The rheology of hydrogels based on chitosan–gelatin (bio)polyelectrolyte complexes

Influence of the chitosan concentration in the low-concentrated acidic hydrogels formed by (bio)polyelectrolyte chitosan–gelatin complexes (at a constant gelatin concentration of 1%) was studied by shearing in steady flow and linear oscillations. These complexes, including native gelatin, demonstrate clearly expressed viscoelastic properties. Viscoelastic properties correlated well with the non-Newtonian behavior of hydrogels (according to the Cox–Merz rule). Increasing the chitosan concentration (from 0.1% to 0.6%) results in exponential growth of the apparent viscosity, yield stress, and storage modulus. However, a further increase in chitosan concentration to 0.8% leads to a reduction in these rheological parameters due to the electrostatic repulsion of similarly charged polyelectrolyte complexes under the high concentration of these complexes. The macro-rheological properties of chitosan–gelatin gels are mainly determined by the colloidal structure of sol-precursors in solutions. The yield stress dependence on the radius of the dispersed particles is of square type. Electron photomicrographs showed that the introduction of even small quantities of chitosan leads to radical changes in the supramolecular structure of the gelatin gel.     

Highly sensitive and selective assay method for iodide ion determination based on gold nanoparticles conjugated with glycol chitosan

A sensitive colorimetric method for the determination of iodide ions was developed using gold nanoparticles (AuNPs) functionalised with glycol chitosan (GCS). The iodide ions were at the centre of the O–I^––O coordination structure, formed with the GCS-AuNPs, reducing their interparticle distance and inducing aggregation. Time-of-flight secondary ion mass spectrometry analyses showed that the bound iodide ions were coordinated to the oxygen atoms of the ethylene glycol in GCS, with this aggregation leading to a considerable variation in colour from light red to dark violet. Using this GCS-AuNP probe, the iodide ion concentration in environmental, biological and pharmaceutical samples could be determined by both the naked eye and UV-Vis spectroscopy. Additionally, the sensitivity of the detection was found to be markedly enhanced at pH 6, where a more pronounced colour change was observed. The absorption ratio A₇₀₀/A₅₂₁ of the functionalised AuNP solution correlated linearly with the iodide ion concentration within the range 0.0–10.0 mg/L, and the limits of detection in tap water, pond water, and bovine serum solution were 3.5, 3.6, and 3.4 μg/L, respectively. The present assay method can thus be utilised to rapidly measure the concentration of iodide ions in aqueous samples.     

庆大霉素对羟基磷灰石/壳聚糖复合材料性能的影响

羟基磷灰石/壳聚糖-庆大霉素(HA/CS-G)缓释材料为骨髓炎的定点缓释给药提供了一种有效的局部药物缓释体系。为了研究抗生素对羟基磷灰石/壳聚糖材料性能的影响,采用共沉淀法制备了HA/CS-G缓释材料。利用红外光谱(IR)、X射线衍射(XRD)和扫描电子显微镜(SEM)对材料进行了表征。以不载药的羟基磷灰石/壳聚糖(HA/CS)为对照,研究了庆大霉素对HA/CS复合材料抑菌性能、力学性能和降解性能等的影响。实验结果表明,HA/CS-G有良好的抑菌效果。负载庆大霉素后HA/CS的机械强度明显增强,而材料的降解速率有所下降。本文采用的二次成型技术显著增大了材料的机械强度。     

磁性壳聚糖去除水中腐殖酸的研究

采用高温水热法合成了磁性壳聚糖,并研究了其对水中腐殖酸(HA)的吸附、脱附行为。表征结果表明,磁性壳聚糖粒径大小为200～300nm,氨基含量1.29mmol·g-1,BET比表面积36.00m2·g-1,饱和磁化强度为38.78emu·g-1,易于磁性分离。HA在磁性壳聚糖上的吸附等温线可用Freundlich方程模拟,吸附动力学符合拟二级动力学方程。HA的吸附量随溶液pH值的升高而降低,随不同阳离子浓度增加而增加,不同类型的阳离子对HA吸附效果影响的大小顺序为:Ca2+Mg2+Na+K+。经5个脱附再生循环,磁性壳聚糖仍能保持79.8%的吸附量,表明该吸附剂再生性好,可循环使用。     

羟乙基壳聚糖的合成及其与聚乳酸的相容性

本文以异丙醇为溶剂,碱化壳聚糖与2-氯乙醇反应制备了羟乙基壳聚糖,对产物的结构与性能进行了分析表征;然后以二甲基亚砜为溶剂,采用溶液共混法制备了一系列不同组成的壳聚糖/聚乳酸和羟乙基壳聚糖/聚乳酸复合膜,对两组分间的相容性进行了研究。结果表明,羟乙基化反应在-OH和-NH2上均有发生,壳聚糖单元糖环上的羟乙基取代度为2.46;改性后,壳聚糖结晶性能和起始热分解温度下降,溶解性能得到改善。复合膜的电镜结果显示,在壳聚糖/聚乳酸复合膜中,相分离现象显著存在,壳聚糖在聚乳酸基体中的分散不均匀,有团聚现象,随着壳聚糖含量增加,两组分间的相分离程度增大,团聚现象更为严重,当壳聚糖含量达到50%时,已难以制备完整的复合膜;与之相反,羟乙基壳聚糖/聚乳酸复合膜中两种组分之间的相容性有所改善,相分离现象不明显,并且,当羟乙基壳聚糖含量从10%增加到50%,复合膜中两种组分之间的相容性变化不大。     

O-季铵化-N-壳聚糖Schiff碱的合成及表征

对壳聚糖氨基和羟基进行化学改性,合成了水溶性双功能化壳聚糖衍生物O-季铵化-N-壳聚糖Schiff碱(O-HTCCS);用红外光谱表征了产物的结构;确定了O-HTCCS的最佳合成条件,并测定了其溶解性能.结果表明,合成O-HTCCS的最佳条件为:壳聚糖Schiff碱/缩水甘油三甲基氯化铵(GTMAc)摩尔比为1∶5;反应时间24 h;反应温度70℃.在最佳条件下合成O-HTCCS的产率为78.5%,季铵化度为89.7%.与此同时,O-HTCCS的水溶性随季铵化度的增大而提高,季铵化度达到70%以上能溶于水;且其在有机溶剂中的溶解性优于壳聚糖.     

Quantitative characterization of membrane formation process of alginate–chitosan microcapsules by GPC

The semi-permeable membrane of alginate–chitosan (AC) microcapsules has been proven important to control the microcapsule stability and selective substance diffusion rate. Therefore, a novel and operable methodology based on gel permeation chromatography (GPC) was established for quantitative characterization of the membrane formation process, so as to provide guidance on performance improvement of AC microcapsules in biomedical applications. Not only the molecular weight (M_w) and its distribution of chitosan can be obtained by GPC, but also the area integral of molecular weight peaks can be linearly correlated to chitosan concentration in certain range. The dynamic membrane formation process was then obtained by quantitatively analyzing reaction amount of chitosan with time, which showed that for chitosan molecules with wide M_w distribution, only parts of molecules bind with alginate to form microcapsule membrane. Moreover, the contribution of chitosan molecules participating in the membrane formation process was also different. These new findings, therefore, are helpful for adjusting and controlling the membrane formation process and properties of microcapsule membrane.     

阿司匹林-蒙脱土-壳聚糖缓释微球的制备及其体外释放性能

利用溶液法预先制备壳聚糖(Cs)-蒙脱土(MMT)复合材料(Cs-MMT),以Cs-MMT、Cs为原料,采用反相悬浮聚合法制得一种新型药物缓释体系阿司匹林-蒙脱土-壳聚糖载药微球(Asp-MMT-Cs)。采用FT-IR、SEM表征了Cs-MMT和Asp-MMT-Cs载药微球的结构及形态;设计正交实验优化了Asp-MMT-Cs载药微球的制备工艺;通过体外释放实验探讨了载药微球在不同模拟释放液中的释药规律。结果表明:所得微球球形度好,粒径分布较均匀;最优工艺制得的载药微球平均粒径为81.20μm,载药量为9.61%,包封率为76.78%。该缓释体系具有pH敏感性,更倾向于在pH较高的磷酸盐缓冲溶液中释放。     

胺基化壳聚糖树脂吸附分离茶多酚的研究

对珠状壳聚糖树脂进行胺基化改性,制备了胺基化珠状壳聚糖树脂,并用FTIR对胺基化珠状壳聚糖树脂进行了结构表征。利用该树脂对绿茶中茶多酚进行吸附分离,探讨了其吸附条件,考察了其吸附性能。结果表明,胺基化壳聚糖树脂对茶多酚的吸附既符合Langmuir等温式,也符合Freundlich等温式;本实验最佳吸附条件为:温度25℃,茶汤溶液pH值5,吸附时间2h;最大吸附量达到486.0mg/g。     

Antibacterial activity of N-quaternary chitosan derivatives: Synthesis, characterization and structure activity relationship (SAR) investigations

Quaternary N-(2-(N,N,N-tri-alkyl ammoniumyl and 2-pyridiniumyl) acetyl) derivatives of chitosan polymer, chitooligomer, and glucosamine (monomer) were synthesized for the purpose of investigating the structure activity relationship (SAR) for the antibacterial effect. Novel methods were used in the synthesis. The final chitosan and chitooligomer derivatives could thus be obtained in two steps without prior protection of the hydroxyl groups. However, in order to obtain chitosan derivatives with the bulky N,N-dimethyl-N-dodecyl- and N,N-dimethyl-N-butyl side chains three steps were needed, starting from 3,6-O-di-tert-butyldimethylsilyl chitosan (3,6-O-di-TBDMS chitosan) as the key intermediate. The quaternary ammoniumyl acetyl derivatives of glucosamine were synthesized from glucosamine or tetra-O-acetylglucosamine. N,N,N-trimethyl chitosan (TMC) was used as reference compound for investigation of antibacterial activity. Clinical Laboratory Standard Institute (CLSI) protocols were used to determine MIC and MLC for activity against clinically important Gram-positive strains Staphylococcus aureus (ATCC 25923), and S. aureus (MRSA) (ATCC 43300), and Gram-negative strains of Escherichia coli (ATCC 25922), P. aeriginosa (ATCC 27853) and Enterococcus facialis (ATCC 29212). The MIC values for the compounds ranged from 8 to ?8192 mg/L. In general the N-(2-(N,N-dimethyl-N-dodecyl ammoniumyl) acetyl) derivatives of chitooligomer and glucosamine monomer were more active against bacteria than derivatives with shorter alkyl chains. In contrast the N-(2-(N,N-dimethyl-N-dodecyl ammoniumyl) acetyl) derivatives of chitosan were less active than derivatives with N-(2-N,N,N-trimetylammoniumyl) acetyl or N-(2-(N-pyridiniumyl) acetyl) quaternary moiety. N,N,N-trimethyl chitosan (TMC) was the most active compound in this study.