导电水凝胶的制备

作为一种新型的功能材料,导电水凝胶已经引起广泛的关注。本文根据目前的研究现状,将导电水凝胶大致分为聚电解质导电水凝胶,酸掺杂导电水凝胶,无机物添加导电水凝胶以及导电高分子基导电水凝胶等几大类,并综述了它们的制备方法。另外,由于大分子体系的导电高分子和水凝胶都有着独特和重要的性能,这使得它们具有广阔的应用价值。所以,本文在综述导电水凝胶制备进展的同时着重综述了导电高分子基导电水凝胶的制备进展。     

高储能密度聚酰亚胺/钛酸钡/水滑石复合薄膜的制备与性能

利用零维纳米粒子与二维纳米片在聚合物基体中的协同分散,构筑纳米粒子/二维纳米片/聚酰亚胺(PI)三元复合体系,系统研究了零维-二维组合纳米填料对复合材料介电常数、击穿强度、储能密度以及机械性能的影响.结果表明:采用氟碳表面活性剂插层修饰可以将水滑石剥离为水滑石二维纳米片(HT),在此纳米片溶液中分散钛酸钡纳米粒子(BT),并进行聚酰亚胺的原位聚合.在聚合物溶液形成薄膜的过程中,二维纳米片和纳米粒子的协同作用抑制了各自的团聚,改善了2种纳米填料在聚合物薄膜中的分散状况.在所制备的PI/BT/HT复合薄膜中,HT有利于改善BT在PI基体中的均匀分散,提高了薄膜的击穿强度,进而提升了复合薄膜的储能密度.与仅加入20%BT相比,在聚酰亚胺中同时加入2种填料20%BT和1%HT时,击穿强度达到354.4 kV/mm,储能密度达到2.58 J/cm3,分别提高了12.4%和14.6%.因此,在纳米粒子/聚合物复合材料中增加少量二维纳米片就可以显著改善其性能,这种方法有望在更多纳米复合功能材料领域得到应用.     

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.     

仿生多尺度功能水凝胶的设计与制备:从二维界面到三维网络

水凝胶是以大量水为分散介质的三维高分子网络.高分子网络和水分子之间的氢键将水束缚在网络内部,从而使体系丧失流动性并转变成一种准固态物质.水凝胶能够在多种外界刺激下改变形状和体积,因此在软体机器人、柔性电子器件和传感器等领域具有广泛的应用前景,也引起了科研人员的关注.在生物软组织中,多尺度结构(如表面微/纳米结构,有序三维网状结构)的存在对于生物材料的自清洁、耐冻、环境适应性和优异的机械性能等功能至关重要.受生物水凝胶结构与功能特性的启发,研究人员开发了一系列对各种机械和环境条件具有高度适应性的仿生多尺度水凝胶.本文将从水凝胶的二维界面和三维网络的设计2个方面总结和讨论近年来仿生多尺度水凝胶的研究成果.二维界面设计包括表面化学/物理修饰、表面微/纳米结构构筑,能够调节水凝胶的表面浸润性和黏附性,拓展水凝胶在生物医学、海洋防污等领域的应用;三维网络设计,如引入非共价交联作用、设计有序网络结构、复合异质网络等,能够赋予水凝胶自修复性能、各向异性、高强度、形状记忆性能及抗冻性等优异的特性,拓展了水凝胶在可穿戴设备、软体机器人等领域以及复杂环境中的应用.最后我们对仿生水凝胶网络的设计、异质网络的分散以及无损表征等方面未来的发展以及该领域所存在的挑战作出展望.     

侧基含纳米构筑单元的甲壳型液晶高分子的多层次自组装

甲壳型液晶高分子可以呈现超分子柱或片层的链构象,因此可以作为超分子液晶基元形成多种液晶相态,如六方柱状相、柱状向列相、六方柱状向列相、近晶相等.将纳米构筑单元,如一维的二联苯、二维的苯并菲、三维的多面体低聚倍半硅氧烷(POSS)等,引入到甲壳型液晶高分子中,所得聚合物可以自组装形成在亚十纳米和近纳米尺度的多级有序结构.这些结构具有尺寸可控及单分散的优点,可望在有机光电、纳米多孔膜以及纳米光刻等领域有着广阔的应用前景.本文主要介绍了将二联苯、偶氮苯、棒状多苯结构、苯并菲和POSS基元引入到甲壳型液晶高分子中制备多级组装结构的相关工作.     

聚硫辛酸基多功能水凝胶的构建及在感染皮肤伤口修复中的应用

以α-硫辛酸(LA)为单体,借助其强还原性与浓度和温度诱导开环聚合,一步法制备了负载纳米银(AgNPs)的氢键交联高分子水凝胶,并对其可注射性、自修复性、粘接能力、光热效应、抗氧化能力以及生物相容性进行了详细地研究.在细菌感染的大鼠全层皮肤损伤模型中,该高分子水凝胶敷料可以通过光热效应杀死细菌,同时有效降低伤口处的活性氧(ROS)水平,进而调控组织损伤的炎症反应,促进感染伤口的加速愈合.     

具有三维导电网络结构的锡纳米颗粒/石墨烯纳米片复合电极材料的储镁性能研究

镁二次电池具有安全性高、价格低廉等优点,是一种具有潜在应用前景的高能量密度电池体系.目前,镁二次电池的研究重点之一是寻找合适的电极材料.最近,我们通过水热和热处理相结合的方法成功制备了具有三维导电网络结构的锡纳米颗粒/石墨烯纳米片复合电极材料.研究发现,在石墨烯的三维导电网络片层上,均匀分布了粒径小于100 nm的锡纳米颗粒.将锡纳米颗粒/石墨烯纳米片复合材料作为镁二次电池电极材料,当电流密度为15 mA·g^-1和300 mA·g^-1时,首次放电容量分别达到了545.4 mAh·g^-1和238.8 mAh·g^-1,经过150圈后,容量保持率达到了93%,库伦效率为99%,表现出了较高的电化学活性.研究还发现,镁离子嵌入复合材料中形成镁锡合金,当镁离子脱出后,再次形成锡纳米颗粒/石墨烯纳米片复合电极材料,镁离子的脱出和嵌入具有很高的可逆性.这对未来研究设计高性能镁离子电极材料具有十分重要的意义.     

具有三维导电网络结构的锡纳米颗粒/石墨烯纳米片复合电极材料的储镁性能研究（英文）

镁二次电池具有安全性高、价格低廉等优点,是一种具有潜在应用前景的高能量密度电池体系.目前,镁二次电池的研究重点之一是寻找合适的电极材料.最近,我们通过水热和热处理相结合的方法成功制备了具有三维导电网络结构的锡纳米颗粒/石墨烯纳米片复合电极材料.研究发现,在石墨烯的三维导电网络片层上,均匀分布了粒径小于100 nm的锡纳米颗粒.将锡纳米颗粒/石墨烯纳米片复合材料作为镁二次电池电极材料,当电流密度为15 mA·g~(-1)和300 mA·g~(-1)时,首次放电容量分别达到了545.4 mAh·g~(-1)和238.8 mAh·g~(-1),经过150圈后,容量保持率达到了93%,库伦效率为99%,表现出了较高的电化学活性.研究还发现,镁离子嵌入复合材料中形成镁锡合金,当镁离子脱出后,再次形成锡纳米颗粒/石墨烯纳米片复合电极材料,镁离子的脱出和嵌入具有很高的可逆性.这对未来研究设计高性能镁离子电极材料具有十分重要的意义.     

二维自组装聚合制备寡层有机-氧化硅纳米杂化材料

设计、合成了一种两亲性硅氧烷前驱体(PABI),一端为羧基,另一端为具有反应性的硅氧烷基团.利用两亲性分子在水溶液中的自组装特性,研究了它的"二维自组装聚合".实验结果表明,PABI的二维自组装聚合行为与介质、碱的种类和碱的用量等因素有关.我们发现用四甲基胍(TMG)为碱时,PABI在水中通过自组装聚合可以形成寡层二维有机-氧化硅纳米杂化材料.透射电子显微镜(TEM)和原子力显微镜(AFM)的测试结果显示,片层的尺寸为几百纳米到几微米,片层的厚度为6～9 nm.当在水/有机溶剂(如DMSO、DMF、THF或MeOH)的混合溶液中进行自组装聚合时,均未得到层状结构的杂化材料.当用三乙胺和氢氧化钠为碱时,在水中只能得到多层堆积的杂化材料.本研究结果表明,通过二维自组装聚合,可以获得寡层甚至单层二维有机-氧化硅杂化材料.     

导电水凝胶基柔性电子传感系统——柔性电子创新实验设计

导电水凝胶兼具生物医用材料和导电材料特征,可应用于医疗康复、运动监测和人机交互等领域。为提高柔性电子学专业本科生的创新意识与实验技能,本实验设计了一种纳米凝胶材料交联的导电水凝胶,通过探索加聚型水凝胶聚合过程中引发剂浓度和交联机制,阐明材料结构组分对水凝胶基柔性电子器件使用耐久性能及传感性能的影响。通过创新实验设计,柔性电子学专业本科生可以学习到高分子乳液聚合、水凝胶制备以及应力应变传感性能表征等知识点,深入理解交联剂结构设计对材料功能性的影响。此外,本实验还设计了基于水凝胶柔性电子传感器的可穿戴传感系统,通过集成可控制小车移动的智能手套,以及用于控制电脑游戏的水凝胶控制器,将前沿科研与本科实验教学任务紧密结合,有利于激发柔性电子、材料、电子信息等专业本科生对于科研的兴趣和创新探索的科研精神。     

Synthesis of conducting polymer hydrogels with 2D building blocks and their potential-dependent gel-sol transitions

Conducting polymer hydrogels with unusual 2D building blocks were synthesized in one step via a combination of oxidative coupling polymerization and non-covalent crosslinking of an amphiphilic thiophene derivative. Chemicals with standard electrode potentials higher than 0.8 V triggered disbanding of the resulting conducting polymer hydrogels, indicating the occurrence of potential-dependent gel-sol transitions.     

Two‐Dimensional Mesoscale‐Ordered Conducting Polymers

Despite the availability of numerous two‐dimensional (2D) materials with structural ordering at the atomic or molecular level, direct construction of mesoscale‐ordered superstructures within a 2D monolayer remains an enormous challenge. Here, we report the synergic manipulation of two types of assemblies in different dimensions to achieve 2D conducting polymer nanosheets with structural ordering at the mesoscale. The supramolecular assemblies of amphipathic perfluorinated carboxylic acids and block co‐polymers serve as 2D interfaces and meso‐inducing moieties, respectively, which guide the polymerization of aniline into 2D, free‐standing mesoporous conducting polymer nanosheets. Grazing‐incidence small‐angle X‐ray scattering combined with various microscopy demonstrates that the resulting mesoscale‐ordered nanosheets have hexagonal lattice with d‐spacing of about 30 nm, customizable pore sizes of 7–18 nm and thicknesses of 13–45 nm, and high surface area. Such template‐directed assembly produces polyaniline nanosheets with enhanced π–π stacking interactions, thereby resulting in anisotropic and record‐high electrical conductivity of approximately 41 S cm^?1 for the pristine polyaniline nanosheet based film and approximately 188 S cm^?1 for the hydrochloric acid‐doped counterpart. Our moldable approach creates a new family of mesoscale‐ordered structures as well as opens avenues to the programmed assembly of multifunctional materials.     

Two‐Dimensional Fullerene Assembly from an Exfoliated van der Waals Template

Two‐dimensional (2D) materials are commonly prepared by exfoliating bulk layered van der Waals crystals. The creation of synthetic 2D materials from bottom‐up methods is an important challenge as their structural flexibility will enable chemists to tune the materials properties. A 2D material was assembled using C₆₀ as a polymerizable monomer. The C₆₀ building blocks are first assembled into a layered solid using a molecular cluster as structure director. The resulting hierarchical crystal is used as a template to polymerize its C₆₀ monolayers, which can be exfoliated down to 2D crystalline nanosheets. Derived from the parent template, the 2D structure is composed of a layer of inorganic cluster, sandwiched between two monolayers of polymerized C₆₀. The nanosheets can be transferred onto solid substrates and depolymerized by heating. Electronic absorption spectroscopy reveals an optical gap of 0.25 eV, narrower than that of the bulk parent crystalline solid.     

Synthetic Strategies for Constructing Two‐Dimensional Metal‐Organic Layers (MOLs): A Tutorial Review

Two‐dimensional (2D) metal‐organic layers (MOLs) are the 2D version of metal‐organic frameworks (MOFs) with nanometer thickness in one dimension. MOLs are also known as 2D‐MOFs, 2D coordination polymers, ultrathin MOF nanosheets (UMOFNs) or coordination nanosheets in literature. This new category of 2D materials has attracted a lot of interests because of the opportunity in combining molecular chemistry, surface/interface chemistry and material chemistry of low dimensional materials in these systems. Several synthetic strategies have been developed for the construction of 2D MOLs, but the general synthesis of MOLs still presents a challenge. This tutorial level review summarizes the recent progress in the fabrication of novel 2D MOLs and aims to highlight challenges in this field.     

High water content clay–nanocomposite hydrogels incorporating guanidinium‐pendant methacrylamide: Tuning of mechanical and swelling properties by supramolecular approach

Novel clay–polymer composite hydrogels with high water content (up to 98 wt %) are developed, in which mechanical properties are reinforced by the formation of multiple ion‐pairs between the polymer chains and clay nanosheets (CNS). When a small amount of guanidinium‐pendant methacrylamide (0.1–0.2 wt %) is copolymerized with a neutral monomer (0.5–2.0 wt %) in an aqueous dispersion of CNS (1.0–3.0 wt %), a self‐standing hydrogel with satisfactory mechanical toughness and elasticity results, despite its high water content (95–98 wt %). The mechanical properties and swelling behaviors of the hydrogels can be tuned by the amount of the guanidinium‐pendant acrylamide. A systematic study indicates that the ion pairs, formed between the guanidinium groups in the polymer chains and the oxyanions on the surfaces of the CNS, serve as crosslinking points in the three‐dimensional network developed in these hydrogels. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 839–847     

Hybrid organic-inorganic, rod-shaped nanoresistors and diodes

The electrical properties of template-synthesized three- and four-component rodlike nanostructures consisting of metal and conducting polymer domains have been studied. These structures behave like nanometer-scale resistors and diodes, depending upon their compositions and spatial distribution of the different compositional blocks. In the two-component systems, the conducting polymer block dictates the electrical properties of the nanostructure, and the metal blocks act as leads to facilitate the connection with microscopic circuits. In the three-component systems, the metal blocks provide an additional design flexibility, allowing one to prepare Schottky junctions.     

聚苯胺/贵金属复合纳米材料的可控合成及催化应用

导电高分子/贵金属复合纳米材料因其在催化、传感、表面增强拉曼、光热治疗等诸多领域的应用前景而受到广泛关注.本文主要介绍我们课题组近年来利用可控合成策略制备的负载型和包埋型两种结构聚苯胺/贵金属复合纳米材料,以及利用复合纳米材料的结构和功能特性,对其在多相催化领域的应用、结构与催化性能之间构效关系的探索.     

Physics of engineered protein hydrogels

Artificially engineered proteins and synthetic polypeptides have attracted widespread interest as building blocks for polymer hydrogels. The biophysical properties of the proteins, such as molecular recognition abilities, folded chain structures, and sequence-dependent thermodynamic behavior, enable advances in functional, responsive, and tunable gels. This review discusses the design of polymer hydrogels that incorporate protein domains, highlighting new challenges in polymer physics that are presented by this emerging class of materials. Five types of engineered protein hydrogels are discussed: (a) physically associating protein polymer gels, (b) amorphous artificially engineered protein networks, (c) engineered proteins with crystalline domains, (d) stretchable protein tertiary structures in gels, and (e) protein gels with biological recognition properties. The physics of the protein component and the physical properties of the resulting hydrogels are summarized, illustrating how advances in understanding these systems are leading to exciting novel biofunctional hydrogels. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

一维纳米纤维构筑的导电聚合物三维结构及其可控的浸润性

微/纳米结构的导电聚合物由于具有高导电性、易合成以及优异的环境稳定性从而在许多先进的研究领域备受关注,并有望在分子导线、化学和生物传感器、发光器件等领域获得广泛应用。 特别是,复杂的三维自组装结构在获得高性能和功能化的材料方面提供了巨大的潜在应用价值。本文主要介绍了我们利用胶束的软模板和自组装驱动力的协同效应,实现由一维纳米结构组装的三维微米结构导电聚合物方面的研究进展。该制备技巧在于低表面自由能的含氟有机酸具有软模板、掺杂剂、自组装驱动力,以及诱导超疏水性的多重作用实现导电聚合物三维结构的组装和多功能化。介绍了利用环境湿度调整分子的自组装驱动力,实现导电聚合物由一维纳米结构向三维微米结构的组装。此外,还介绍了利用导电聚合物可逆的化学掺杂/脱掺杂机制,实现导电聚合物表面浸润性的可逆转化。最后介绍了在液/液/固三相体系中,通过外加电场刺激,可实现油滴在导电聚合物表面的浸润性和黏附力的控制。     

Chiral,pH responsive hydrogels constructed by N‐Acryloyl‐alanine and PEGDA/α‐CD inclusion complex: preparation and chiral release ability

Chiral, pH‐responsive hydrogels are constructed by poly(ethylene glycol) diacrylate/α‐cyclodextrin (PEGDA/α‐CD) inclusion complex and L‐N‐acryloyl‐alanine or D‐N‐acryloyl‐alanine (L‐NAA or D‐NAA) by an effective free radical polymerization approach. PEGDA containing two C=C end groups was used simultaneously to introduce α‐CD units in the resulting hydrogels and to serve as a cross‐linking agent, by which forming the designed hydrogels in quantitative yield. Hydrophilic α‐CD moieties acted as pore‐forming agent, while the L(D)‐NAA‐based polymer chains bearing –COOH groups enabled the hydrogels to display remarkable swelling–deswelling behavior in response to pH variation. The chiral NAA monomer‐derived polymer chains rendered the hydrogels with intriguing optical activity, according to circular dichroism spectra. Scanning electron microscopy revealed the uniformly porous microstructures of hydrogels. More remarkably, the L‐NAA‐based hydrogels preferentially adsorbed trans‐4‐hydroxy‐d ‐proline and preferentially released trans‐4‐hydroxy‐l ‐proline, while D‐NAA‐based hydrogels provided opposite results. The hydrogels also demonstrated remarkable enantioselective release ability towards chiral drug ibuprofen. Copyright © 2015 John Wiley & Sons, Ltd.