简单对流自组装制备层数可控有序阵列（英文）

利用简单的方法和较少的胶体乳液,在没有任何特殊设备的情况下制备出了二维和三维的有序阵列。通过控制胶体乳液浓度获得了层数可控的胶体晶体有序阵列。通过使用现有成膜模型模拟沉积行为揭示胶体晶体阵列在生长过程中控制冷凝蒸发过程的机理,对自组装过程中颗粒转移和溶剂蒸发之间的平衡细节进行了详细的讨论。利用阵列横截面的SEM显微照片来观测样品的厚度和均匀性,通过反射光谱来观察样品的光学性质。     

胶体晶体自组装排列进展

自组装排列胶体晶体是发展光子晶体等亚微米周期有序结构及新型光电子器件十分重要的环节.高电荷密度单分散胶体球在较弱的离子强度和稀浓度下会自发排列形成紧密堆积的周期性结构(ccp),常常是面心立方(fcc),科学家们以此为基础发展了多种结晶化胶体粒子的方法,包括重力场沉积、电泳沉积、胶体外延技术、垂直沉积、流通池、物理束缚排列及其他的许多方法.目前排列的胶体粒子基本为球形,材料也多为SiO2、PS、PMMA,此外一些复合粒子,主要为核壳粒子的排列这里也稍作介绍,这些方法及其变通的使用可以形成类蛋白石及反蛋白石结构,最终实现光子带隙及其它多种用途。     

溶剂散逸自组装制备高分子有序微透镜阵列

利用水珠为模板制备了聚苯乙烯有序多孔膜.在溶剂挥发的制冷作用下,水珠能够在冷的高分子溶液表面凝结形成有序的阵列,溶剂蒸发完毕后,高分子材料按照水珠排列形貌空隙形成有序多孔膜,一种两性共聚物被加入到溶液中稳定水珠而获得有序的多孔结构. 将聚乙烯醇水溶液填充入多孔膜中,蒸干后用氯仿洗去聚苯乙烯,得到聚乙烯醇的整球微透镜阵列. 聚苯乙烯有序针垫阵列是由有序多孔膜撕掉上层制备的,这种针垫结构内部具有半球结构的空间,并以此为模板制备了聚乙烯醇半球微透镜阵列. 2种微透镜阵列均具有微观显影功能. 通过2种微透镜的显像对比证实,半球微透镜阵列比整球微透镜阵列具有更为清晰的多重显像效果.     

蒸发自组装法制备聚苯乙烯胶体晶体

采用乳液聚合法制得亚微米级聚苯乙烯单分散微球,并用蒸发自组装法在乳液气-液界面进行自上而下的层层组装,制得了厚度在450μm以上的三维有序胶体晶体。结果表明,影响胶体晶体有序性的关键因素是对蒸发速度的控制,促使胶体晶体规则排列的最主要作用力为溶液的毛细管力。在胶体晶体组装末期,随着溶剂量的减少,空间阻力逐渐增大,微球对流能力下降,造成胶体晶体的有序性降低。     

卟啉可控自组装及其应用

卟啉是具有大π共轭结构的环状分子,可在非共价键的作用下通过可控自组装形成有序的纳米结构,通过分子间协同作用实现光电性质的有效调控.然而,精确调控自组装过程以获得形貌可控、尺寸均一、内部结构有序的自组装纳米结构,并阐明控制性能的关键因素仍然是一个巨大的挑战.本文综述了近年来卟啉自组装纳米结构的溶液相自组装策略及其在光催化、化学传感和生物光疗领域中应用的最新进展,并初步总结了卟啉自组装纳米结构的形貌、尺寸和内部结构与性能的构效关系.     

自组装方法制备有序微孔薄膜

本文对近年来自组装方法制备有序微孔薄膜的研究进行了综述,总结了固体基板展开法制备有序微孔薄膜的形成机理,对成膜材料,成膜的影响因素和微孔阵列排列的形成条件等方面进行了详细的介绍和分析,并对自组装方法制备微孔薄膜的应用前景作了探讨。     

溶剂散逸自组装制备导电各向异性的金属有序阵列

通过溶剂散逸自组装法制备了聚苯乙烯(PS)有序多孔膜. 利用水珠在冷的PS溶液表面凝结形成有序阵列, 使PS以水珠阵列为模板形成有序多孔膜. 将有序多孔膜的上层剥离并附着在可收缩性高分子表面, 并进行离子溅射, 除掉有序多孔膜后在可收缩膜上留下了有序的金属圆盘阵列. 经过收缩, 有序阵列不仅光学性质发生了改变, 而且实现了导电的各向异性.     

胶体颗粒在聚电解质多层膜表面的可控组装

利用原子力显微镜和扫描电子显微镜研究了磺化聚苯乙烯胶体颗粒在由聚二甲基二烯丙基氯化铵和聚苯乙烯磺酸钠层状自组装而成的多层膜表面的组装.该组装受表面性质影响,通过对多层膜的最外层的组装条件或利用盐溶液对多层膜进行后处理可以控制胶体颗粒在膜表面的组装密度.     

基于生物刺激源的响应性聚合物及其可控自组装

基于生物刺激源的响应性大分子自组装体系对智能聚合物领域的发展具有重要的意义。本文回顾并综述了近年来在该领域内针对生物大分子及各种小分子作为刺激源的大分子自组装体系及其研究现状。依据不同类型的刺激源进行分类,论述了近年来的研究进展,并合理展望了该领域未来的发展前景。     

“可控自组装体系及其功能化”重大研究计划取得系列重要研究成果

In 2005, the Science magazine, in commemorating the 125th anniversary of its founding, proposed 25 most challenging scientific issues in the future. One of the issues, "How far can we push chemical self-assembly?" has attracted the attention of scientists all over the world. During the 11th Five Year Plan period, NSFC convened scientists from various fields and proposed a major research project, "Controllable self-assembly system and its functionalization". Since the implementation of this project, Chinese scientists have developed and recognized a variety of noncovalent interactions, constructed numerous assembly building blocks with the "Chinese label", established a new assembly method similar to an organic "name reaction", realized the functions of multi-component and multi-level assemblies, and constructed a batch of controllable self-assembly systems having scientific importance and potential practical value. They have achieved great leap forward from following to original innovation, and brought the research of chemical self-assembly in China to move forward to the center of international stage. In this study, we examined the overall scientific goals, general layout of the plan, and ideas for implementation of the major research program "Controllable Self-Assembly System and its Functionalization", as well as an array of significant research accomplishments made possible through the funding received by the program.     

聚苯乙烯胶晶的组装

采用自然沉降法、离心法和垂直沉积法组装了聚苯乙烯胶晶。实验结果表明,所得胶晶都具有面心立方结构,结构有序性相当高。自然沉降法和离心法适用于块体胶晶的组装,自然沉降法适用于胶晶膜的组装。     

Facile Assembly of 3D Binary Colloidal Crystals from Soft Microgel Spheres

It still remains a big challenge to fabricate binary colloidal crystals (binary CCs) from hard colloidal spheres, although a lot of efforts have been made. Here, for the first time, binary CCs are assembled from soft hydrogel spheres, PNIPAM microgels, instead of hard spheres. Different from hard spheres, microgel binary CCs can be facilely fabricated by simply heating binary microgel dispersions to 37 °C and then allowing them to cool back to room temperature. The formation of highly ordered structure is indicated by the appearance of an iridescent color and a sharp Bragg diffraction peak. Compared with hard sphere binary CCs, the assembly of PNIPAM microgel binary CCs is much simpler, faster and with a higher “atom” economy. The easy formation of PNIPAM microgel binary CC is attributed to the thermosensitivity and soft nature of the PNIPAM microgel spheres. In addition, PNIPAM microgel binary CCs can respond to temperature change, and their stop band can be tuned by changing the concentration of the dispersion.

     

Facile Synthesis of Ordered Mesoporous Zirconia for Electrochemical Enrichment and Detection of Organophosphorus Pesticides

Highly crystallized mesoporous ZrO₂ nanomaterials were synthesized by solvent evaporation induced self‐assembly approach. Ordered mesoporous ZrO₂ nanomaterials were characterized by TEM, SEM, BET, XRD and UV‐Vis spectroscopy. The obtained nanomaterials exhibit the close‐packing mesopores with average pore size of 7 nm and a highly crystallized framework with tetragonal phase. A non‐enzyme electrochemical sensor based on ordered mesoporous ZrO₂ is established for selective detection of methyl parathion (MP). The online extraction of MP is firstly achieved by ZrO₂ modified electrode at open‐circuit potential for 5 min., and the sensitive detection of MP is performed by differential pulse voltammetry (DPV) method. By comparison, DPV responses of mesoporous ZrO₂ are 40 times and 25 times larger than that of mesoporous silica and mesoporous carbon with the similar pore structure, implying the specific affinity advantage of zirconia to phosphoric group. The quantitative analysis result shows that the voltammetric currents are linear with concentrations of MP ranging from 1 ng/ml to 2 μg/ml with a detection limit of 0.53 ng/ml. The sensor also exhibits good stability and high selectivity against interfering species. The excellent analytical performances are owed to the accessible and uniform mesoporous structures, highly crystallized frameworks of ZrO₂ and its specific affinity to phosphate groups.     

有序大孔材料的制备及其应用

本文综述了近年来有序大孔材料的制备及应用.有序大孔材料的制备方法有胶态晶体模板法、生物模板法及其它模板法,重点阐述了用胶态晶体为模板制备有序大孔材料,如大孔金属、大孔无机氧化物、大孔碳、大孔半导体、大孔无机盐、大孔碳/无机氧化物复合物和大孔有机聚合物.用胶态晶体为模板制备有序大孔材料在催化、吸附、分离、传感器、光子晶体和声学等领域有潜在的应用.     

Synthesis,Optoelectronic and Self‐Assembly Properties of Diazadioxaacene Derivatives

Two novel diazadioxaacene derivatives ( ADOP and ADOQ ) have been successfully synthesized and characterized. Their single crystal analyses disclose that molecule ADOP forms a twisted topology configuration, whereas ADOQ adopts reclining‐chair architecture. Both of them emit strong blue fluorescence in organic solvents. Moreover, they can self‐assemble to form regular nanobelts and nanowires, respectively, via a simple surfactant‐assisted method.     

三维有序大孔炭的设计构筑、性能及应用研究

多孔炭材料具有高的比表面积、发达的孔结构、耐热、耐腐蚀、无毒无害、价廉、易操作等特点,以其为研究核心,在学术界和工业界均具有广阔的应用前景。通过胶晶模板法合成孔径在亚微米范围内的三维有序大孔炭,其高度规整的孔道结构,在吸附分离、催化和电极等领域已展现出巨大的应用潜能。利用双模板法将介孔结构融汇于三维有序大孔炭的孔壁中,设计构筑出三维有序大孔-介孔炭,势必会显著增强其应用价值。本文主要阐述了以胶晶为主体模板制备三维有序大孔炭的各种路径;采用双模板法将介孔引入大孔通道内获取三维有序大孔-介孔炭;探索影响孔结构参数的主要因素,并与各种功能材料复合增强其性能;着重对三维有序大孔炭及大孔-介孔炭在环境净化和新型能源转化与储备领域的应用进行概述。     

SiO2胶体颗粒的三维有序自组装

由SiO2胶体颗粒的三维有序自组装可以得到面心立方三维结构,它具有折射率周期性变化的特点。它的制备涉及胶体化学、材料科学等学科的前沿领域。其自组装方法包括胶体颗粒的沉降自组装、胶体颗粒在物体限制下的自组装、胶体颗粒的连续对流自组装和利用胶体颗粒表面电性质的自组装。本文对这些组装方法进行了介绍。     

Template‐Free Supracolloidal Self‐Assembly of Atomically Precise Gold Nanoclusters: From 2D Colloidal Crystals to Spherical Capsids

We report supracolloidal self‐assembly of atomically precise and strictly monodisperse gold nanoclusters involving p‐mercaptobenzoic acid ligands (Au₁₀₂‐pMBA₄₄) under aqueous conditions into hexagonally packed monolayer‐thick two‐dimensional facetted colloidal crystals (thickness 2.7 nm) and their bending to closed shells leading to spherical capsids (d ca. 200 nm), as controlled by solvent conditions. The 2D colloidal assembly is driven in template‐free manner by the spontaneous patchiness of the pMBA ligands around the Au₁₀₂‐pMBA₄₄ nanoclusters preferably towards equatorial plane, thus promoting inter‐nanocluster hydrogen bonds and high packing to planar sheets. More generally, the findings encourage to explore atomically precise nanoclusters towards highly controlled colloidal self‐assemblies.     

A Facile Synthesis of Dispiro-Ring Compounds Via Telluronium Ylides

The cyclopropanation reaction of α,α′-bis (substitutedbenzylidene)cycloalkanones with telluronium ylides was studied. The products were proved to be the derivative of dispiro[2, 1, 2, 2]nonane-4-one and dispiro[2, 1, 2, 3]decane-4-one.