壳聚糖及其衍生物水凝胶的研究进展

综述了近年来壳聚糖及其衍生物水凝胶的研究工作进展,介绍了水凝胶的制备方法和应用,尤其是在生物医药方面的广泛应用,并对其未来进行了展望。     

荧光探针法研究壳聚糖在水溶液中的聚集态行为

本文用两种结构类似的分子内电荷转移化合物,3-羟基-6甲基-4-N,N-二甲氨基黄酮丙酸酯(PF)和3-甲氧基-4’-N,N-二甲氨基黄酮(DMMF),作为荧光探针,研究了壳聚糖在水溶液中的聚集状态.研究结果发现,当壳聚糖浓度增大到1×10^-3 kg/L或以上时,PF在430 nm处的荧光强度有一突增现象.利用DMMF作为荧光探针,研究了它在不同壳聚糖溶液中的稳态偏振,研究发现,随着壳聚糖浓度的增大,其偏振度也明显增大.这些结果进一步证实了壳聚糖在水溶液中的聚集特性,同时也为分子内电荷转移化合物——黄酮类化合物作为荧光探针研究生物大分子在水溶液中的构象提供了有益的尝试.     

荧光探针法研究可聚合有机分子(BMDM)/二苯醚的凝胶化过程

用荧光素作荧光探针 ,研究了可聚合凝胶因子 4,4′ 二 (α 甲基丙烯酰氧基 1 ,3 亚乙氧基羰基丙酰氨基 )二苯甲烷 (BMDM)在二苯醚的凝胶化过程中的聚集状态 .研究结果发现 ,与荧光素在二苯醚溶液中的荧光光谱相比 ,在凝胶中出现了 1 0～2 5nm的红移 ;而且发现分子凝胶的凝胶化时间随着BMDM浓度的增加而减小 .偏振荧光法研究分子凝胶的取向发现 ,该分子凝胶的形成过程是从各向同性的溶液(P0 =0 )向各向异性的溶胶 (P>0 )转变 ,再向各向同性的凝胶 (Pgel≈ 0 )转变的过程     

壳聚糖与聚乙二醇交联水凝胶研究

研究对壳聚糖(CS)进行化学修饰得到了不同丙烯酰基取代度(1.03%,3.55%和5.21%)的丙烯酰化羟丙基壳聚糖(AHCS);通过自由基引发反应,AHCS与聚乙二醇二丙烯酸酯(PEGDA)交联得到壳聚糖(CS)与聚乙二醇(PEG)为主体的交联水凝胶。通过SEM观察其为通透性良好的多孔性支架材料。水凝胶的溶胶含量和溶胀度随丙烯酰基取代度的增加而降低,水凝胶中壳聚糖的降解速率也随丙烯酰基取代度的升高而降低。对于同一取代度的交联水凝胶,其在酸性和碱性条件下的溶胀度大于中性环境。细胞试验表明,壳聚糖与聚乙二醇交联水凝胶具有良好的生物相容性。     

Cu(Ⅱ)自旋探针法研究温度敏感性水凝胶的相行为

本文采用Cu(Ⅱ)自旋探针法研究了N- 取代基丙烯酰胺水凝胶在不同温度时的ESR谱,发现不同的温度敏感性水凝胶.其Cu(Ⅱ)探针的ESR各向异性谱的变化也不同.这主要是由于取代基与Cu(Ⅱ)的相互作用不同所致.对于具有LCST相行为的NNPA 和NIPA水凝胶,当温度达到并超过其相转变温度时,即可测得其Cu(Ⅱ)自旋探针各向异性的ESR倒置谱,这种倒置谱是由于凝胶相变后,网格塌陷,网络缠裹水化Cu(Ⅱ)离子的结果.运用Cu(Ⅱ)自旋探针研究凝胶的相结构及其微观相行为是一种可行的方法     

壳聚糖纳米粒子荧光探针的制备和表征

通过低分子量的壳聚糖(LCS)聚阳离子与三聚磷酸钠(TPP)的静电作用制备纳米级壳聚糖微球,并利用壳聚糖链上丰富的氨基与荧光素异硫氰酸酯(FITC)反应从而制备纳米壳聚糖微球荧光探针(NFCS)。结果表明,当壳聚糖分子量为60000,LCS与TPP的质量比为6∶1时,可得到粒度均一的球形纳米粒子,平均粒径为40±3 nm。荧光倒置显微镜观察证实FITC结合到壳聚糖微球上。荧光光谱分析显示NFCS的最大激发波长、最大发射波长与游离态FITC无显著差异。光漂白实验证实NFCS的稳定性比游离态FITC有显著提高。     

芘荧光探针法研究C60-胶束水溶液体系的微环境性质

首次运用芘荧光探针法考察了Ｃ６０－胶束水溶液体系的微环境性质,发现Ｃ６０的介入可以改变非离子表面活性剂所形成胶束的结构而破坏胶束的有序情,从而使胶束的体积变大。Ｃ６０能显著猝灭芘单分子的荧光,而几乎不会破坏芘单体与其激基二聚体的平衡,表明Ｃ６０主要是同芘单分子之间发生ＣＴ作用。同时Ｃ６０对芘单分子荧光的猝灭在有机体系中主要呈现静态猝灭而在胶束体系中则主要呈现动态猝灭。     

荧光探针法测定甜菜碱cmc的研究

荧光探针法测定甜菜碱ｃｍｃ的研究任学贞，李干佐，王弘立，翟立民，隋卫平，徐欣艳（山东大学化学系，济南，２５０１００）关键词甜菜碱，芘，临界胶束浓度Ｅｋｗａｌｌ等［１］发现，表面活性剂的溶液能够增溶多环芳烃并发射较强的荧光．在常用的测定表面活性剂临界胶...     

羧甲基纤维素-壳聚糖水凝胶球的制备及性能

采用物理交联法制备了羧甲基纤维素(CMC)-壳聚糖(CS)共混水凝胶球;研究了共混球的耐酸碱性、溶胀性及对亚甲基蓝的吸附性能.结果表明,水凝胶球在弱酸和弱碱中具有一定的稳定性;随着羧甲基纤维素与壳聚糖质量比的增大,水凝胶的吸水溶胀率增加.在CMC与CS质量比为1∶4时制备的水凝胶呈规则球状.     

N-异丙基丙烯酰胺温度敏感性水凝胶相转变动力学研究及其应用

 研究指出表观二级动力学方程可以很好地描述N-异丙基丙烯酰胺水凝胶的溶胀和消溶胀动力学.即溶胀动力学方程为dR/dt=k₁(R_e-R)²,消溶胀动力学方程为-dR/dt=k_c(R-R_e)².把这种水凝胶用于分离高分子水溶液时可引入“单位溶张比分离循环的合理时耗”这样一个参量.它根据溶胀和消溶胀过程中的起始溶胀比、平衡溶胀比、表观溶胀动力学常数和表观消溶胀动力学常数求出.具体公式为△t₁(T_s,T_c)=2/[R_c(T_s)-R₀(T_s)]²k_s(T_s)+15/[R₀(T_c)- R_s(T_c)]²k_c(T_c)^1/2在理想情况下,分离过程的“总合理时耗”与△t_1成正比,比例系数为分离过程中的除水总量与干凝胶用量的比值,即△t_r=W_W/WG·△t₁.当根据二个动力学方程求得的总时耗计算值处于(0.9△t_r,1.1△t_r)范围内时,表明所选干凝胶用量和循环溶胀比区段均合适.     

A fluorescence probe study of the mixed surfactant vesicles

Vesicle can be prepared from aqueous mixtures of simple commercially available, single-tailed canonic and anionic surfactants. In this work, the I3/I1 value, Ie/ Im value, and fluorescence lifetime of pyrene in different systems (see the preparation of samples) were determined. Hie essential affecting factors in the formation of vesicle can be deduced from the obtained results. It showed that large vesicle must form naturally before sonication in 0.082 M octyltrimethylammonium bromide and sodium laurate pH = 9.2 aqueous solution. While after sonication, only small vesicle exists, which can be proved further through electron microscope.     

Effect of the water state on the electrical bending behavior of chitosan/poly(diallyldimethylammonium chloride) hydrogels in NaCl solutions

Semi‐interpenetrating polymer network (SIPN) hydrogels, composed of chitosan (CS) and poly(diallyldimethylammonium chloride) (PDADMAC), were prepared, and they exhibited electrically sensitive behavior. The swelling behavior of the CS/PDADMAC SIPN hydrogels was studied through the immersion of the gels in various concentrations of aqueous NaCl solutions, and their responses to stimuli in electric fields were also investigated. When the swollen SIPN hydrogels were placed between a pair of electrodes, they exhibited bending behavior upon the application of an electric field, which was stepwise and dependent on the magnitude of the field. To clarify the relationship between the equilibrium‐swelling ratio and the bending behavior of the SIPN hydrogels, the state of water in the SIPN hydrogels was also investigated with differential scanning calorimetry. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 914–921, 2004     

Accessibility of the gel phase in macroporous network polymers: A comparison of the fluorescence probe and inverse steric exclusion chromatography techniques

Two independent methods of analysis were employed to evaluate accessibility of the gel phase in macroporous network polymers. Fluorescence probes, covalented incorporated into the gel during polymerization, can provide a qualitative assessment of accessible surface area from an analysis of the solvatochromic shift of fluorescence emission. These findings are corroborated by inverse steric exclusion chromatography (ISEC). The data permits quantification of the polymers surface character in the solvated state. The results call attention to the inadequacy of dry surface area technique (e.g., BET analysis) in providing information of this type.     

CdTe量子点荧光探针测定氯霉素含量的研究

在水溶液体系中制备出了具有高质量荧光性能,巯基乙酸(TGA)修饰的CdTe量子点(QDs),基于量子点与氯霉素混合后发生荧光猝灭作用,建立CdTe量子点作为荧光探针测定氯霉素的新方法。在Tris-HCl缓冲液(pH 7.00,0.10 mol·L-1)中,反应时间为10min时,氯霉素浓度在10～70μg·mL-1范围内与CdTe量子点的荧光猝灭程度呈良好的线性关系,相关系数为0.9981,检出限为0.799μg.mL-1。方法简便快速,灵敏度高,可用于实际样品中氯霉素的检测。     

Molecular dynamics of star‐shaped poly(L‐lactide)s in tetrahydrofuran as solvent monitored by fluorescence spectroscopy

Linear telechelic, α,ω‐ditelechelic, and star‐shaped tri‐, tetra‐, penta‐, and hexa‐arm poly(L ‐lactide)s (PLAs) fitted at every arm with pyrene end group have been prepared. Internal dynamics and mobility of the PLA chains in tetrahydrofuran solution at 25 °C, with regard to the number of PLA arms in one macromolecule and the individual arm average degree of polymerization, was followed by fluorescence spectroscopy. Analysis of both static and time‐resolved spectra of the star‐shaped polymers revealed dynamic segmental motion resulting in end‐to‐end cyclization, accompanied by an excimer formation. Probability and rate of the latter reaction increased with increasing number of arms and with decreasing their polymerization degree. Moreover, time‐resolved measurements revealed that for macromolecules containing few arms (2 or 3) the pyrene moieties are located in the interior of the star‐shaped PLAs, whereas in the instance of the higher number of arms (4–6) they are located at the periphery of the star‐shaped PLAs. Thus, increasing the number of arms leads to their stretching away from the center of the star‐shaped PLA macromolecule. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4586–4599, 2005     

Preparation and properties of chitosan‐poly(N‐isopropylacrylamide) semi‐IPN hydrogels

Chitosan (CS), CS‐poly(N‐isopropylacrylamide)(PNIPAM) and their dyed (pyrene) hydrogels were prepared using glutaraldehyde (Glu) as a crosslinker. The gelation rate, swelling behaviors in ethanol/water mixtures, electricity‐induced contraction and thermoresponse of the gels were investigated using fluorescence probe technique. Results showed that CS/Glu, and PNIPAM‐containing CS/Glu gels exhibited similar properties in all aspects examined, except that the transparence of the CS‐PNIPAM/Glu gel is very dependent upon the temperature. The CS‐PNIPAM/Glu gel is transparent below 30°C, whereas opaque above 32°C. It is expected that this observation may be useful for the design and preparation of new kinds of hydrogel devices. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 474–481, 2000     

荧光猝灭研究芳醚树枝形聚合物构象

本工作分别合成了外围修饰一个芘基团和核心修饰一个芘基团两个系列的芳醚树枝形聚合物Py-Gn-OH和Gn-CH₂-Py(n=1~4)。Py-Gn-OH和Gn-CH₂-Py的发光随代数增加而增强,荧光寿命增加。荧光猝灭实验结果表明,树枝形聚合物Py-Gn-OH和Gn-CH₂-Py的双分子猝灭速率常数均随代数增加而减小,表明树枝形聚合物发生了构象折叠,位于核心和外围的芘基团均被树枝形聚合物骨架包裹,随代数增加树枝形聚合物骨架增大,对芘基团包裹作用增强,导致猝灭剂接近芘基团的位阻增大。Gn-CH₂-Py体系的双分子猝灭速率常数均比相应代数Py-Gn-OH体系略小,说明树枝形聚合物骨架对连接在核心的芘基团的包裹程度比对连接在外围的芘基团略强。本工作为新型功能芳醚树枝形聚合物设计和应用提供了参考。     

LCST类水凝胶开关效应的研究进展

本文综述了LCST水凝胶的研究进展,详细论述了水凝胶的各种体积相变机理,以及亲疏水基团、介质的离子性、pH值等因素对凝胶性能的影响,分析探讨了这类水凝胶的开关效应在药物控释、物质分离、酶的固定以及电磁感应元件等方面的应用。     

Preparation and Characterization of pH-sensitive Hydrogel Film of Chitosan/Poly(acrylic acid) Copolymer

A hydrogel film of chitosan/poly(acrylic acid) (CS/PAAc) copolymer with the property of pH sensitivity, was prepared by irradiating the chitosan film, which was then swelled by aqueous AAc solutions of different concentrations. The effects of the feed ratio of chitosan and AAc on the properties of the hydrogels, such as swelling ratio and pH-sensitivity, were determined. Fourier transform infrared (FT-IR) spectroscopy was applied in the attenuated total reflectance (ATR) mode for analyzing the structure change of the hydrogels after the treatment in buffer solutions of different pHs.     

Regioselective grafting of poly(ethylene glycol) onto chitosan and the properties of the resulting copolymers

PEG was grafted onto chitosan regioselectively at the hydroxyl groups with phthaloylchitosan as an intermediate. After the graft reaction, the phthaloyl groups were deprotected to give chitosan-g-PEG copolymers with free amino groups. The chemical structure of the graft copolymers was confirmed by FT-IR, (1)H and (13)C NMR spectroscopy. The resulting graft copolymers showed improved thermal stability compared to the original chitosan, and showed a lower thermal transition temperature at around 185 degrees C. Chitosan-g-PEG exhibited a high affinity not only for aqueous acid but also for some organic solvents because of the presence of abundant free amino groups and PEG branches, and it exhibited higher hygroscopicity and moisture retention ability than chitosan. [structure: see text]