chitosan-alginate beads in single metal system were 34.98, 14.24 and 60.27 mg/g, respectively. However, the adsorption capacity of Pb（II） ions were reduced in the binary metal system due to the competitive adsorption between Pb（II） and Cu（II） ions. Based on the ion exchange study, the release of Ca2＋, Mg2＋, K＋ and Na＋ ions played an important role in the adsorption of Pb（II） ions by all three adsorbents but only at lower concentrations of Pb（II） ions. Infrared spectra showed that the binding between Pb（II） ions and the adsorbents involved mostly the nitrogen and oxygen atoms. All three adsorbents showed satisfactory adsorption capacities and can be considered as an efficient adsorbent for the removal of Pb（II） ions from aqueous solutions.

Synthesis,characterization,and antioxidant activity of carboxymethyl chitosan derivatives containing sulfonium salt

To improve the solubility and bioactivity of chitosan,a new class of carboxymethyl chitosan derivatives possessing sulfonium salts was successfully designed and synthesized,including Methyl sulfi de carboxymethyl chitosan(MCMCS),Ethyl sulfi de carboxymethyl chitosan(ECMCS),Propyl sulfi de carboxymethyl chitosan(PCMCS),and Butyl sulfi de carboxymethyl chitosan(BCMCS).To determine the structure of the new class of the derivatives,methods of the Fourier transform infrared spectroscopy(FT-IR),^(1)H nuclear magnetic resonance spectrometer(^(1)H NMR),and^(13)C nuclear magnetic resonance spectrometer(^(13)C NMR)were used.Moreover,the antioxidant activity of the derivatives for three types of free radicals,i.e.,hydroxyl radical,superoxide radical,and 1,1-diphenyl-2-picrylhydrazyl(DPPH)radical was evaluated in vitro.In addition,the L929 cells were adopted to test the cytotoxicity of chitosan and its derivatives by CCK-8 assay.The class of the carboxymethyl chitosan derivatives showed a strong scavenging ability against the three free radicals at 1.6 mg/mL,with scavenging rate of over 70%and some up to 100%.At this high rate,the overall cell viability in the toxicity test reached more than 80%,indicating that the synthetic derivative had a little cytotoxicity.The results show that the introduction of carboxymethyl group to chitosan increased the water-solubility of chitosan,and the combination of sulfonate ions with diff erent chain lengths further enhanced the antioxidant activity of chitosan.Therefore,the sulfonium-containing carboxymethyl chitosan derivatives had excellent bioactivity with good application prospects in food,biomedicine,and medical fi elds.

Effects of Sulfate Chitosan Derivatives on Nonalcoholic Fatty Liver Disease

Sulfate chitosan derivatives have good solubility and therapeutic effect on the cell model of NAFLD. The aim of this study was to examine the therapeutic effect of sulfate chitosan derivatives on NAFLD. The male Wistar rats were orally fed high fat emulsion and received sulfate chitosan derivatives for 5 weeks to determine the pre-treatment effect of sulfate chitosan derivatives on NAFLD. To evaluate the therapeutic effect of sulfate chitosan derivatives on NAFLD, the rats were orally fed with high concentration emulsion for 5 weeks, followed by sulfate chitosan derivatives for 3 weeks. Histological analysis and biomedical assays showed that sulfate chitosan derivatives can dramatically prevent the development of hepatic steatosis in hepatocyte cells. In animal studies, pre-treatment and treatment with sulfate chitosan derivatives significantly protected against hepatic steatohepatitis induced by high fat diet according to histological analysis. Furthermore, increased TC, ALT, MDA, and LEP in NAFLD were significantly ameliorated by pre-treatment and treatment with sulfate chitosan derivatives. Furthermore, increased TG, AST, and TNF-α in NAFLD were significantly ameliorated by treatment with sulfate chitosan derivatives. Sulfate chitosan derivatives have good pre-treatment and therapeutic effect on NAFLD.

Adsorption of methyl orange from aqueous solution by composite magnetic microspheres of chitosan and quaternary ammonium chitosan derivative

Novel composite magnetic microspheres containing chitosan and quaternary ammonium chitosan derivative(CHMMs) were prepared by inverse suspension method,and used for the methyl orange(MO) removal from aqueous solutions.The CHMMs were characterized by a scanning electron microscope,a transmission electron microscope,and Fourier transform infrared spectroscopy,respectively.Compared with the chitosan beads,the incorporation of quaternary ammonium chitosan derivative significantly reduced the particle size.The MO adsorption by CHMMs was investigated by batch adsorption experiments.The adsorption kinetics was conformed to the pseudo second-order kinetics equation.The adsorption isotherm followed the Langmuir model better than the Freundlich model and the calculated maximum MO adsorption capacity was 266.6 mg·g^-1 at 293 K.Thermodynamic studies indicated that the MO adsorption was endothermic in nature with the enthalpy change(△H°) of 99.44 kJ·mol^-1.The CHMMs had a stable performance for MO adsorption in the pH range of 4-10,but high ionic strength deteriorated the MO removal due to the shielding of the ion exchange interaction.A 1 mol·L^-1 NaCl solution could be used to regenerate the exhausted CHMMs.The proposed CHMMs can be used as an effective adsorbent for dye removal or recovery from the dye wastewater.

Synthesis of a new chitosan derivative and assay of Escherichia coli adsorption

A new chitosan derivative is prepared using chitosan.Ethyl chlorocarbonate was first introduced to the hydroxyl group of phthaloylchitosan through a nucleophilic reaction.Hydrazine was then added to recover the amino groups of chitosan and promote cross-linking.The structure of this new chitosan derivative was characterized by Fourier transform infrared（FT-IR）and proton nuclear magnetic resonance（1H NMR）spectroscopy,and its physical properties were determined by X-ray diffraction（XRD）,differential scanning calorimetry（DSC）,and thermogravimetric analysis（TGA）.The thermal and chemical stabilities of the new derivative were improved compared with those of native chitosan.Assay of Escherichia coli adhesion on a film based on this chitosan derivative showed good adsorption and biofilm formation.

LYOTROPIC LIQUID CRYSTALLINE BEHAVIOR OF FIVE CHITOSAN DERIVATIVES

Five chitosan derivatives, i.e. O-butyryl chitosan, O-benzoyl chitosan, N-phthaloyl chitosan, N-maleoyl chitosan and O-cyanoethyl chitosan, were prepared from chitosan. All of them had better solubility than chitosan, and demonstrated lyotropic liquid crystalline behavior in various solvents. The critical liquid crystalline behavior of three O-substituted chitosan derivatives was evidently different from two N-substituted analogues. Typical fingerprint textures of cholesteric phase were only observed in three O-substituted derivatives. The critical concentration (v/v%) of three O-substituted derivatives does not depend on the acidity of acidic solvents.

PREPARATION AND CHARACTERIZATION OF NOVEL CHITOSAN DERIVATIVES:ADSORPTION EQUILIBRIUM OF IRON(Ⅲ) ION

The adsorption of Fe(Ⅲ)ions from aqueous solution by chitosan alpha-ketoglutaric acid(KCTS)and hydroxamated chitosan alpha-ketoglutaric acid(HKCTS)was studied in a batch adsorption system.Experiments were carried out as function of pH,temperature,agitation rate and concentration of Fe(Ⅲ)ions.The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms and isotherm constants were determined.The Langmuir model agrees very well with experimental data.The pseudo-first-order a...

Three novel dendritic chitosan derivatives for inhibiting acid corrosion of petroleum pipelines

In the process of exploration and development of oil and gas fields, the acidic environment of oil reservoir, production and transport processes cause corrosion of pipelines and equipment, resulting in huge economic losses and production safety risks. Corrosion inhibitors were widely used in oil industry because of simple operation process and economical. In this study, three environmentally friendly corrosion inhibitors were synthesized based on the natural polysaccharide chitosan. Corrosion inhibition of three dendritic chitosan derivatives (We name them BH, CH and DH) on mild steel in 1 mol/L HCl solution with natural ventilation system was evaluated by weight loss experiment, electrochemical analysis and surface morphology characterization. The experimental results showed that when the three dendritic chitosan derivatives added in the corrosive medium were 500 mg L^(−1), the corrosion inhibition efficiencies were all more than 80%. Based on quantum chemical calculation, inhibition mechanisms of three dendritic chitosan derivatives were investigated according to molecular structures. The results showed that the benzene ring, Schiff base and N atom contained in the molecule were the active centers of electron exchange, which were more likely to form a film on the carbon steel surface, thereby slowing or inhibiting corrosion. The results also predicted the corrosion inhibition effect BH > DH > CH, which was consistent with the experimental conclusion.

Advancements in Chitosan and Its Derivatives for Enhanced Wound Healing

In recent years,the academic community has continued to explore effective methods to promote wound healing and prevent scar hyperplasia.This research area is both challenging and has attracted significant attention.Wound healing is a complex and orderly process involving the precise coordination of various growth factors,inflammatory cells,and repair cells.To optimize this intricate process,researchers have developed a series of innovative synthetic dressings designed to improve the wound healing environment.Among these dressings,the natural polymer chitosan has emerged as a preferred material due to its cost-effectiveness,renewable nature,and exceptional biocompatibility and biodegradability,as demonstrated in the biomedical field,particularly in the area of wound dressings.

Adsorption of Heavy Metal Ions,Dyes and Proteins by Chitosan Composites and Derivatives-A Review

Chitosan composites and derivatives have gained wide attentions as effective biosorbents due to their low costs and high contents of amino and hydroxyl functional groups.They have showed significant potentials of removing metal ions,dyes and proteins from various media.Chemical modifications that lead to the formation of the chitosan derivatives and chitosan composites have been extensively studied and widely reported in literatures.The aims of this review were to summarize the important information of the bioactivities of chitosan,highlight the various preparation methods of chitosan-based active biosorbents,and outline its potential applications in the adsorption of heavy metal ions,dyes and proteins from wastewater and aqueous solutions.

Synthesis and characterization of an amphiphilic chitosan bearing octyl and methoxy polyethylene

An amphiphilic N-octyl-O-methoxy poly (ethylene glycol) chitosan was successfully prepared by grafting successively octyl groups onto amino groups at chitosan’s C-2 position as hydrophobic moieties and methoxy polyethylene glycol (MPEG) groups onto hydroxyl groups at C-6, C-3 as hy-drophilic ones. A certain amount of -NH2 was retained in the structure of chitosan derivatives through protection by phthalic anhydride. The chemical structures and degree of N-and O-substitution of chitosan derivatives were characterized by FTIR, 1H NMR, GPC and elemental analysis, respectively. The amphiphilic property for convenient self-assembly and the preserved -NH2 groups for progressive chemical cross-linking make the resultant Nocyl-O-MPEG chitosan soluble in water and potentially applicable in preparing stable chitosan hollow microspheres, a demanding drug-carrier in medical and pharmaceutical sciences.

Novel nanoparticles composed of chitosan and β-cyclodextrin derivatives as potential insoluble drug carrier

This research was aim to develop novel cyclodextrin/chitosan （CD/CS） nanocarriers for insoluble drug delivery through the mild ionic gelation method previously developed by our lab. A series of different β- cyclodextrin （β-CD） derivatives were incorporated into CS nanoparticles including hydroxypropyl-β- cyclodextrin （HP-β-CD）, sulphobutylether-β-cyclodextrin （SB-β-CD）, and 2,6-di-O-methy-βcyclodex- trin （DM-β-CD）. Various process parameters for nanoparticle preparation and their effects on physicochemical properties of CD/CS nanoparticles were investigated, such as the type of CD derivatives, CD and CS concentrations, the mass ratio of CS to TPP （CS/TRP）, and pH values. In the optimal condition, CDICS nanoparticles were obtained in the size range of 215-276 nm and with the zeta potential from 30.22 mV to 35.79 mY. Moreover, the stability study showed that the incorporation of CD rendered the CD/CS nanocarriers more stable than CS nanoparticles in PBS buffer at pH 6.8. For their easy preparation and adjustable parameters in nanoparticle formation as well as the diversified hydrophobic core of CD derivatives, the novel CD/CS nanoparticles developed herein might represent an interesting and versatile drug delivery platform for a variety of poorly water-soluble drugs with different physicochemical properties.

Protein adsorption on the poly(L-lactic acid) surface modified by chitosan and its derivatives

Surface modification of biomaterials has been adopted over the years to improve their biocompatibility. In this study, aiming to promote hydrophilicity and to introduce natural recognition sites onto poly(L-lactic acid) (PLLA) films, chitosan and its derivatives, carboxymethyl chitosan(CMC) and N-methylene phosphonic chitosan (NPC), were used to modify the surface of PLLA films by an entrapment method. Radiolabeled (125I) proteins were used to measure the amount of protein adsorbed to PLLA surfaces. Fibronectin (Fn) was used to study the protein adsorption on the modified PLLA surfaces, including isotherm adsorption and adsorption kinetics of single protein, competitive adsorption of binary proteins system and serum multi-proteins and the desorption behavior in serum solution. The results showed that in the isotherm adsorption, Fn had a larger adsorption capacity on the CS-modified surface at lower concentrations, but had a high adsorption capacity at CMC-modified surface at higher concentrations. In the study of absorption kinetics, Fn had a fastest adsorption equilibrium and a highest equilibrium adsorption capacity at the CS-modified surface, while it was opposite at the PCS-modified surface. When BSA and serum were added, it had the greatest effect on the adsorption of Fn on the PCS-modified surface. After 6 hours soaking in the desorption study, Fn had reached desorption equilibrium on all the modified surfaces, which had different effects on the desorption rate and the remaining percentage of Fn.

Compatibility of Chitosan-Gelatin Films with Adipose Tissue Derived Stromal Cells

Chitosan has been shown to be a promising material for various applications in tissue engineering. Recently, adipose tissue derived stromal cells （ADSCs） have been investigated as an alternative source of seed cells for tissue engineering. The compatibility of chitosan and chitosan-gelatin complexes with ADSCs is not known. In the present study, ADSCs were isolated and characterized by phenotype using fluorescence-activated cell sorting （FACS）. The morphology, viability, and the ability of the ADSCs to differentiate on chitosan and chitosan-gelatin composite films with 60 wt.% gelatin were evaluated. Results show that the ADSCs are positive for CD29, CD44, and CD105, but negative for CD31, CD34, and CD45. ADSCs adhere and grow better on the composite films than on the chitosan films. The ability of ADSCs to differentiate into osteogenic and adipogenic lineage cells is not affected by their being cultured on chitosan-gelatin composite films. Therefore, chitosan-gelatin composite films are compatible with ADSCs and do not impair the ability of ADSCs to differentiate into osteogenic and adipogenic lineage cells.

Differentiation of adipose-derived stem cells toward nucleus pulposuslike cells induced by hypoxia and a three-dimensional chitosan-alginate gel scaffold in vitro

Background Injectable three-dimensional （3D） scaffolds have the advantages of fluidity and moldability to fill irregularshaped defects,simple incorporation of bioactive factors,and limited surgical invasiveness.Adipose-derived stem cells （ADSCs） are multipotent and can be differentiated toward nucleus pulposus （NP）-Iike cells.A hypoxic environment may be important for differentiation to NP-like cells because the intervertebral disc is an avascular tissue.Hence,we investigated the induction effects of hypoxia and an injectable 3D chitosan-alginate （C/A） gel scaffold on ADSCs.Methods The C/A gel scaffold consisted of medical-grade chitosan and alginate.Gel porosity was calculated by liquid displacement method.Pore microstructure was analyzed by light and scanning electron microscopy.ADSCs were isolated and cultured by conventional methods.Passage 2 BrdU-labeled ADSCs were co-cultured with the C/A gel.ADSCs were divided into three groups （control,normoxia-induced,and hypoxia-induced groups）.In the control group,cells were cultured in 10％ FBS/DMEM.Hypoxia-induced and normoxia-induced groups were induced by adding transforming growth factor-β1,dexamethasone,vitamin C,sodium pyruvate,proline,bone morphogenetic protein-7,and 1％ ITS-plus to the culture medium and maintaining in 2％ and 20％ O2,respectively.Histological and morphological changes were observed by light and electron microscopy.ADSCs were characterized by flow cytometry.Cell viability was investigated by BrdU incorporation.Proteoglycan and type Ⅱ collagen were measured by safranin O staining and the Sicool method,respectively.mRNA expression of hypoxia-inducing factor-1α （HIF-1α）,aggrecan,and Type Ⅱ collagen was determined by reverse transcription-polymerase chain reaction.Results C/A gels had porous exterior surfaces with 80.57％ porosity and 50-200 μm pore size.Flow cytometric analysis of passage 2 rabbit ADSCs showed high CD90 expression,while CD45 expression was very low.The morphology of induced ADSCs resembled that of NP cells.BrdU immunofluorescence showed that most ADSCs survived and proliferated in the C/A gel scaffold.Scanning electron microscopy showed that ADSCs grew well in the C/A gel scaffold.ADSCs in the C/A gel scaffold were positive for safranin O staining.Hypoxia-induced and normoxia-induced groups produced more proteoglycan and Type Ⅱ collagen than the control group （P ＜0.05）.Proteoglycan and Type Ⅱ collagen levels in the hypoxia-induced group were higher than those in the normoxia-induced group （P ＜0.05）.Compared with the control group,higher mRNA expression of HIF-1α,aggrecan,and Type Ⅱ collagen was detected in hypoxia-induced and normoxiainduced groups （P ＜0.05）.Expression of these genes in the hypoxia-induced group was significantly higher than that in the normoxia-induced group （P ＜0.05）.Conclusion ADSCs grow well in C/A gel scaffolds and differentiate toward NP-like cells that produce the same extracellular matrix as that of NP cells under certain induction conditions,which is promoted in a hypoxic state.

Applications of chitosan-based biomaterials:a focus on dependent antimicrobial properties

Marine-derived chitosan has been widely examined for its use in developing biomedical materials.Not only is it non-toxic,biocompatible,and degradable,it has also shown unique antimicrobial properties.The antimicrobial properties of chitosan are restricted by neutral and physiological conditions because it is insoluble in water and its pKa values is 6.5.One solution to this problem is to graft chemically modified groups onto the backbone of chitosan.The aim of this paper is to review the mode of antimicrobial action of chitosan and chitosan derivatives.Using chitosan alone may not meet the demands of various applications.However,the introduction of additional polymers and antimicrobial agents is commonly used to enhance the antimicrobial potential of chitosan-based biomaterials.Chitosan-based composite biomaterials have been developed that allow diversified formulations to broaden applications,including nanoparticles,hydrogels,films,sponges,fibers,or even microspheres.These along with recent advances on chitosan-based composite biomaterials used for wound healing,food packaging,textile sector,3D printing and dental materials,were reviewed in detail.

Synthesis and evaluation of methionine and folate co-decorated chitosan self-assembly polymeric micelles as a potential hydrophobic drug-delivery system

In this study, an amphiphilic copolymer folate-succinyl-methionine-chitosan-octyl (FSMCO) was successfully synthesized step by step for self-assembling polymeric micelles. The copolymers formed micelle-like nanoparticles by their amphiphilic characteristics and structures were examined by UV-Vis absorption and Fourier transform spectroscopy. The sizes of blank and ICG derivativeloaded micelles measured by dynamic light scattering were about 170 and 140 nm, respectively, which were spherical in shape with an average zeta potential of 10 mV. Further studies on the stability showed that the micellar solutions maintain their sizes at room temperature for 1 month without distinct aggregation or dissociation. ICG derivative was much better photostable after being entrapped by the new carrier. The prepared FSMCO micelles displayed a good drug loading content (11.7%), entrapment efficiency (66.5%) and sustained release rate for the model drug fluorescein. The copolymers demonstrated weeny cytotoxicity toward Bel-7402, L02 and A549 cells when incubated for 2 d. Ligands modified micelles endowed preferable cell targeting capability and beautiful cell inhibition of HCPT-FSMCO on Bel-7402 tumor cells. This kind of polymeric micelles may be a promising nanovehicle in delivering near-infrared dyes for tumors imaging and chemotherapeutic drugs for cancer therapeutics.

用FTIR测定羧酰化壳聚糖和氰乙基壳聚糖的取代度

从壳聚糖 (脱乙酰度分别为 84%和 70 % )合成不同取代度的羧酰化壳聚糖和氰乙基壳聚糖作为标样 ,标样的取代度 (DS)由NMR或元素分析确定 .研究以FTIR作为工具测定这两个系列衍生物的取代度的方法 .吸光度用基线法得到 ,对所有不同探针谱带 ,参比谱带和基线作图法的组合进行比较 ,并通过 (A探针/A参比) /DS的平均相对偏差评价每种组合的优劣 .结果表明 ,对羧酰化壳聚糖 ,最合适的A探针/A参比 是A174 0 /A152 7;对氰乙基壳聚糖 ,最合适的A探针/A参比 是A2 2 4 9/A1590 .前者不仅适用于不同取代度的同一种O 羧酰化壳聚糖 (如丙酰化壳聚糖 )而且适用于不同取代度且不同碳数的 4个O 脂肪酸羧酰基取代的壳聚糖样品 .这两种组合的工作曲线的斜率分别为 2 .1(对A174 0BL1/A152 7BL1) ,0 .5 9(对A2 2 4 9/A1590BL1)和 0 .6 6 (对A2 2 4 9/A1590BL2 ) .实验还表明 。

壳聚糖的吸附行为及其FTIR光谱研究

用自制的壳聚糖对几种酸性染料和碱性染料模拟废水进行了吸附行为的研究,考察了吸附时间、壳聚糖脱已酰度及废水pH值对吸附效果的影响。研究表明,在吸附开始的20min内,壳聚糖对碱性品红和番红花红的吸附已基本达到平衡,且用量只为活性炭用量的2/3的情况下,对染料的吸附效果与活性炭几乎相当;它对酸性大红的吸附过程呈现一级反应动力学特征。文章还采用傅里叶变换红外光谱对壳聚糖吸附染料的机理进行了探讨,研究发现,壳聚糖分子中存在的大量羟基参与了对碱性品红和番红花红的吸附。