电子辐照PVA/CMC共混水凝胶的成胶研究

本试验利用电子辐照PVA/CMC共混水凝胶,通过外观透明度、凝胶分数、溶胀度和红外光谱分析,研究了样品中结构的变化与外观透明度、凝胶分数和溶胀度的关系,以及辐照剂量对样品中结构和性能的影响.结果表明,不同比例的PVA与相同比例的CMC组成的共混水凝胶,经电子辐照后呈现不同的宏观特性.辐照样品萃取后得到的凝胶比萃取前的混合凝胶拥有更强的吸水性,表明辐照PVA/CMC共混凝胶形成了网状结构凝胶.几种竞争反应导致不同辐照剂量下混合凝胶中凝胶含量随PVA含量的变化变得复杂.辐照后样品的红外光谱分析显示,辐照使凝胶中部分仲醇中C上链接的H原子被取代而转变为叔醇,从而产生交联.     

PNaAA吸水性树脂凝胶强度的研究

采用外加交联剂的反相悬浮法合成了聚丙烯酸钠（PNaAA）吸水性树脂，用抗压形变量来表征PNaAA树脂的凝胶强度。探讨了交联剂用量、单体中和度、共聚单体组成等因素对树脂凝胶强度的影响。结果表明，树脂的交联密度是影响凝胶强度的最主要因素；而树脂的饱和吸水性对凝胶强度有一定的抑制作用。同时探讨了PNaAA树脂凝胶的流变性能，发现它具有假塑性流变行为。     

A study of hydrogel thermal-dynamics using Fourier transform infrared spectrometer

A rapid and reliable method was presented for studying hydrogel dynamics/kinetics. Two temperature-sensitive hydrogels, poly-N-isopropylacrylamide (poly(NIPAAm)) and the copolymer of N,N-diethylacrylamide and sodium methacrylate (molar ratio=97:3, poly(NDEAAm-co-MAA)) were synthesized. The thermal-behaviors of the gels were studied through the absorbance intensities of both swollen water and gel frame components, and the peak positions of amide band along heating/cooling pathways under dynamic Fourier transform infrared (FTIR) probing. The results showed that the lower critical solution temperature (LCST) of poly(NIPAAm) is about 33-35 °C, which is consistent with reported value of ∼34 °C. Compared to poly(NIPAAm), poly(NDEAAm-co-MAA) has relatively continuous volume phase transition, starting at ∼35 °C and a better thermal-reversibility with similar swelling and deswelling profiles over a larger temperature range (10-80 °C for poly(NDEAAm-co-MAA) vs. 10-33 °C for poly(NIPAAm)). The H-bonding water along phase transition was also studied, showing a less reversibility of poly(NIPAAm) compared to poly(NDEAAm-co-MAA). In addition, FTIR spectrometer was also used to study the volume changes of poly(NDEAAm-co-MAA) under variations in environmental salinity.     

PVA/明胶/淀粉水凝胶的制备及性能

采用反复冷冻一解冻法制备了不同配比的聚乙烯醇／明胶／淀粉水凝胶膜。测试了共混膜的力学性能、脱水率和溶胀度，用扫描电镜观察了共混膜的断面形貌。结果表明：除1：1配比的水凝胶膜成膜性差，其他配比的水凝胶成膜性较好，膜表面比较光滑。m（PVA）：m（明胶）为6：1时力学性能较好。脱水率和溶胀度均随PVA和明胶比例增大而减小。扫描电镜显示，水凝胶膜内部具有多孑L结构，可以用作组织工程支架材料。     

Microscale analysis of patterning reactions via FTIR imaging: Application to intelligent hydrogel systems

A novel application of FTIR imaging for real-time characterization of patterning polymerization processes with microscale spatial resolution is presented. These methods will enable the microscale analysis of the reactions of polymeric systems with various substrates and devices. Specifically, intelligent hydrogels containing ionic groups (pH responsive) and poly(ethylene glycol) have been micropatterned onto gold surfaces, and the free-radical polymerization reaction has been characterized. It was demonstrated that differences in the reaction rates across a patterned region could be successfully resolved and characterized. This novel characterization method based on FTIR imaging will facilitate the optimization of integration processes of patterned polymeric films leading to enhanced (and reproducible) application of these materials as functional components in a variety of microdevices.     

pH响应性P(AA-co-C8PhEO10Mac) 水凝胶的制备及其对L-抗坏血酸的控释性能

采用自由基交联共聚法合成了具有pH敏感性的水凝胶聚丙烯酸-co-甲基丙烯酸辛基酚聚氧乙烯醚酯〔P(AA-co-C8PhEO10Mac)〕,考察了不同单体配比的水凝胶在不同pH的缓冲溶液中的溶胀性、溶胀动力学和退溶胀动力学。通过浸泡法在水凝胶中载入L-抗坏血酸,初步研究了模拟胃肠液中,凝胶对L-抗坏血酸的释放行为。结果表明,凝胶兼具快速的溶胀和退溶胀速率,良好的pH敏感性等特征;载药凝胶在模拟肠液(SIF,pH=7.4)中对药物的累计释放率明显大于在模拟胃液(SGF,pH=1.4)中的累计释放率,增大丙烯酸的用量使累计释放率先升高后降低。采用滤纸片法研究了甲基丙烯酸辛基酚聚氧乙烯醚酯(C8PhEO10Mac)对大肠杆菌、酿酒酵母的抑制作用,结果显示,在10～50 mmol/L的测试浓度水平,C8PhEO10Mac对二者均无明显的抑制作用。     

Effect of maleic acid content on the thermal stability, swelling behaviour and network structure of gelatin-based hydrogels prepared by gamma irradiation

The highly swelling Poly (acrylamide/maleic acid/gelatin) P(AAm/MA/G) hydrogels were prepared by gamma-irradiation at low dose rate (0.94 kGy/h) and moderate dose rate (3.84 kGy/h). The hydrogels were confirmed by FTIR. The effect of copolymer composition, dose and dose rate on the swelling behaviour was discussed. Increasing of MA content and G in the initial mixture leads to an increase in the amount of MA and G in the gel system and decrease in the gelation %. The swelling behaviours of the hydrogel prepared at moderate dose rate increased with increasing MA mole content in the gel system but, there is no systematic dependence of swelling on MA content was observed for the hydrogels obtained at low dose rate. Pore structure of the hydrogels was monitored by using scanning electron microscopy. Thermogravimetric analysis (TGA) and the rate of the thermal decomposition of P(AAm/MA/G) hydrogels has been evaluated to give a better understanding of the thermal stability of polymers, The X-ray data of P(AAm/MA/G) hydrogels was discussed to investigate some features namely the degree of ordering and crystallite size.     

Agarose-based hydrogel as an electrografting cell

An agarose gel was used as an electrochemical cell to graft vinylic polymer layers on conductive surfaces by electro-initiated radical electrografting of various water-soluble and hydrophobic vinylic monomers in the presence of diazonium ions. The process was followed by in situ electrochemical measurements and the resulting grafted layer was characterized by infrared (IRRAS) and photoelectron (XPS) spectroscopy. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

“Click” reactions in polysaccharide modification

Polysaccharide chemistry is enjoying accelerating development thanks to advances in synthetic techniques, biochemistry and solvents, which enable polysaccharide materials to be useful in a variety of demanding applications. Among the synthetic advances, click chemistry has reconfigured the realm of polysaccharide modification that previously was dominated by conventional synthetic approaches such as esterification and etherification. “Click” reactions provide mild, modular, and efficient modification pathways, and equally importantly allow us to synthesize derivatives with novel functionality, architecture, and properties, that are otherwise difficult to obtain via conventional methods. Herein, we review application in polysaccharide modification of six groups of click reactions; CuAAC (copper catalyzed alkyne/azide cycloaddition), metal-free [3+2] cycloaddition, Diels–Alder reaction, oxime click, thiol-Michael reaction, and thiol-ene reaction, as well as one click-like reaction that is the subject of our own research, olefin cross-metathesis.     

How the interactions with humic acids affect the mobility of ionic dyes in hydrogels – Results from diffusion cells

The complexation of charged compounds by humic acids represents the process of exceptional environmental importance. Nevertheless, traditional methods utilized in the complexation studies do not address the way, how these interactions affect the transport of ions in humic-rich environments. To overcome this dilemma, the diffusion cells technique is proposed as an innovative reactivity mapping technique. Using this method, the diffusion of methylene blue was studied in aqueous solutions and in agarose gels with and without the addition of humic acids. Experimental results clearly illustrate the immobilizing effects of humic acids on the transport of methylene blue in gels. The partitioning of methylene blue at the solution-gel interface and the specific interactions between methylene blue and humic acids is discussed on the basis of experimental data. Effective structural parameters of hydrogels (effective porosity, tortuosity factor) were calculated, as well as some standard diffusion and interaction parameters (diffusion and partition coefficients and apparent equilibrium constants).