生物还原响应的酶交联可注射水凝胶

可注射水凝胶作为生物材料被广泛用于生物医学领域. 合成了含有二硫键的葡聚糖衍生物(Dex-SS-PA), 使用辣根过氧化酶化学交联制备出新型的生物还原响应的可注射水凝胶. 系统研究了这些水凝胶的物理化学属性, 包括成胶时间、胶含量及降解性, 同时使用生死染色实验和噻唑蓝比色法实验评价了它们的细胞生物相容性. 研究结果表明, 葡聚糖的分子量越大、根皮酸的取代度越高、Dex-SS-PA 的浓度越大, 获得的水凝胶成胶时间越短、胶含量越高. 在还原环境中, Dex-SS-PA 水凝胶能够被降解. 此外, 这些水凝胶没有明显的细胞毒性. 因此, 这类新的水凝胶预示着较好的生物医学应用前景.     

Multi-membrane hydrogels

Polysaccharide-based hydrogels are useful for numerous applications, from food and cosmetic processing to drug delivery and tissue engineering. The formation of hydrogels from polyelectrolyte solutions is complex, involving a variety of molecular interactions. The physical gelation of polysaccharides can be achieved by balancing solvophobic and solvophilic interactions. Polymer chain reorganization can be obtained by solvent exchange, one of the processing routes forming a simple hydrogel assembly. Nevertheless, many studies on hydrogel formation are empirical with a limited understanding of the mechanisms involved, delaying the processing of more complex structures. Here we use a multi-step interrupted gelation process in controlled physico-chemical conditions to generate complex hydrogels with multi-membrane 'onion-like' architectures. Our approach greatly simplifies the processing of gels with complex shapes and a multi-membrane organization. In contrast with existing assemblies described in the literature, our method allows the formation of free 'inter-membrane' spaces well suited for cell or drug introduction. These architectures, potentially useful in biomedical applications, open interesting perspectives by taking advantage of tailor-made three-dimensional multi-membrane tubular or spherical structures.     

甲基纤维素温敏水凝胶的凝固及体外释药特性

为研究新型反向温敏凝胶在植入型药物释放系统中的应用,通过粘度跟踪法考察了“甲基纤维素聚乙二醇柠檬酸钠”三组分体系在体温下的凝固特性,分析了凝胶配方对于凝固过程的影响;以5-氟尿嘧啶为模型药物,研究了凝胶配方对体外释放特性的影响。结果表明,甲基纤维素使体系具有反向温敏性,高分子量聚乙二醇具有加速胶凝的作用,柠檬酸钠的盐析作用能降低成胶温度。通过调整凝胶配方,能使体系在体温下在10m in内迅速凝固,并使5-氟尿嘧啶的释放时间达到24 h以上。     

Novel enzymatically crosslinked chitosan hydrogels with free-radical-scavenging property and promoted cellular behaviors under hyperglycemia

The impairment of regenerative processes induced by high blood-glucose level (hyperglycemia) and excessive reactive oxygen species (ROS) contributes to the diabetic complication progression and development. In this study, an injectable, in situ crosslinkable chitosan hydrogel with ROS-scavenging capability was developed by conjugating gallic acid onto the chitosan backbone (CGA). We hypothesized that gallic acid serves as both antioxidant and crosslinking moieties to form hydrogel in situ by means of enzymatic crosslinking with horseradish peroxidase (HRP). The rapid gelation (from 30 s) was observed by vial tilting. The mechanical properties and microstructures of CGA hydrogels can be well controlled by varying the concentrations of H₂O₂. The ROS-scavenging ability of these CGA hydrogels was demonstrated against DPPH radical, hydroxyl radical, and total reducing power. Notably, in an in vitro hyperglycemia environment, CGA hydrogels significantly improved the proliferation and migration of human dermal fibroblast cells, which are closely related to diabetic wound healing. These results suggest that CGA hydrogels have potential as advanced materials for the treatment of diabetes-related diseases via attenuating the excessive ROS production and improving cellular behaviors.     

Gelation of particles with short-range attraction

Nanoscale or colloidal particles are important in many realms of science and technology. They can dramatically change the properties of materials, imparting solid-like behaviour to a wide variety of complex fluids. This behaviour arises when particles aggregate to form mesoscopic clusters and networks. The essential component leading to aggregation is an interparticle attraction, which can be generated by many physical and chemical mechanisms. In the limit of irreversible aggregation, infinitely strong interparticle bonds lead to diffusion-limited cluster aggregation (DLCA). This is understood as a purely kinetic phenomenon that can form solid-like gels at arbitrarily low particle volume fraction. Far more important technologically are systems with weaker attractions, where gel formation requires higher volume fractions. Numerous scenarios for gelation have been proposed, including DLCA, kinetic or dynamic arrest, phase separation, percolation and jamming. No consensus has emerged and, despite its ubiquity and significance, gelation is far from understood-even the location of the gelation phase boundary is not agreed on. Here we report experiments showing that gelation of spherical particles with isotropic, short-range attractions is initiated by spinodal decomposition; this thermodynamic instability triggers the formation of density fluctuations, leading to spanning clusters that dynamically arrest to create a gel. This simple picture of gelation does not depend on microscopic system-specific details, and should thus apply broadly to any particle system with short-range attractions. Our results suggest that gelation-often considered a purely kinetic phenomenon-is in fact a direct consequence of equilibrium liquid-gas phase separation. Without exception, we observe gelation in all of our samples predicted by theory and simulation to phase-separate; this suggests that it is phase separation, not percolation, that corresponds to gelation in models for attractive spheres.     

Preparation of 3D graphene-based architectures and their applications in supercapacitors

Three dimensional (3D) graphene-based architectures such as 3D graphene-based hydrogels, aerogels, foams, and sponges have attracted huge attention owing to the combination of the structural interconnectivities and the outstanding properties of graphene which offer these interesting structures with low density, high porosity, large surface area, stable mechanical properties, fast mass and electron transport. They have been extensively studied for a wide range of applications including capacitors, batteries, sensors, catalyst, etc. There are several reviews focusing on the 3D graphene-based architectures and their applications. In this work, we only summarise the latest development on the preparation of 3D graphene-based architectures and their applications in supercapacitors, with emphasis on the preparation strategies.     

刺激响应水凝胶材料的研究进展

凝胶具有独特的基于化学键或物理作用交联形成的三维网状结构.刺激响应水凝胶在外界环境变化时通常展现出独特的响应性溶胀行为.近年来,科研人员构建了各种各样的pH响应水凝胶、温度响应水凝胶和光响应水凝胶等水凝胶材料,并对其响应机制进行了研究.文章综述了近年来科研人员在刺激响应水凝胶材料的构建及响应机制研究方面开展的工作,并对刺激响应水凝胶的应用进行了展望.     

从高分子构象与动力学到蛋白质折叠

针对作用在聚合物刷上的键拉力研究表明作用在接枝基面上的力随着聚合物刷接枝密度的增大反而减小,然而尾端单体上的拉伸张力并没有消失.高分子的构象和动力学转变决定了其物性和多种多样的应用,而生物大分子蛋白质作为由二十种不同属性的氨基酸构成的序列,更是具有由其序列所决定的特别的三维自然结构.本文就聚合物刷、聚合物纳米复合材料、聚合物网络等几种高分子体系的构象与动力学过程,及蛋白质构象和其折叠与去折叠的动力学过程做了介绍.特别是蛋白质的折叠与去折叠速率在单分子操纵实验中受到拉力的调控,通过测量这种拉力依赖的动力学过程、蛋白质的自由能曲面和折叠去折叠路径可以得到系统全面的研究.本文以肌肉蛋白titin的免疫球蛋白结构域I27为例对蛋白质折叠研究进行了阐述.     

Highly stretchable and tough hydrogels

Hydrogels are used as scaffolds for tissue engineering, vehicles for drug delivery, actuators for optics and fluidics, and model extracellular matrices for biological studies. The scope of hydrogel applications, however, is often severely limited by their mechanical behaviour. Most hydrogels do not exhibit high stretchability; for example, an alginate hydrogel ruptures when stretched to about 1.2 times its original length. Some synthetic elastic hydrogels have achieved stretches in the range 10-20, but these values are markedly reduced in samples containing notches. Most hydrogels are brittle, with fracture energies of about 10?J?m(-2) (ref. 8), as compared with ～1,000?J?m(-2) for cartilage and ～10,000?J?m(-2) for natural rubbers. Intense efforts are devoted to synthesizing hydrogels with improved mechanical properties; certain synthetic gels have reached fracture energies of 100-1,000?J?m(-2) (refs 11, 14, 17). Here we report the synthesis of hydrogels from polymers forming ionically and covalently crosslinked networks. Although such gels contain ～90% water, they can be stretched beyond 20 times their initial length, and have fracture energies of ～9,000?J?m(-2). Even for samples containing notches, a stretch of 17 is demonstrated. We attribute the gels' toughness to the synergy of two mechanisms: crack bridging by the network of covalent crosslinks, and hysteresis by unzipping the network of ionic crosslinks. Furthermore, the network of covalent crosslinks preserves the memory of the initial state, so that much of the large deformation is removed on unloading. The unzipped ionic crosslinks cause internal damage, which heals by re-zipping. These gels may serve as model systems to explore mechanisms of deformation and energy dissipation, and expand the scope of hydrogel applications.     

自修复水凝胶的研究进展及油气田应用

针对自修复水凝胶能够模仿自然界中植物受损后从分子水平上对受损部位进行自修复的现象,对自修复水凝胶设计和合成基本原理进行了归纳总结。自修复水凝胶主要分为化学型自修复水凝胶和物理型自修复水凝胶。化学型自修复水凝胶大体上又可分为基于Diels-Alder加成反应的自修复水凝胶、基于可逆二硫键的自修复水凝胶和基于酰腙键的自修复水凝胶;物理型自修复水凝胶大体上可分为基于氢键作用的自修复水凝胶、基于主客体相互作用的自修复水凝胶和基于静电相互作用的自修复水凝胶等类型。自修复水凝胶不仅保留了传统水凝胶良好的吸水保水性、生物相容性等性能,而且其具有的自修复性能可以有效地延长材料的使用寿命、降低材料的使用成本。在此基础上,分析讨论了自修复水凝胶在油气田、生物医药等领域的潜在应用价值和应用情况,并对自修复水凝胶在油气田领域的发展趋势进行了展望。     

Improper ferroelectricity in perovskite oxide artificial superlattices

Ferroelectric thin films and superlattices are currently the subject of intensive research because of the interest they raise for technological applications and also because their properties are of fundamental scientific importance. Ferroelectric superlattices allow the tuning of the ferroelectric properties while maintaining perfect crystal structure and a coherent strain, even throughout relatively thick samples. This tuning is achieved in practice by adjusting both the strain, to enhance the polarization, and the composition, to interpolate between the properties of the combined compounds. Here we show that superlattices with very short periods possess a new form of interface coupling, based on rotational distortions, which gives rise to 'improper' ferroelectricity. These observations suggest an approach, based on interface engineering, to produce artificial materials with unique properties. By considering ferroelectric/paraelectric PbTiO3/SrTiO3 multilayers, we first show from first principles that the ground-state of the system is not purely ferroelectric but also primarily involves antiferrodistortive rotations of the oxygen atoms in a way compatible with improper ferroelectricity. We then demonstrate experimentally that, in contrast to pure PbTiO3 and SrTiO3 compounds, the multilayer system indeed behaves like a prototypical improper ferroelectric and exhibits a very large dielectric constant of epsilon(r) approximately 600, which is also fairly temperature-independent. This behaviour, of practical interest for technological applications, is distinct from that of normal ferroelectrics, for which the dielectric constant is typically large but strongly evolves around the phase transition temperature and also differs from that of previously known improper ferroelectrics that exhibit a temperature-independent but small dielectric constant only.     

壳聚糖基水凝胶药物控制释放体系

水凝胶具有良好的亲水性,充分膨胀后具有与机体组织相似的物理性质,如柔软、有弹性、与生物液之间的界面张力低等。另外,水凝胶还具有孔径、机械强度和尺寸可调性等优点,适于作为药物控制释放的载体形式。壳聚糖是一种天然高分子材料,具有生物活性、良好的生物相容性、完全可降解性及无毒性等优点,是良好的药物控制释放载体材料。以壳聚糖为基材,通过物理方法或化学方法,可制备出pH敏感型、温敏型、光敏型等多种形式、不同性能的水凝胶。就壳聚糖基水凝胶的制备方法进行了详细地论述,包括通过物理作用形成水凝胶的方法及通过化学交联作用制备水凝胶的方法,探讨了壳聚糖基水凝胶对药物的担载和释放,并对其未来的发展前景进行了展望。     

Preparation of dicholesteryl-derivatives: The effect of spatial configuration upon gelation

To investigate the effect of spatial configuration on the gelation properties of low molecular mass gelators(LMMGs),four novel di-cholesteryl derivatives have been specially designed and synthesized by introducing the cis-/trans-isomers of butene diacid and the optical isomers of D/L-phenylalanine into the linker between two cholesteryl moieties.These isomers have been denoted as MaDC,FaDC,MaLC and FaLC,respectively.The gelation properties of the compounds were examined in 26 organic solvents,and it was found that the trans-configuration is more favorable for the gelation,but the chirality of the linker shows little effect to the gelation.FaDC has the strongest gelation ability among the four isomers.Interestingly,FaDC and FaLC display phase-selective gelation of benzene,toluene and xylene from their mixtures with water at room temperature,which establishes a foundation for the purification of water contaminated by oil or aromatic solvents.SEM and CD spectroscopy studies revealed that the spatial configuration of the linkers of the gelators affects significantly the aggregation mode,the morphologies and the chirality of the network of the gels.Moreover,the different aggregation behaviors also have an impact on mechanical properties of the gels,which are consistent with the results from rheological studies.Furthermore,temperature-and concentration-dependent 1 H NMR and FTIR measurements demonstrated that intermolecular hydrogen bonding and-stacking are the main driving forces for the formation of the gels.     

(NIPAAm)类三元共聚及IPN水凝胶的合成与温敏性能的研究

采用自由基聚合法合成了P(AAm-co-NIPAAm-co-DMAA)三元共聚水凝胶和P(NIPAAm-co-AAm)/PDMAA互穿聚合物网络(IPN)水凝胶。研究了两种水凝胶的温敏及溶胀性能,并考察了DMAA含量对两种凝胶性能的影响。结果表明,P(AAm-co-NIPAAm-co-DMAA)三元共聚水凝胶和P(NIPAAm-co-AAm)/PDMAA互穿聚合物网络(IPN)水凝胶都具有热缩温敏性,DMAA的摩尔分数增加(7%～22%),两种水凝胶的LCST从40℃升高到45℃;三元共聚水凝胶平衡溶胀比(SR)由8.33提高至14.50,IPN水凝胶平衡溶胀比(SR)由5.61提高至11.66;两种水凝胶都能在30min内达到消溶胀平衡,并且失水率在80%左右。IPN水凝胶的凝胶形态稳定性较三元共聚水凝胶明显提高。     

Mechanical and Dynamic Properties Studies of in-situ Hybrid Composites

1IntroductionUnsaturated polyester resins are well known as commercially available polymeric materials with numerousapplications . They are usedin a wide range of products ,for example coating materials ,structural parts of au-tomobiles , building materials and engineering materials etc[1]. Unfortunately, these resins contain estergroupsintheir chain,which have highsensitivityto hydrolysis .In order toi mprove the mechanical propertiesand thermal stability of UP,in our work,the modification o…     

Immobilized ZnO based nanostructures and their environmental applications

In the research of semiconductor metal oxides, zinc oxide(ZnO) nanomaterials have been committed to design and exploration because of their unique physical and chemical properties. ZnO has many structural characteristics and has considerable practical applications in the field of environmental technology. However, ZnO nanomaterials used for environmental functions are often presented in the form of powders. After use, they need to go through recovery processes such as centrifugation and filtrati...     

A general strategy for nanocrystal synthesis

New strategies for materials fabrication are of fundamental importance in the advancement of science and technology. Organometallic and other organic solution phase synthetic routes have enabled the synthesis of functional inorganic quantum dots or nanocrystals. These nanomaterials form the building blocks for new bottom-up approaches to materials assembly for a range of uses; such materials also receive attention because of their intrinsic size-dependent properties and resulting applications. Here we report a unified approach to the synthesis of a large variety of nanocrystals with different chemistries and properties and with low dispersity; these include noble metal, magnetic/dielectric, semiconducting, rare-earth fluorescent, biomedical, organic optoelectronic semiconducting and conducting polymer nanoparticles. This strategy is based on a general phase transfer and separation mechanism occurring at the interfaces of the liquid, solid and solution phases present during the synthesis. We believe our methodology provides a simple and convenient route to a variety of building blocks for assembling materials with novel structure and function in nanotechnology.     

智能型水凝胶改性研究进展

智能型水凝胶是一类具有广泛应用前景的功能高分子材料,但由于传统水凝胶存在一些缺点因而限制了其应用,因此近年来围绕提高传统水凝胶的性能做了大量研究工作.该文从4个主要方面综述了近年来智能型水凝胶改性的研究进展.     

用渗流模型模拟和考察化学凝胶化反应

提出一个改进的渗流模型，把化学凝胶化体系本身的化学特点考虑进去，从而更真实地模拟化学凝胶化过程；部分地验证了用急冷法测试的化学凝胶化体系的临界行为；展示了进一步改进模型使之更符合实际的可能性。     

AM/DMDAAC共聚水凝胶的电场敏感性能

 为研究阳离子性DMDAAC共聚物水凝胶的电场敏感性能,以丙烯酰胺(AM)和二甲基二烯丙基氯化铵(DMDAAC)为单体,N,N'-亚甲基双丙烯酰胺为交联剂,过硫酸铵和亚硫酸氢钠为氧化还原引发剂,采用水溶液聚合法制备了AM/DMDAAC共聚物水凝胶,考查样品水凝胶在外加直流电场刺激下的消溶胀动力学和弯曲行为。研究表明,DMDAAC单体含量、施加电压的时间和施加电压大小以及所在溶液的离子强度对水凝胶的电敏感性能有着显著影响,有望使其在化学阀、仿生驱动器方面得到应用。在低浓度NaCl溶液中向正极弯曲,随着NaCl质量分数的增加,向正极弯曲角度逐渐减小,并进一步向负极弯曲。影响凝胶弯曲角度转变的临界NaCl质量分数为0.3%—0.4%,不同的单体配比,其临界NaCl质量分数也不一样。