A small-angle neutron scattering and rheology study of the composite of chitosan and gelatin

The composite chitosan/gelatin solutions and films formed from these solutions were studied by rheological measurements, SANS and tensile tests. The relationship between the inter-molecule interactions with microstructure, rheological behaviour of a solution and eventually the mechanical performance of formed films was established. It was found that the complex formed between chitosan and gelatin was mainly through hydrogen bond but the size of the structure was also affected by electrostatic repulsions. The local structure (correlation length) and the global structure (large inhomogeneous structure size) in the composite solutions were found to be highly correlated to each other. It was also found that the interactions between these two polymers in solution were closely related to the mechanical properties of the formed films. This work will enable one to design films with desired mechanical properties through the combination of different polymers at optimum weight ratios.     

Cell outer membrane mimetic modification of a cross-linked chitosan surface to improve its hemocompatibility

A novel strategy has been developed to improve the hemocompatibility of chitosan surface by cell outer membrane mimetic structure able to reduce protein adsorption and cell adhesion. Phosphorylcholine dichloride was synthesized and grafted onto a glutaraldehyde-cross-linked chitosan (CS-GA) film surface to prepare phosphorylcholine-coated CS-GA film (CS-GA-PC) through a heterogeneous reaction process. The spectroscopic and contact angle characterization show that a cell outer membrane mimetic structure was formed on the cross-linked chitosan surface, and the significantly improved hemocompatibility of the modified surface was shown by a suppression of 94% on platelet adhesion, a suppression of 60–70% for bovine plasma fibrinogen and bovine serum albumin adsorptions. These results demonstrated that this cell outer membrane mimetic surface modification with phosphorylcholine dichloride is a promising strategy to improve the hemocompatibility of chitosan.     

共价键合修饰壳聚糖pH传感器的研制

以共价键合的方法将壳聚糖修饰到玻碳电极上制成了pH传感器,探讨了该传感器的性能及作用机理.结果表明该传感器在pH 0.7～11.0的范围内电极电势与pH符合Nernst响应,斜率为58.3 mV/pH,可准确测定较高酸度溶液的pH,克服了玻璃pH传感器的"酸误差"的缺点.该传感器内阻小,易微型化,在一定的pH范围内对温度不敏感且具有较好的准确度和重现性,较快的响应速度.可用于雨水和饮料等实际样品溶液的pH的测定.     

Using NaCl particles as porogen to prepare a highly adsorbent chitosan membranes

Macroporous chitosan membranes were prepared by using NaCl particles porogen and genipin as cross-linking agent. For characterization and sorption behavior comparison, other genipin cross-linked chitosan membranes were prepared by either freeze drying or by using silica particles as porogen. The mean pore diameter, the porosity, the crystallinity index (CrI) as well as the effect of the drying procedures of these chitosan membranes were examined. NaCl reduced the CrI of the chitosan membrane. The oven drying (OD) procedure decreased the mean pore diameter, the porosity, and increased the CrI of the chitosan membranes when compared with the vacuum drying (VD) procedure. The heat treatment of chitosan membrane in aqueous NaOH to attract silica porogen increased the CrI of the membrane. Under the same conditions, the membranes prepared with NaCl had better sorption performance on RR 189 and Cu²⁺ than other membranes. The maximum sorption capacity (q_e) reached 1836.17 mg RR 189/g chitosan and 151.98 mg Cu²⁺/g chitosan. The pore diameter (d_pore) of the membranes was much larger than the diameter of the adsorbate molecules (d_adsorbate), such that the ratio of d_pore/d_adsorbate had little influence on q_e. The porosity and the amorphous extent of the membranes were almost the same on q_e. When using tyrosinase catalyzing, the hydrocaffeic acid (HCA) grafted on the NaCl treated chitosan membrane was almost 10 times more than on chitosan beads. The chitosan membrane prepared with NaCl can be used as a good adsorbent with high loading capacity for implanting molecules (such as ligands, enzymes, etc.) on.     

Structure and properties of chitosan derivatives modified calcium polyphosphate scaffolds

Organic and inorganic composite material is becoming a solution on making the mechanical and degradation properties of biomaterial more suited. Porous calcium polyphosphate was immersed into different concentrations of carboxymethyl chitosan before immersing 10% alginate dialdegyde. After freeze-drying, the scaffolds were performed in physiologic saline. At stated day, the weightloss, Ca²⁺ concentration, pH value and morphology were measured. The biocompatibility of the composite was demonstrated by extract and direct contact tests. As the results showed, the degradation rates of composites were faster, and the compressive strength became bigger because of the cross-linked network formed by Carboxymethyl chitosan (CMC) and alginate dialdehyde (ADA). The pH value of composite was higher than that of calcium polyphosphate (CPP) due to the organic part of composite’s pH was in slight alkaline. From the SEM, the cross-linked network structure could be observed clearly. Because the glycosaminoglycans-like chains in CMC molecules, which are typically presented in extracellular matrix (ECM), extractions of composite material gave the cells good adhesion and growth condition. All the results testified the composite scaffold was a good candidate for bone repair.     

Synthesis and cell activity of novel galactosylated chitosan as a gene carrier

It is important for gene carrier to transport DNA into target cells. Although viral vectors are very efficient gene-transfer vehicles, significant drawbacks limit their applications. Chitosan (CS) has been researched widely as a non-viral vector. However, the low cell specificity and low transfection efficiency of chitosan need to be overcome. In order to conquer the drawback of chitosan, the present paper is concerned with the synthesis of novel galactosylated chitosan (GC) through etherization of chitosan and galactose in THF using BF₃·OEt₂ as promoter. The final product was characterized and confirmed by FT-IR and ¹H NMR. The degree of O-substitution (DS) of chitosan by galactose was measured to be 10.38% using anthrone-sulfuric acid colorimetric method. The mean particle diameter and average zeta potential of the GC/DNA complex were 350 nm and +22.1 mV, respectively. The GC/DNA nanoparticle was tested to transfect HEK293 cells, and the viability of HEK293 cells was not affected by the GC/DNA nanoparticle compared to that of the control.     

Self-aggregates of deoxycholic acid-modified chitosan as a novel carrier of adriamycin

A novel and simple method for delivery of adriamycin (ADR) was developed using self-aggregates of deoxycholic acid-modified chitosan. Deoxycholic acid was covalently conjugated to chitosan via EDC-mediated reaction to generate self-aggregated chitosan nanoparticles. ADR was physically entrapped inside the self-aggregates and the characteristics of ADR-loaded chitosan self-aggregates were analyzed by dynamic light scattering, fluorescence spectroscopy, and atomic force microscopy (AFM). The maximum amount of entrapped ADR reached 16.5 wt% of chitosan self-aggregates, suggesting a loading efficiency of 49.6 wt%. The size of ADR-loaded self-aggregates increased with increasing the loading content of ADR. AFM images showed spherical shape of ADR-loaded self-aggregates, and ADR was slowly released from chitosan self-aggregates in PBS solution (pH 7.2). Received: 24 April 2000/Accepted: 11 July 2000     

New approach to the quaternization of chitosan and its amphiphilic derivatives

Regioselective quaternization of chitosan and its amphiphilic derivatives has been carried out by means of reaction with betaine in the presence of the coupling reagent 2-ethoxy-1-ethoxycarbonyl-1,2-dihydroquinoline (EEDQ) in aqueous media at pH 5.5 ± 0.5. This reaction results in preparation of N-/(trimethylammonio)acetyl/chitosan chloride and its amphiphilic derivatives. The degree of quaternization increases with increasing EEDQ/chitosan ratio and is partly accompanied by N-ethoxycarbonylation. That side-product formation can be minimized by increasing betaine/EEDQ ratio.     

Advancement of chitin and chitosan as promising biomaterials

Biopolymers like cellulose, polysaccharides, chitosan, starch, chitin, and alginates have sparked an increasing curiosity in creating natural replacements for synthetic polymers during the last several decades. Chitin is a major part of fungi’s cell walls, the crustaceans’ exoskeletons, like lobsters, crabs, and shrimps, cephalopod beaks, the radulae of mollusks, and fish and lissamphibians scales. Since the late 1970 s, biopolymer chitosan has gathered interest in basic science and applied research due to its incredible macromolecular framework, physicochemical properties, and biological activities, which differ from those of synthetic polymers. Chitin and derivatives thereof have practical usages in chemistry, the agriculture sector, medicine, cosmetics, as well as textile and paper industries. Chitosan has also received a lot of recent interest in the fields of dentistry, ophthalmology, veterinary science, biomedicine, the drink industry, hygiene and personal care, catalysis, chromatography, sewage treatment, and biotechnology. Numerous fundamental investigations have been conducted on chitin and chitosan. This article presents a short compact summary of research over the last two decades in an attempt to highlight the works on chitin and chitosan applications.     

肝靶向甘草次酸修饰的壳聚糖纳米粒子的合成和表征

合成了修饰甘草次酸的壳聚糖(GA-CTS), 采用离子交联法制备了GA-CTS纳米粒子. 该材料可能具有肝细胞主动靶向作用, 为进一步的肝靶向药物控释的研究奠定了基础.     

Self-aggregated nanoparticles of cholesterol-modified chitosan conjugate as a novel carrier of epirubicin

Cholesterol-modified chitosan conjugate with succinyl linkages (CHCS) was synthesized and characterized by fourier transform infrared (FTIR) and proton nuclear magnetic resonance (¹H NMR). The degree of substitution (DS) of cholesterol moiety determined by elemental analysis was 7.3%. The self-aggregation behavior of CHCS was evaluated by the fluorescence probe technique and the critical aggregation concentration (CAC) was 1.16 × 10⁻² mg mL⁻¹ in 0.1 M acetic acid solution. CHCS formed monodisperse self-aggregated nanoparticles with a roughly spherical shape and a mean diameter of 417.2 nm by probe sonication in aqueous media. Epirubicin (EPB), as a model anticancer drug, was physically entrapped inside CHCS self-aggregated nanoparticles by the remote loading method and the characteristics of EPB-loaded CHCS self-aggregated nanoparticles were analyzed using dynamic laser light scattering (DLLS), transmission electron microscopy (TEM) and fluorescence spectroscopy. EPB-loaded CHCS self-aggregated nanoparticles were almost spherical in shape and their size increased from 338.2 to 472.9 nm with the EPB-loading content increasing from 7.97% to 14.0%. The release behavior of EPB from CHCS self-aggregated nanoparticles was studied in vitro by dialysis method. The results showed that EPB release rate decreased with the pH increase of the release media. In phosphate buffered saline (PBS, pH 7.4), the EPB release was very slow and the total release amount was about 24.9% in 48 h.     

Effect of chitosan and ions on actuation behavior of cellulose–chitosan laminated films as electro-active paper actuators

Cellulose-chitosan laminated films were made for Electro-Active Paper (EAPap) actuators and the effect of chitosan and different types of free ions namely, Cl⁻, NO₃⁻ and CF₃COO⁻ were investigated on the actuation behavior. The fabrication process of the films was explained and the actuation performance was tested in terms of bending displacement of the actuators. It was observed that, chitosan content and type of free ions influence the tip displacement of the actuators. Cl⁻ was found the best free ion among others, and detail observations are explained. By laminating chitosan layer on the cellulose films, the humidity sensitiveness of cellulose EAPap actuators was reduced.     

壳聚糖及其衍生物基因载体的研究进展

壳聚糖是一种天然的生物可降解性,生物相容性好而且安全无毒的多糖,因而它成为基因治疗载体研究的热点。本文就近年来壳聚糖及其衍生物作为基因载体转染的研究进展和现状作简要的综述,并对转染率的影响因素如壳聚糖的分子量、粒径、脱乙酰度等进行着重介绍。     

Swelling of hydrophobically modified poly(acrylamide) and poly(acrylamide)-co-(acrylic acid) gels in surfactant solutions

A series of hydrophobically modified polyacrylamide and polyacrylamide-co-poly(acrylic acid) gels with systematically varying hydrophobicity were prepared by free-radical polymerization of acrylamide, n-alkylacrylamides (n = 10, 12, and 14), and acrylic acid. The swelling of these gels was examined in water and in both anionic and cationic surfactant solutions. It was found that the gels which incorporated acrylic acid showed extremely high swelling in water. Maximum swelling was observed in gels which incorporated 10 mol% acrylic acid. The swelling of these gels was much less in solutions of both anionic and cationic surfactants than in water. The gels which did not incorporate acrylic acid demonstrated little swelling in water, but showed increased swelling in both anionic and cationic surfactant solutions with increased hydrophobicity of the gel. Received: 1 February 1999 Accepted in revised form: 5 March 1999     

Adsorption of Cu2+ by modified chitosan microspheres and its application in homocoupling of arylboronic acid

The CC bond coupling reactions have a wide range of applications in the synthesis of natural substances and the synthesis of physiologically active compounds. We first prepared modified chitosan microspheres by emulsification and investigated the performance of the chitosan adsorbent for the adsorption of copper ions. We then evaluated the catalytic performance of chitosan-supported copper microspheres in the self-coupling of arylboronic acids using 4-methoxybenzene as the model substrate, while exploring a wide range of substrates including aryl boronic acid derivatives and heterocyclic arylboronic acids, including aldehyde, nitro, and aldehyde groups. The experimental results show that good to excellent yields (55%-95%) of the desired dimer products were obtained under mild conditions at room temperature and in air, and the catalytic material could be reused up to five times with no significant decrease in catalytic activity.     

Use of quasi-isoelectric buffers as anolyte and catholyte to improve capillary isoelectric focusing performances

The use of quasi-isoelectric anolytes and catholytes has been investigated to improve CIEF performances. Narrow pH cuts of carrier ampholytes (NC) have been compared to more conventional couples of anolytes/catholytes (phosphoric acid/sodium hydroxide and glutamic acid/lysine). First, a CIEF setup that consists in a bare silica capillary and 70:30 water/glycerol separation medium has been used. The experiments have shown that when using NC instead of more classical anolytes and catholytes, an increase in the protein detection time was observed and the resolutions obtained for neutral and acidic proteins were doubled. Moreover, according to the NC fraction used, the resolution was modified. In order to investigate further the mechanisms involved, a second setup using a capillary coated with hydroxypropylcellulose was used. With this setup no difference has been observed when changing anolyte and catholyte nature. A simple methodology has then been developed to evaluate EOF during focusing and mobilization steps of CIEF experiments. It highlighted the crucial role played by EOF when using a bare silica capillary. EOF indeed decreased by 33% during mobilization step when using NC instead of classical anolytes and catholytes.     

聚合度3～6甲壳寡糖的制备与TOF-MS分析

本文用自制酸性蛋白酶粗酶液降解壳聚糖,研究了降解过程中温度、pH值、反应时间、酶用量及壳聚糖脱乙酰度(DD)对酶降解能力的影响。以85.5%脱乙酰度(DD)、分子量(Mw)为56.0×104的壳聚糖为底物,45℃、pH4.6降解数小时,降解产物由红外光谱、分子量测定(GPC)和基体辅助激光解吸电离飞行时间质谱(MALDI TOF MS)表征。主要降解产物的脱乙酰度有所降低;酶解8h,其水解产物用NaOH调至pH9无沉淀,9h分子量降为0.93×103,经MALDI TOF MS分析产物为聚合度3～6的甲壳寡糖,3～6糖中各糖含量分别为13.3%、27.3%、49.0%、10.1%。     

Adsorption behavior of uranium(VI) and other ionic species on cross-linked chitosan resins modified with chelating moieties

Cross-linked chitosan resins with catechol (catechol-type chitosan, type 1 and type 2), iminodiacetic acid (IDA-type chitosan), iminodimetylphosphonic acid (IDP-type chitosan), phenylarsonic acid (phenylarsonic acid-type chitosan), or serine (serine-type chitosan) were prepared for the collection and concentration of uranium(VI). The adsorption behavior of U(VI) and other ionic species, such as metal ions and oxo-acid ions, on the cross-linked chitosan (base material) and chitosan resins modified with chelating moieties was examined using a column procedure. Especially, the catechol-type chitosan (type 2) adsorbed U(VI) at pH 2-7, and selectively collected U(VI) at acidic pH regions by forming a stable chelate with hydroxyl groups of catechol moiety introduced to the chitosan. Also, the adsorption properties of cationic and anionic species present in aquatic media were elucidated. The adsorption ability for U(VI) was in the order: catechol-type chitosan (type 2) > serine-type chitosan > phenylarsonic acid-type chitosan > the others. The catechol-type chitosan (type 2) was useful for the collection and concentration of uranium(VI).     

一种新的液晶高分子——丁酸壳聚糖的合成与表征

甲壳素几乎不溶于任何溶剂,由于其脱乙酰化产物壳聚糖含自由氨基,能被酸质子化而溶解,所以壳聚糖的应用领域远多于甲壳素.但是壳聚糖也仅能溶于酸性介质中,并不能溶于纯水和普通有机溶剂,因而人们对甲壳素或壳聚糖进行各种化学改性[1,2],寻求溶解性更好尤其能溶于水的衍生物,以扩大其应用范围.本文按文献[2～4]方法合成了O-丁酰化壳聚糖(简称丁酸壳聚糖),首次报道它具有溶致液晶性.     

Preparation and evaluation of stable coating for capillary electrophoresis using coupled chitosan as coated modifier

A coated capillary modified with a coupled chitosan (COCH) was developed by using a simple and fast (60 min) process that could be easily automated in capillary electrophoresis instrument. The COCH coating was achieved by first attaching chitosan to the capillary inner wall, and then coupling with glutaraldehyde, and rinsing chitosan again to react with glutaraldehyde. The COCH coating was stable and showed amphoteric character over the pH range of 1.8-12.0. When the pH value was lower than 4.5, the capillary surface possessed positive charges, which caused a reversal in the direction of the electroosmotic flow (EOF). The normal EOF direction could be obtained when the pH value was higher than 4.5. The COCH coating showed strong stability against 0.1 mol/L HCl, 0.1 mol/L NaOH and other solvents compared with conventional chitosan coating. The relative standard deviation of the run-to-run, day-to-day and capillary-to-capillary coating was all below 2% for the determination of EOF. The COCH-modified capillary was applied to acidic and basic proteins analyses and high efficiency could be attained. The comparison between unmodified capillary, chitosan-modified and COCH-modified capillary for the separation of real sample, extract from Elaphglossum yoshinagae with water, was also studied. Better results could be obtained on COCH-modified capillary than the other two capillaries.