超分子金属凝胶

近年来,超分子凝胶已逐渐发展为一类具有广阔应用前景的智能/功能性纳米材料。目前研究的大部分超分子凝胶利用的是氢键或者分子堆积作用,而配位键这一在超分子化学中同样重要的作用在凝胶合成上的应用则远远不足。由于引入金属离子后能够给凝胶带来光电、催化、氧化还原等新的性能,因此超分子金属凝胶的研究也在近年来得到升温。本文首先给出超分子金属凝胶的定义,接着通过实例具体介绍基于凝胶因子和配位聚合物两种形式的超分子金属凝胶,将分子结构特别是其中的配体基团、所用金属离子和凝胶的性质、功能联系起来,最后简介异常的超分子金属凝胶行为。     

基于脲基氢键组装的功能超分子凝胶

有机小分子化合物在分子间氢键、π-π堆积、亲疏水作用、范德华力等非共价键弱相互作用力驱动下,自组装形成三维网络结构的物理凝胶称为超分子凝胶。含有脲基的凝胶因子由于其强氢键缔合能力以及与阴离子、金属离子、卤素化合物等作用的可调变多样性,成为组装超分子凝胶中特别有效的氢键组装单元。本文分别从单脲基、双脲基和多脲基的凝胶因子分类综述了基于脲基氢键组装的功能超分子凝胶的研究工作,特别是近几年来的重要进展。对一些成功例子,从分子设计及成胶操作条件控制等方面的精细调谐如何解决聚集-溶解这对主要矛盾,从而实现溶胶-凝胶的转化及其可能的应用前景进行了评述。本文展望了该领域的发展方向与趋势,指出超分子凝胶研究经过多年的快速发展,深化对其蕴含机制以及动力学过程的认识与调控以实现具有多种刺激响应、多重信号输出的多组分复合功能凝胶体系的加工制备是发展趋势与必然要求,展现出广泛的应用前景也极富挑战性。     

基于胆固醇的有机超分子智能凝胶

胆固醇分子具有特色的多环、多手性碳结构,因此可用于构筑有机超分子凝胶智能材料。该凝胶体系除了对温度有良好的感知响应性外,对其他的外界刺激,如光、pH、超声等也能够感知并响应。由于胆固醇分子是生命体中普遍存在的生物分子,基于胆固醇的有机超分子智能凝胶在生命现象模拟、药物输运等方面具有天然的优势。本文先根据胆固醇凝胶体系的不同种类,包括光响应型、氧化还原响应型、酸碱响应型、超声响应型,金属离子响应型以及触变响应型等,对该体系的结构与性能进行了介绍,然后介绍了对凝胶因子的修饰方法,最后结合目前的研究现状,探讨了胆固醇有机超分子凝胶的应用方向及前景。     

智能性水凝胶

“智能”材料具有传感、处理和执行功能，水凝胶作为智能材料其应用前景良好。本文综述了智能水凝胶的近期研究发展，以Ｆｌｏｒｙ的溶胀理论着重探讨了刺激响应性，并介绍了化学机械现象及凝胶相转变。     

刺激响应型超分子凝胶

随着超分子化学的日益发展,刺激响应型超分子凝胶作为一种超分子材料受到人们广泛关注。超分子凝胶是由非共价键作用力自组装而成,基于这一特性,当超分子凝胶受到外界刺激（如温度、光、pH、化学物质、机械力等）时,该凝胶能够产生响应,如溶胶-凝胶转化、颜色变化或荧光变化等。刺激响应型超分子凝胶在离子识别材料、自修复材料、生物材料等领域展现出了非常好的应用前景。本文综述了近五年来刺激响应型超分子凝胶的研究进展,并根据刺激种类的不同,将超分子凝胶分为以下几类：热敏感型超分子凝胶、化学物质和pH响应型超分子凝胶、光敏感型超分子凝胶、氧化还原响应型超分子凝胶、机械力刺激响应型超分子凝胶和多重刺激响应型超分子凝胶。本文根据上述分类对超分子凝胶进行了介绍,同时对该研究领域作了展望。     

基于苯硼酸的树枝状凝胶及其刺激响应

具有葡萄糖识别性质的超分子凝胶体系在医学诊断领域具有广泛的应用前景。本文通过简单的缩合反应成功构筑了基于苯硼酸和聚芳醚单元的树枝状凝胶因子,其结构利用核磁共振谱和质谱进行了表征。研究了该凝胶因子的凝胶化能力,利用UV-Vis、SEM和SAXS研究了其自组装机理和形貌。构筑的凝胶对热、酸碱和D-葡萄糖表现出多重刺激响应行为。本研究为构筑具有多功能性的软材料提供了一定的理论研究基础。     

气态酸和有机胺响应的超分子凝胶

超分子凝胶是由有机分子在非共价键作用力驱动下自组装形成的一种具有液态和固态双重性质的软物质。超分子凝胶能对多种外界刺激做出响应,广泛应用于催化和传感等领域。与传统的小分子探针相比,超分子凝胶传感器显示出了多种检测模式和多信号输出的优点,如超分子凝胶材料的内部三维网络结构和较大的接触面积有利于分析物的快速渗透,并且其凝胶状态的变化可以作为检测过程中的输出信号。此外,干凝胶薄膜材料还具有三维网络结构,在检测气体分析物方面表现出优异的检测性能。本文重点介绍了超分子凝胶在气态酸和有机胺检测中的应用以及相关超分子凝胶的设计和检测机理,为构建用于气态酸和有机胺检测的新型超分子凝胶提供了参考。最后总结了超分子凝胶在气态酸和有机胺检测中存在的问题及应用前景。     

聚乙二醇基智能水凝胶的研究进展

聚乙二醇是一种常见的水溶性高分子,其水凝胶低毒,生物相容性好,广泛应用于生物医学和药学材料;PEG分子链的末端为活泼性基团—羟基,很容易发生化学反应得到聚乙二醇功能单体,利用这种大分子单体很容易制备出结构和性能各异的水凝胶;而且其分子量的应用范围很宽(从几百到几万)。因此利用PEG为基体制备水凝胶具有独特的优势。此外,聚乙二醇基水凝胶以其众多的刺激响应功能显示出了广阔的应用前景,引起了人们的广泛关注。本文综述了近年来聚乙二醇基水凝胶研究方面的进展,包括水凝胶的合成、结构与性能的关系等,并特别强调了点击化学与超分子化学在水凝胶的设计与合成方面的重要性。     

石墨烯基水凝胶的研究进展

石墨烯具有独特的导电、导热和力学性能,既能够自组装为电化学性能优良的石墨烯水凝胶,又可以与小分子和聚合物进行复合制备多功能性复合水凝胶,大幅度地拓展了传统水凝胶的应用范围。本文主要分为四部分来综述近些年来石墨烯基水凝胶的研究进展。第一部分简要介绍了石墨烯的研究背景和石墨烯基水凝胶的研究意义。第二部分主要根据石墨烯基水凝胶的组成将其分为石墨烯水凝胶、石墨烯/小分子和石墨烯/聚合物复合水凝胶三类,分别介绍了它们的制备方法、形成机理和凝胶性能。其中,对石墨烯/小分子复合水凝胶的介绍以石墨烯基超分子水凝胶为主,而对石墨烯/聚合物复合水凝胶的介绍以智能型水凝胶为主。第三部分主要介绍了石墨烯基水凝胶在超级电容器、水处理、控释药物、微流体开关、催化剂载体等方面的应用和发展。最后,对该领域所面临的挑战进行了总结和展望。     

环糊精超分子凝胶的构筑及其功能

环糊精作为一种具有良好的水溶性和生物兼容性的大环主体,因其对无机、有机和生物底物的特异性键合而倍受关注。凝胶材料则凭借其结合了固体弹性以及液体流动性等特性而有着广泛的应用。环糊精超分子凝胶融合了环糊精和凝胶的优势,在软材料领域研究中有着特殊的重要意义。本文从环糊精凝胶的构筑出发,从氢键、主-客体键合和离子相互作用等方面对其形成超分子凝胶的驱动力进行讨论,并对超分子凝胶在生物、检测、吸附及智能材料（包括滑动环类材料）领域的最新研究进展进行综述,为构筑新型环糊精超分子凝胶、开发该类凝胶的新功能提供参考。最后,对环糊精超分子凝胶的应用前景进行了展望。     

Computational approaches for understanding and predicting the self-assembled peptide hydrogels

Self-assembled peptide hydrogel is a promising biomaterial and has been widely applied in many fields. As a typical self-assembly material, peptide hydrogel exhibits properties different from traditional polymer hydrogel, and has unique features in molecular design, structural elements of hydrogel, and control strategies. With the desire to apply the principles of self-assembly to the design and prediction of peptide hydrogels, there has more and more emphasis on understanding the driving forces and microscopic behaviors involved in the self-assembly process. Computational methods have played an increasingly important role in recent research in helping to reveal the relationship between molecular chemical structure and self-assembly processes as well as assembled morphologies, thus determining the ability of supramolecular gelation. This review aims to summarize the application of computational tools to obtain a better fundamental understanding of the multi-scale structural details of self-assembled peptide hydrogels and to predict the gelation behavior of supramolecular nanofibers. It is expected that researchers will consider using these computational tools when investigating and designing novel peptide hydrogel materials.     

A hybrid hydrogel based on clay nanoplatelets and host–guest inclusion complexes

In this work,a monomer with double bond was introduced to the surface of clay nanosheets via inclusion complexation between cyclodextrin(CD)host and azobenzene(Azo)guest,as well as electrostatic interaction between clay nanoplatelets and cations of azobenzene derivatives.The obtained suprastructure acts as a supramolecular cross-linker in its copolymerization with macromonomer PEG resulting in a hybrid supramolecular hydrogel.Only viscous liquid was obtained in the absence of clay nanoplatelets,revealing the supramolecular cross-linker played an important role in the hydrogel formation.Such hybrid supramolecular hydrogel exhibited good stability and shear thinning property.     

Supramolecular hydrogel formed by glucoheptonamide of l-lysine: simple preparation and excellent hydrogelation ability

We describe the simple preparation of new l-lysine derivatives with a gluconic or glucoheptonic group, their hydrogelation properties, and the thermal and mechanical properties of the supramolecular hydrogels. The l-lysine derivatives with a gluconic group have no hydrogelation ability, while the l-lysine-glucoheptonamide derivatives functioned as hydrogelators. Their hydrogelation abilities increased with the decreasing length of the spacer between the l-lysine segment and the glucoheptonic group. The compound, which has no spacer, formed a supramolecular hydrogel at 0.05 wt % in pure water. The thermal stability and high mechanical strength of the supramolecular hydrogels based on this compound significantly depended on the aqueous solutions. Electron microscopy and FTIR studies demonstrated that the hydrogelators created a three-dimensional network through hydrogen bonding and hydrophobic interactions in the supramolecular hydrogel. In addition, it was found that hydrophobic interactions played an important role in the thermal stability of the supramolecular hydrogel.     

A Hybrid Supramolecular Polymeric Hydrogel with Rapid Self‐Healing Property

A hybrid supramolecular polymeric hydrogel is conveniently constructed via host–guest interaction of a host cyclodextrin polymer (poly‐CD) with a guest α‐bromonaphthalene polymer (poly‐BrNp) and mixing with 6‐thio‐β‐cyclodextrin (β‐SH‐CD) modified gold nanoparticles (GPCDs) in aqueous solution. According to the dynamic oscillatory data, the hydrogel exhibits markedly enhanced stiffness compared with the GPCD‐free one (both G′ and G“ values are almost twice as high as those of the original GPCD‐free hydrogel) due to the introduction of the inorganic gold nanoparticles. This hybrid supramolecular polymeric hydrogel has a rapid and excellent self‐healing property (only about 1 min, and the G′ and G” of the self‐healed hydrogel almost turned back to their original levels after 1 hour) in air (without adding any solvent or additive).     

Organic Dye Adsorption by Amphiphilic Tris‐Urea Supramolecular Hydrogel

The development of an effective adsorbent for cleansing polluted water is required for environmental purification. In this respect, a supramolecular hydrogel constructed by the self‐assembly of small molecules could be a strong candidate. Adsorption experiments of organic dyes were performed using supramolecular hydrogels of amphiphilic tris‐urea 1 . Cationic organic dyes were adsorbed efficiently; indeed, the adsorption of methylene blue was as high as 4.19 mol equivalents relative to 1 . Two luminescence peaks were observed in the rhodamine 6G‐adsorbed supramolecular hydrogels, and their ratios varied with the amount of dye adsorbed. Fluorescence microscopy images of the supramolecular hydrogel at lower dye levels exhibited fibrous fluorescence consistent with the fibrous aggregates of 1 . According to these results, adsorption may proceed gradually, that is, occurring initially on the fibers and later in the aqueous spaces of the supramolecular hydrogel.     

Three-dimensional encapsulation of live cells by using a hybrid matrix of nanoparticles in a supramolecular hydrogel

From a library of glyco-lipid mimics with muconic amide as the spacer, we found that 1, a glyco-lipid that has N-acetyl glucosamine and methyl cyclohexyl groups as its hydrophilic head and hydrophobic tails, respectively, formed a stable hydrogel (0.05 wt %) through hierarchical self-assembly of the lipid molecules into supramolecular nanofibers. The formation of the supramolecular hydrogel was verified by rheological measurements, and the supramolecular nanofiber was characterized as the structural element by transmission electron microscopy and atomic force microscopy observations. Absorption and circular dichroism spectroscopic measurements revealed that the muconic amide moieties of 1 are arranged in a helical, stacked fashion in the self-assembled nanofibers. Moreover, we unexpectedly found that the homogeneous distribution of the supramolecular nanofibers of 1 was greatly facilitated by the addition of polystyrene nanobeads (100-500 nm in diameter), as evaluated by confocal laser scanning microscopic observations. It is interesting that the obtained supramolecular hybrid matrix can efficiently encapsulate and distribute live Jurkat cells in three dimensions under physiological conditions. This supramolecular hybrid matrix is intriguing as a unique biomaterial.     

Low-molecular-weight photoresponsive supramulecular hydrogel based on a dicationic azobenzene-bridged pyridinium hydrogelator

Photoresponsive supramolecular hydrogel was fabricated from a small azobenzene-bridged dicationic pyridinium salt in the aqueous solution. The UV-vis light triggered reversible gel-sol transformation of such low-molecular-weight supramolecular hydrogel was systematically investigated through various analytical techniques.     

Synthesis of a Bis‐Urea Dimer and Its Effects on the Physical Properties of an Amphiphilic Tris‐Urea Supramolecular Hydrogel

The successful development of stiff supramolecular gels is an important goal toward their practical application. One approach to stiffen supramolecular gels is to introduce covalent cross‐links. The bis‐urea dimer 2 , having a structure similar to that of the low‐molecular‐weight gelator 1 , was synthesized. Supramolecular hydrogels were formed from mixtures of 1 and 2 in appropriate ratios, with 2 acting as a covalent cross‐linker to connect the fibrous aggregates formed by the self‐assembly of 1 . The introduction of these covalent cross‐links greatly influenced the dynamic viscoelasticity of the supramolecular hydrogels. In the supramolecular hydrogel of 1 mixed with 5 % 2 , the storage modulus was 1.35 times higher than that of the supramolecular hydrogel of 1 alone, and the crossover strain was extended from 5 % to over 20 %. The supramolecular hydrogel of 1 and 2 was free‐standing and supported 13 times its own weight.     

Self‐Healing Supramolecular Hydrogels for Tissue Engineering Applications

Self‐healing supramolecular hydrogels have emerged as a novel class of biomaterials that combine hydrogels with supramolecular chemistry to develop highly functional biomaterials with advantages including native tissue mimicry, biocompatibility, and injectability. These properties are endowed by the reversibly cross‐linked polymer network of the hydrogel. These hydrogels have great potential for realizing yet to be clinically translated tissue engineering therapies. This review presents methods of self‐healing supramolecular hydrogel formation and their uses in tissue engineering as well as future perspectives.     

Photo gel-sol/sol-gel transition and its patterning of a supramolecular hydrogel as stimuli-responsive biomaterials

In a focused library of glycolipid-based hydrogelators bearing fumaric amide as a trans-cis photoswitching module, several new photoresponsive supramolecular hydrogelators were discovered, the gel-sol/sol-gel transition of which was pseudo-reversibly induced by light. Studying the optimal hydrogel by NMR spectroscopy and various microscopy techniques showed that the trans-cis photoisomerization of the double bond of the fumaric amide unit effectively caused assembly or disassembly of the self-assembled supramolecular fibers to yield the macroscopic hydrogel or the corresponding sol, respectively. The entanglement of the supramolecular fibers produced nanomeshes, the void space of which was roughly evaluated to be 250 nm based on confocal laser scanning microscopy observations of the size-dependent Brownian motion of nanobeads embedded in the supramolecular hydrogel. It was clearly shown that such nanomeshes become a physical obstacle that captures submicro- to micrometer-sized substrates such as beads or bacteria. By exploiting the photoresponsive property of the supramolecular nanomeshes, we succeeded in off/on switching of bacterial movement and rotary motion of bead-tethered F(1)-ATPase, a biomolecular motor protein, in the supramolecular hydrogel. Furthermore, by using the photolithographic technique, gel-sol photopatterning was successfully conducted to produce sol spots within the gel matrix. The fabricated gel-sol pattern not only allowed regulation of bacterial motility in a limited area, but also off/on switching of F1-ATPase rotary motion at the single-molecule level. These results demonstrated that the photoresponsive supramolecular hydrogel and the resulting nanomeshes may provide unique biomaterials for the spatiotemporal manipulation of various biomolecules and live bacteria.