糠醛改性O-季铵化壳聚糖衍生物的合成及其抗菌性能

在制备水溶性较好的O-季铵化壳聚糖基础上,进一步与糠醛反应制备O-季铵化-N-呋喃亚甲基壳聚糖席夫碱及还原产物O-季铵化-N-呋喃亚甲基壳聚糖衍生物,用FTIR、1H NMR、EA（元素分析）、TG（热重分析）对产物进行表征。测定产物的最低抑菌浓度和抑菌率,并与O-季铵化-N-苯亚甲基壳聚糖席夫碱的抑菌效果进行比较。结果表明,产物对革兰氏阳性菌S.aureus的抗菌效果优于革兰氏阴性菌E. coli,在pH值5.5的条件下抗菌效果优于pH 值7.2。并且O-季铵化-N-呋喃亚甲基壳聚糖的抗菌效果>O-季铵化-N-呋喃亚甲基壳聚糖席夫碱>O-季铵化-N-苯亚甲基壳聚糖席夫碱 > O-季铵化-壳聚糖。研究表明,含呋喃杂环的壳聚糖衍生物的抗菌活性明显优于不含杂环的壳聚糖衍生物。     

交联壳聚糖树脂的制备及对Cr（Ⅵ）的吸附研究

以壳聚糖为原料,通过反相悬浮交联法制备交联壳聚糖树脂,将其用于吸附Cr（Ⅵ）,考察了吸附时间、溶液pH、树脂用量、Cr（Ⅵ）的初始浓度和介质等因素对吸附的影响。实验结果表明,吸附平衡时间为20 min,最佳吸附pH为6.0,最佳用量为10 mg,Cr（Ⅵ）起始浓度为6 mg/mL,介质对吸附的影响大小顺序：Cu2＋〉Na＋。重复使用3次,再生性能好。     

Cationic polyelectrolytes from natural building blocks of chitosan and inulin

Novel chitosan-N-inulin graft copolymers with different degree of substitution (DS) of chitosan were synthesized via water-soluble 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide mediated reaction. Chemical structure and composition of the chitosan derivatives was confirmed by chemical analysis, FT-IR, XPS, ¹H and ¹³C NMR spectroscopy, and potentiometry. Chitosan–inulin copolymers were high-molecular-weight hydrophilic products soluble in water in a wide pH range forming extraordinary viscous solutions. Intrinsic viscosity of N-modified chitosans was sharply suppressed by added electrolyte and had tendency to decrease at higher DS of chitosan. pK_α values of the chitosan–inulin copolymers determined from potentiometric titration data using Henderson–Hasselbalch equation were in the range 6–7 slightly increasing at higher DS. Novel water-soluble chitosan copolymers retained cationic properties of chitosan and could be used as surface conditioners.     

壳聚糖黏均分子量对其作表面施胶剂应用效果的影响

利用过氧化氢对壳聚糖进行氧化降解,获得了一系列不同黏均分子量的壳聚糖。用不同黏均分子量的壳聚糖对纸张表面进行施胶,研究施胶对纸张性能的影响。结果表明:壳聚糖黏均分子量的降低不利于其表面施胶效果,并通过扫描电镜图进行了证实;在相同条件下,相比于单独使用氧化淀粉,少量壳聚糖与氧化淀粉共混作用于纸张表面,对纸张表面强度增强效果更佳。     

Chitosan-conjugated thermo-responsive polymer for the rapid removal of phenol in water

Chitosan-conjugated thermo-responsive polymers (PNIPAAm-CSs) containing 2.0–8.7% (w/w) chitosan were readily synthesized by the condensation of chitosan and poly(N-isopropylacrylamide-co-acrylic acid) with 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide. PNIPAAm-CSs were water-soluble at 30 °C, while they deposited above the lower critical solution temperature (LCST, ca. 34 °C in 50 mM sodium phosphate, pH 6.8). Tyrosinase-induced phenol oxidation was performed in the dilute aqueous polymer solution at 30 °C for the rapid binding of oxidized compounds to the amino moiety of PNIPAAm-CS. By heating and shaking the solution, the polymer containing highly concentrated oxidized compounds deposited and agglutinated to a condensed coagulate. Increasing polymer concentration and chitosan content in the polymer increased the removal of phenol and its oxidized compounds. When 1.0 g of PNIPAAm-CS containing 8.7% chitosan was employed for treating 1 l of contaminated water, the concentration of phenol (19 mg l⁻¹) was reduced below the detection limit (0.08 mg l⁻¹) within 2 h.     

Preparation and rheological behaviors of 6‐carboxy‐chitosan

The hydroxymethyl groups of 2‐amino‐2‐deoxy‐D ‐glucose units in chitosan were selectively oxidized to carboxyl groups with NO₂ gas to form 6‐carboxy‐chitosan in aqueous 0.5 mol/L acetic acid. In optimal conditions, the 52.5% hydroxymethyl groups in chitosan could be converted into carboxyl groups. When the pH value of the solution is lower than 4.0 or more than 5.4, 6‐carboxy‐chitosan has common characteristics of a polycation or polyanion electrolyte, respectively, and when the pH value of the solution is 4.0—5.4, 6‐carboxy‐chitosan has common characteristics of an amphoteric polyelectrolyte. 6‐Carboxy‐chitosan has same macromolecular backbones as chitosan, and its isoelectric point (pI) value is 4.9. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1126–1130, 2004     

烷基化壳聚糖的制备及载药膜的释放行为研究

用不同碳链长度的卤代烷与壳聚糖反应制成N－烷基化壳聚糖。红外和X－射线衍射结果表明壳聚糖引入烷基基团后分子间氢键和结晶度受到削弱。采用氧化葡萄糖作交联剂，测定了不同pH条件下烷基化壳聚糖膜对维生素B2的渗透系数，并考察了该交联膜的细胞毒性，结果表明该膜无细胞毒性。     

Gel formation in polymeric composites for modification of fibrous materials

The possibility of using oxidized nucleotides and nuclosides as cross-linking reagents for preparing chitosan hydrogels with a broad range of applications was examined. It was found that the ratio of dialdehyde to chitosan amine and the reaction medium pH affected gel formation in aqueous acetic acid solutions of chitosan in the presence of the cross-linking reagents glutaraldehyde and oxidized nucleic acid derivatives. IR spectra of chitosan and its derivatives were recorded and characterized. Immobilization of the proteolytic enzyme trypsin in chitosan films on fibrous materials was studied.     

水溶性马来酰化壳聚糖的制备及其pH响应研究

以碳酸钠为催化剂,室温下制备了水溶性的马来酰化壳聚糖.由红外光谱分析的结果说明了马来酸酐成功接枝到壳聚糖分子上,且酰化反应后的壳聚糖的热性能较壳聚糖有了很大提高.采用MPT-2自动滴定仪和Nano-ZS粒度仪对不同pH值下的颗粒粒径和Zeta电位进行测定,发现存在2个等电点:pH=2.24和pH=5.45.     

水溶性壳聚糖稀土配合物的合成、表征及其抑菌性研究

以水溶性壳聚糖(CS)与稀土离子La3+, Nd3+, Sm3+, Eu3+和Dy3+在常温和pH值为4~5的条件下制备了水溶性壳聚糖稀土配合物CS-La, CS-Nd, CS-Sm, CS-Eu和CS-Dy. 并运用FT-IR, UV和TG-DTA对其配合物进行表征,并研究了配体和配合物的热稳定性及配合物的抑菌活性. 结果表明,5种配合物均有选择性抑菌性能;其对大肠杆菌和金黄色葡萄球菌均有很好的抑菌作用;其对5种菌的最小抑菌浓度(MIC)为120~500 mg/mL,低于800 mg/mL,且抑菌效果明显优于单独的壳聚糖和稀土硝酸盐. CS-Sm对大肠杆菌的抑菌性最好,MIC为125 mg/mL;而CS-Nd和CS-Sm对金黄色葡萄球菌的抑菌性最强,MIC均为120 mg/mL.     

Stimuli responsive gels based on interpenetrating network of chitosan and poly(vinylpyrrolidone)

New spherically shaped crosslinked IPN hydrogels based on chitosan and poly(vinylpyrrolidone) were prepared. The IPN hydrogels were synthesized in two steps: (1) chitosan (CHT) crosslinked beads were obtained by reaction of chitosan with ethyleneglycol diglycidyl ether (EGDE); (2) absorption of a suitable amount of a solution of vinylpyrrolidone (VP) monomer from the porous CHT beads followed to VP polymerization and crosslinking inside the network. Sequential IPN's at different composition were obtained: they reversibly swell in water at various pH and show sensitive volumetric behaviour.     

壳聚糖季铵盐及其衍生物的应用研究进展

壳聚糖是一种天然无毒多糖,可生物降解,具有生物相容性。在实际应用中壳聚糖水溶性差,只能在酸性介质中溶解。为了提高壳聚糖的溶解度并改善其理化及生物特性以扩大其应用范围,有必要对壳聚糖进行化学修饰。壳聚糖季铵盐是一种常见的壳聚糖修饰产物,属于水溶性壳聚糖衍生物,由于骨架上有强正电荷,因此其pH值溶解范围较宽。综述了壳聚糖季铵盐及其衍生物在抗菌活性、基因运载、给药系统、抗凝血材料、传感器等方面的应用进展,提出改进壳聚糖季铵盐及其衍生物的合成路线,可合成一系列生物学性能改良的壳聚糖季铵盐及其衍生物,有望将其应用于特殊领域。     

壳聚糖季铵化衍生物结构表征及特性研究

采用壳聚糖(CTS)与2,3-环氧丙基三甲基氯化铵(GTA)制备了不同取代度的水溶性壳聚糖季铵盐(HACC),通过红外、扫描电镜对壳聚糖、壳聚糖季铵盐结构进行表征,同时测试了壳聚糖季铵盐的水溶性、表面张力.结果表明:取代主要发生在壳聚糖的氨基上,改性后产物外观与粒度有很大变化;壳聚糖季铵化改性产物具有比壳聚糖更优良的水溶性、表面活性,且随着取代度的增加而提高.     

pH‐ and thermal characteristics of graft hydrogels based on chitosan and poly(dimethylsiloxane)

Graft copolymerization of epoxy‐terminated poly(dimethylsiloxane) (PDMS) onto chitosan was reacted without using a catalyst. pH‐sensitive hydrogels were obtained that are based on two different components: a natural polymer and a synthetic polymer. These PDMS substitutents provide the basis for hydrophobic interactions that contribute to the formation of hydrogels. Various graft hydrogels were prepared from different weight ratios of chitosan and PDMS. Swelling behavior of these hydrogels was studied by immersion of the gels in various buffer solution. Photocrosslinked hydrogels exhibited a high equilibrium water content (EWC). Particularly, the sample CP31 of the highest chitosan–PDMS weight ratio showed the highest EWC in time‐dependent, temperature‐dependent, and pH‐dependent swelling behavior. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2661–2666, 2002     

磁性壳聚糖微球的合成及其在固定化血管紧张素转化酶的应用

以化学共沉淀法合成Fe3O4纳米粒子为磁核,采用乳化交联法制备磁性壳聚糖微球,并对其形貌、结构和磁饱和强度等性质进行了表征。以磁性壳聚糖微球作为载体,固定化猪肺粗提物中的血管紧张素转化酶,并对固定化条件进行研究。结果表明,固定化血管紧张素转化酶的最佳条件为：pH值为8.3,最佳温度为50 ℃,最佳时间为1.5 h,最佳酶溶液蛋白浓度为6 mg/mL,此时固定化酶活力最高为0.048 U/g微球。与游离酶相比,固定化酶的pH值稳定性和热稳定性均得到提高。固定化酶重复使用10次,仍然保持40%以上相对活力,说明磁性壳聚糖微球是固定化血管紧张素转化酶的良好载体。     

微波辐射下香草醛改性壳聚糖的制备及其对金属离子的吸附

应用微波辐射法合成了香草醛接枝壳聚糖,用NaBH4进行还原。探讨了改性壳聚糖在25℃下对Ni2+、Mn2+、Cr6+的吸附及时间、离子浓度、pH值对吸附效果的影响。结果表明,还原后的改性壳聚糖比壳聚糖吸附性能明显改善,其对Ni2+、Mn2+和Cr6+的吸附容量分别可以达到116.23,63.83,47.27 mg/g。     

CdTe量子点的纯化以及作为pH探针的研究

以巯基乙酸为稳定剂在水相中合成了CdTe量子点,并将合成的CdTe量子点进行表征、纯化。通过用0.05 mol.L-1PBS缓冲溶液调节不同的pH来考察量子点的荧光强度和pH的关系。研究发现,水溶性的CdTe量子点是pH敏感的,随着pH值的降低,量子点荧光强度的下降规律与溶液pH值呈现良好的线性关系。结果表明,CdTe量子点是一个令人满意的pH敏感的探针,有潜在的化学和生物传感能力。     

Interaction of chitosan with tetraethyl orthosilicate on the formation of silica nanoparticles: Effect of pH and chitosan concentration

In this paper, we report the interaction of chitosan with tetraethyl orthosilicate on the formation of silica nanoparticles under different conditions of pH (5–9) and chitosan concentration (0–0.001379 mM). The silica nanoparticles were characterized by means of N₂-sorption, scanning electron microscopy and transmission electron microscopy. It was found that chitosan played two different roles on the formation of silica nanoparticles, depending on the pH values. At a low chitosan concentration, chitosan promoted the formation of larger silica nanoparticles in the pH range of 5–6, while it reduced the size of silica nanoparticles when the pH value was increased to the range of 6.5–8.5. However, based on the results of N₂-sorption analysis, two different sizes of silica nanoparticles caused by the growth of silica at different phases were observed. At high chitosan concentration, the size of silica nanoparticles continuously increased in the pH range of 5–6, while only smaller size of silica nanoparticles was obtained in the pH range of 6.5–8.5. At pH 9, chitosan molecules were found to have no significant effect on the formation of silica nanoparticles even though a large amount of chitosan was employed.     

Chitosan/Poly(Vinyl Alcohol)/LDH Biocomposites With pH-Sensitive Properties

The viscometric parameters of chitosan/poly(vinyl alcohol) mixtures determined at 37°C are sensitive to polymer composition and pH changes, giving information about interpolymer complexes formation. Hybrid composites based on interpolymeric chitosan/poly(vinyl alcohol) complexes and the inorganic matrix of layered double hydroxides were synthesized in the presence of glutaraldehyde. The viscoelastic parameters showed a stronger network formation at pH = 5.5 which is not broken down by the mechanical shear forces. The swelling kinetics of hybrid hydrogels is pH sensitive and the type of diffusion of small molecules into the network was established.     

Temperature and pH effects on the stability and rheological behavior of the aqueous suspensions of smart polymers based on N‐isopropylacrylamide,chitosan, and acrylic acid

This study describes the stability and rheological behavior of suspensions of poly(N‐isopropylacrylamide) (PNIPAM), poly(N‐isopropylacrylamide)‐chitosan (PNIPAM‐CS), and poly(N‐isopropylacrylamide)‐chitosan‐poly(acrylic acid) (PNIPAM‐CS‐PAA) crosslinked particles sensitive to pH and temperature. These dual‐sensitive materials were simply obtained by one‐pot method, via free‐radical precipitation copolymerization with potassium persulfate, using N,N′‐methylenebisacrylamide as a crosslinking agent. Incorporation of the precursor materials into the chemical networks was confirmed by elementary analysis and infrared spectroscopy. The influence of external stimuli such as pH and temperature, or both, on particle behavior was investigated through rheological measurements, visual stability tests, and analytical centrifugation. The PNIPAM‐CS particles showed higher stability in acid and neutral media, whereas PNIPAM‐CS‐PAA particles were more stable in neutral and alkaline media, both below and above the lower critical solution temperature of PNIPAM (stability data). This is due to different interparticle interactions as well as those between the particles and the medium (also evidenced by rheological data), which were also influenced by the pH and temperature of the medium. Based on the results obtained, we found that the introduction of pH‐sensitive polymers to crosslinked PNIPAM particles not only produced dual‐sensitive materials but also allowed particle stability to be adjusted, making phase separation faster or slower, depending on the desired application. Thus, it is possible to adapt the material to different media. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013