天然高分子电场敏感水凝胶——大豆蛋白/羧甲基壳聚糖体系

通过将大豆蛋白(SPI)和羧甲基壳聚糖(CMCS)进行溶液共混,并加入环氧氯丙烷作为交联剂,成功制备了一种天然高分子两性荷电水凝胶.这种SPI/CMCS水凝胶在电场的作用下可以快速弯向一侧电极,表现出很好的电场敏感性.由于该水凝胶具有两性荷电的特性,因此其在不同pH值的电解质溶液中既可以弯向阳极(当pH6时),也可以弯向阴极(当pH6时).除了pH的变化,其他诸如施加电压的大小以及水凝胶的厚度也会对SPI/CMCS水凝胶在电场中的行为产生影响.相比于先前报道的另外两种天然高分子电场敏感水凝胶,即壳聚糖/羧甲基纤维素水凝胶和壳聚糖/羧甲基壳聚糖水凝胶,SPI/CMCS水凝胶在酸性较强(pH=3～4)以及中性(pH=7)的环境中仍能表现出良好的电场敏感性,拓展了天然高分子电场敏感水凝胶的应用范围.     

非水介质中明胶水凝胶电场驱动行为的研究

研究了明胶水凝胶在绝缘硅油中的电场响应行为。结果表明,在硅油中,明胶水凝胶在外加高压直流电场作用下可发生运动,其运动由转动和平动两部分组成。存在一个运动所需的最小阈值电场,只有外加电场在此阈值以上时,才可观察到水凝胶明显的运动。水凝胶的运动速度随外加电场的增大而增大,其运动可通过外加电场的大小来调控。由硅油很稳定且在电场中会电解,因此避免了传统电场驱动水凝胶在水介质中响应时不可避免的电解缺点,为建立一种新的电响应凝毅然驱动方式提供了可能。     

磺化明胶水凝胶的制备及其电场响应性能

采用明胶为原料,以甲基丙烯酸缩水甘油酯和亚硫酸氢钠为改性剂,在明胶分子链上引入极性基团磺酸基,制得新型磺化明胶水凝胶。采用红外光谱(FT-IR)、X射线光电子能谱(XPS)和扫描电镜(SEM)对其组成和结构进行了表征。通过动态黏弹谱仪(DMA)测定水凝胶的储能模量,探讨不同外加电场作用下该水凝胶的电场响应性能。随着明胶水凝胶中S元素的原子百分比的增大,在外加电场下,胶体的电场响应能力增强。当外加电场为1.6kV/mm、明胶水凝胶中S的原子百分比为1.59%时,水凝胶对电场作用的响应最明显,储能模量的增加率为31.86%。     

DNA水凝胶的制备及生物应用

DNA具有良好的生物相容性、生物可降解性、分子识别特性、纳米尺寸可控及特异编码等特性。近年来,DNA扮演了多种角色,不仅仅是作为生物体系的遗传物质,同样作为生物材料被用于纳米结构的构建。DNA水凝胶既保持了DNA本来的生物特性又兼具普通凝胶的特性,比如形状可塑性、一定的机械强度、输送物质等特性。DNA水凝胶按照凝胶形成化学键的类型可以分为共价键形成的化学凝胶和非共价键形成的物理凝胶; DNA水凝胶中可以引入特异性响应不同刺激的基团或者序列,从而实现对不同刺激的灵敏性响应进而拓宽DNA水凝胶的应用范围。按照刺激响应性分类可分为pH敏感型、光敏感型、温度敏感型和小分子敏感型等水凝胶。DNA水凝胶的这些特有的性质很好地将DNA纳米技术和生物技术连接起来,为其应用提供了广阔的前景。DNA水凝胶作为一种具有智能响应的材料也越来越多地被应用到生物传感、药物输送、三维细胞培养等方面。本文主要综述了DNA 水凝胶的分类以及近几年来DNA水凝胶中的不同刺激响应型DNA水凝胶的制备及其生物应用,最后对其以后的研究前景进行了展望。     

分子印迹智能水凝胶的研究进展

智能水凝胶可以响应外界环境(如温度、pH、溶剂、离子强度、电场、磁场、光、压力和特异分子等)的变化,发生可逆体积相变,从而具有控制释放的能力.将分子印迹技术引入智能水凝胶,制备分子印迹智能水凝胶,不仅可以保持其环境响应性,更赋予其对特异分子的识别性能,从而可以根据外界环境的变化控制其对特定分子记忆功能的开关,实现自动识别并结合或释放特定分子.它有望应用于药物控释、生物传感和免疫分析等领域.本文综述了分子印迹智能水凝胶的研究现状,讨论了其目前所面临的挑战,并展望了其发展前景.     

电场响应光子晶体

光子晶体是一种介电常数周期变化、具有光子带隙、对光路可控的新型功能材料。将对外界刺激敏感性材料引入光子晶体空隙就得到可响应光子晶体。电场响应光子晶体是由电活性材料与光子晶体结构相结合所得,可以应用于反射型彩色显示并表现出其他显示技术所没有的独特优点。本文重点介绍了电场响应光子晶体器件的结构和响应机理,并按照引入电活性材料的不同将电场响应光子晶体分为基于液晶、聚电解质水凝胶、金属有机聚合物凝胶、导电聚合物以及核壳式电场响应光子晶体,总结了近几年各类电场响应光子晶体的研究进展,提出了在反射型彩色显示器件方面的应用以及存在的问题和展望。     

明胶水凝胶电刺激响应行为的研究

制备了戊二醛交联的明胶水凝胶 ,并研究了其吸水率、力学性能和电刺激响应行为 .结果表明 ,在NaCl溶液中 ,明胶水凝胶的平衡溶胀比随NaCl溶液的浓度增大而减小 ,经 0 0 1mol LNaCl溶液充分溶胀的明胶水凝胶膜其弹性模量为 4.2 9kPa ,抗张强度为 5 11kPa ,断裂伸长率为 110 %.在NaCl溶液中于非接触的直流电场作用下 ,明胶水凝胶向电场负极弯曲 ,凝胶的弯曲速度和弯曲偏转程度随外加电场的增大而增大 ,随NaCl溶液离子强度的增大出现临界最大值 .在周期性电场作用下 ,其弯曲响应行为具有良好的可逆性 .通过聚电解质凝胶弯曲理论初步解释了其弯曲机理 .     

电场驱动的高分子凝胶

本文较系统地阐述了电场驱动的高分子水凝胶、有机凝胶的响应机理，并扼要介绍了此类凝胶应用的最新进展。     

水凝胶流变学研究概况

水凝胶具有良好的生物相容性和生物可降解性,其结构呈三维网状结构,与细胞外基质相似,在药物释放和组织工程等领域具有广阔的应用前景,被广泛地用于生物制药、生物材料和医学等领域。流变学可以描述材料的流动特性和力学性能,水凝胶的粘弹响应对材料内部结构的变化也非常敏感,因此流变行为被视为研究水凝胶的一种重要方法。本文综述了流变学方法在水凝胶研究中的应用,介绍了水凝胶流变学的研究方法,讨论了影响水凝胶流变学特征的因素,并展望了水凝胶流变学的发展前景。     

壳聚糖基智能水凝胶的研究进展

壳聚糖是一种天然高分子,含有氨基和羟基等特征基团;水凝胶是一种高分子交联网络体系,具有亲水性,在水中能够溶胀并保持大量水分而不溶解;“智能化”是自发地对外界环境刺激产生响应的一种特性.壳聚糖基智能水凝胶具有良好的生物相容性和可降解性,正倍受广大研究学者的关注.文章综述了近年来关于pH敏感型、温度敏感型以及pH/温度双重敏感型壳聚糖基智能水凝胶的研究概况,介绍了壳聚糖基水凝胶在医学领域如组织工程、药物释放方面的应用并对其未来的发展方向进行了探讨.     

Modeling and simulation of chemo-electro-mechanical behavior of pH-electric-sensitive hydrogel

A chemo-electro-mechanical multi-field model, termed the multi-effect-coupling pH-electric-stimuli (MECpHe) model, has been developed to simulate the response behavior of smart hydrogels subject to pH and electric voltage coupled stimuli when the hydrogels are immersed in a pH buffer solution subject to an externally applied electric field. The MECpHe model developed considers multiphysics effects and formulates the fixed charge density with the coupled buffer solution pH and electric voltage effects, expressed by a set of nonlinear partial differential governing equations. The model can be used to predict the hydrogel displacement and the distributive profiles of the concentrations of diffusive ionic species and the electric potential and the fixed charge density in both the hydrogels and surrounding solution. After validation of the model by comparison of current numerical results with experiment data extracted from the literature, one-dimensional steady-state simulations were carried out for equilibrium of the smart hydrogels subject to pH and electric coupled stimuli. The effects of several important physical conditions, including the externally applied electric voltage, on the distributions of the concentrations of diffusive ionic species, the electric potential, the fixed charge density, and the displacement of the hydrogel strip were studied in detail. The effects of the ionic strength on the bending deformation of the hydrogels under the solution pH and electric voltage coupled stimuli are also discussed.     

智能水凝胶研究最新进展

综述了近几年国内外智能水凝胶研究现状,重点介绍了对pH、温度、光、电、磁和特定生物分子敏感的水凝胶的研究创新以及智能水凝胶在药物控释载体、组织工程支架、血红蛋白氧栽体、生物传感器、蛋白质检验等生物医学领域应用的最新进展.     

Multiphysical modeling and meshless simulation of electric‐sensitive hydrogels

According to a multiphase mixture theory, we have mathematically developed a multiphysical model with chemoelectromechanical coupling considerations, termed the multieffect‐coupling electric‐stimulus (MECe) model, to simulate the responsive behavior of electric‐sensitive hydrogels immersed in a bath solution under an externally applied electric field. For solutions of the MECe model consisting of coupled nonlinear partial differential governing equations, a meshless Hermite–Cloud method with a hierarchical iteration technique has been used for a one‐dimensional steady‐state analysis of a hydrogel strip. The computed results are compared with the experimental data, and there is very good agreement. Simulations within the domains of both hydrogels and surrounding solutions also present distributions of the ionic concentrations and electric potential as well as the hydrogel displacement. The effects of various physical parameters on the response behavior of electric‐stimulus responsive hydrogels are discussed in detail. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1514–1531, 2004     

Cellulose–halloysite nanotube composite hydrogels for curcumin delivery

Halloysite nanotubes (HNTs) were added to cellulose NaOH/urea solution to prepare composite hydrogels using epichlorhydrine crosslinking at an elevated temperature. The shear viscosity, mechanical properties, microstructure, swelling properties, cytocompatibility, and drug delivery behavior of the cellulose/HNT composite hydrogels were investigated. The viscosity of the composite solution increases with the addition of HNT. The compressive mechanical properties of composite hydrogels are significantly improved compared with pure cellulose hydrogel. The compressive strength of the composite hydrogels with 66.7% HNTs is 128 kPa, while that of pure cellulose hydrogel is only 29.8 kPa in compressive strength. Rheological measurement suggests the resistance to deformation is improved for composite hydrogels. X-ray diffraction and Fourier transform infrared spectroscopy show that the crystal structure and chemical structure of HNT are not changed in the composite hydrogels. Hydrogen bonding interactions between HNT and cellulose exist in the composites. A porous structure of the composite hydrogels with pore size of 200–400 μm was found by scanning electron microscopy. The addition of HNT leads to decreased swelling ratios in NaCl solution and pure water for the composite hydrogels. Cytotoxicity assays show that the cellulose/HNT composite hydrogels have a good biocompatibility with MC3T3-E1 cells and MCF-7 cells. Curcumin is further loaded into the composite hydrogel via physical adsorption. The curcumin-loaded composite hydrogels show a strong inhibition effect on the cancer cells. All the results illustrate that the cellulose/HNT composite hydrogels have promising applications such as anticancer drug delivery systems and anti-inflammatory wound dressings.     

Phase field model simulations of hydrogel dynamics under chemical stimulation

Two decades ago, it has been observed experimentally that hydrogels immersed in a bath solution swells or shrinks under external stimulations (Ric?ka et al., Macromolecules 17:2916?C2921, 1984). Recently, this fact has received renewed interest, since understanding the precise mechanisms underlying that kind of behavior has the potential to tailor most sensitive drug delivery systems based on hydrogels (Segalman and Witkowski, Mater Sci Eng C 2:243?C249, 1995). Here we contribute to a precise understanding of the mechanisms responsible for the hydrogels?? swelling kinetics as well as dynamics by proposing for the first time a model approach that can resolve the inherent short-range correlation effects along the hydrogel?Csolution interface jointly with the long-range ionic transport fields. To that end, we investigate the swelling dynamics of hydrogels, which is a moving boundary problem, by a phase field model, which couples the Nernst?CPlanck equation for the concentration of mobile ions, Poisson equation for the electric potential, mechanical equation for the displacement, and an equation for the phase field variable. Simulation for two-dimensional case reveals that under the chemical stimulation, the hydrogel will swell or shrink if the concentration of mobile ions inside bath solution decreases or increases. This is in agreement with the experimental results qualitatively and validates our new model approach.     

Photolithographically Patterned Hydrogels with Programmed Deformations

Programmed deformations are widespread in nature, providing elegant paradigms to design self‐morphing materials with promising applications in biomedical devices, flexible electronics, soft robotics, etc. In this emerging field, hydrogels are an ideal material to investigate the deformation principle and the structure‐deformation relationship. One crucial step is to construct heterogeneous structures in a facile yet effective way. Herein, we provide a focus review on different deformation modes and corresponding structural features of hydrogels. Photolithography is a versatile approach to control the outer shape of the hydrogel and spatial distribution of the component in the hydrogel, endowing the patterned hydrogels with programmed internal stress and thus controllable deformations. Specifically, cooperative deformations take place in periodically patterned hydrogels with in‐plane gradients, and multiple morphing structures are formed in one patterned hydrogel using selective preswelling to direct the buckling of each unit. The structural control strategy and deformation principles should be applicable to other materials with broad applications in diverse areas.     

温度及pH敏感聚(丙烯酸)-co-(丙烯腈)水凝胶的合成及性能研究

温度及ｐＨ敏感聚（丙烯酸） ｃｏ （丙烯腈）水凝胶的合成及性能研究卓仁禧张先正（武汉大学化学系国家教委生物医用高分子材料开放实验室武汉４３００７２）关键词丙烯酸，丙烯腈，水凝胶，溶胀率关于水凝胶的环境敏感性研究始于八十年代初［１］．随后大量研究表明...     

通过麦克加成反应形成的三臂聚乙二醇丙烯酸酯可注射水凝胶的制备与表征

通过麦克加成反应在磷酸盐缓冲溶液中制备出一种基于三臂聚乙二醇丙烯酸酯的能快速固化的可注射水凝胶.采用倒置法测定了体系的凝胶化时间.通过红外,DMA,溶胀,降解等一系列测试,研究了该水凝胶的结构和物理化学性能.观察到通过控制前体溶液的浓度,可以控制凝胶的成胶时间和所形成凝胶的溶涨率.同时表明该水凝胶具备可注射性和可降解性.细胞毒性评价显示,该水凝胶浸提液无毒性,符合生物材料的安全评价标准.由于麦克加成反应可在人体生理条件(pH7.4,37℃)下快速进行,并且不需要任何引发剂、催化剂和有机溶剂,因此该反应非常适合应用于生物医用材料领域.