DNA-多肽复合分子的设计、组装与应用

DNA-多肽复合分子作为一类新型的自组装分子受到研究人员的广泛关注。DNA分子具有可编程性、高特异性、功能多样等优点,多肽分子是一类重要的生物小分子,能够通过分子自组装形成具有不同结构的纳米材料,因此,将二者通过共价交联,可以获得具有多级自组装行为的DNA-多肽复合分子,能够实现两类重要生物分子功能的集成优化,合成具有不同结构与功能的超分子自组装材料。此外,通过酶催化、DNA杂化、DNA链置换反应等,还可实现对多肽-DNA复合分子自组装行为的动态调控,进而模拟生命系统中复杂动态的自组装结构,强化相关材料在生物、化学、材料等领域的应用。本文讨论了DNA-多肽复合分子的设计、组装与应用方面的最新进展,最后基于目前DNA-多肽复合分子存在的一些问题对DNA-多肽复合分子的研究做了展望。     

层层自组装聚电解质膜光纤传感器的制备和应用

在过去几十年中,光纤的应用已经渗透到多个学科领域。光纤的抗电磁干扰、可远程监控、多重监测、体积小及质量轻等特点,使其在传感器研究领域备受关注。聚电解质层层自组装膜构建的光纤传感器自2000年诞生以来,已快速发展成为传感器领域新的研究热点。该类光纤传感器在微量物质的监测方面具有广泛的应用前景。本文从光纤和光纤传感器优点出发,总结了基于层层自组装多层膜的光纤传感器种类、性能、检测原理以及相应的光纤结构和自组装材料;进而结合作者已做的相关工作,论述了在光纤基底上的聚电解质层层自组装及基于自组装膜的光纤传感器的测试;重点综述了近十年层层自组装膜的光纤pH传感器、湿度传感器、气体传感器、生物传感器及其他类型的光纤传感器的制备与应用,并展望了今后聚电解质层层自组装多层膜光纤传感器的发展。     

有机铟化合物的自组装现象

结合作者近两年来有机铟化合物自组装研究的一系列工作，综述了有机铟化合 物的自组装现象。有机铟化合物可以通过分子间的配位键和次级键连接而形成自组 装的二聚体或多聚体结构。其中一些有机铟化合物可以作为InN，InP，InAs的前体。     

自组装超薄膜及其应用

自组装膜是指以价键或非价键相互作用在一定表面形成的具有某种特定结构、性能的单层或多层超薄膜。在自然界中 ,人们可以看到许多不同的组分通过自组装形成具有层状超分子结构的复杂体系 ,但直到 1 946年 ,人类才在清洁表面制备了单分子层膜[1] 。与分子束外延和化学气相沉积等制备膜的方法相比 ,以自组装方式形成的超薄膜具有有序性高、平整度好、膜的厚度分子水平可控以及不受基底形状限制等优点[2 ] 。近 1 0多年来 ,随着人们对界面化学研究的深入以及对具有特定功能的薄膜材料的需求 ,使自组装超薄膜的研究成为一个热点。本文从分类、…     

苯丙氨酸二肽类分子自组装:分子设计、结构调控与材料应用

近年来,苯丙氨酸二肽类分子的自组装研究受到了广泛关注,已成为超分子化学、生物材料科学研究的前沿领域之一。苯丙氨酸二肽类纳米组装体因具有结构多样、易功能化以及良好的生物相容性等优点,在纳米制造、组织修复等方面展示出巨大的应用潜力。本文从分子设计、组装结构调控与材料应用三个层次系统综述了苯丙氨酸二肽类分子自组装的研究进展。首先总结了苯丙氨酸二肽类分子的修饰改性,包括乙酰基、芳香环、氨基酸、短肽等基团。然后,重点介绍了苯丙氨酸二肽类分子自组装的调控策略和方法,如溶剂、界面、气相、多组分共组装和酶催化组装。最后,介绍了苯丙氨酸二肽类自组装材料在纳米材料合成、传感检测、药物传递及组织修复等方面的应用现状,并分析了该领域今后的发展方向。     

疏基烷氧基喹啉化合物的合成

自组装单分子膜 ( Self- Assembled Monolayer,SAM)由于其致密和高度有序性在分子器件、修饰电极、纳米电子学以及仿生科学等领域有着广泛的应用前景。可用于自组装的材料有脂肪醇、有机硅烷和烷基硫醇类衍生物 [1]。自组装膜的研究大多数集中于巯基化合物在金表面共价吸附形成的单分子膜 ,为了得到具有不同功能的自组装膜就需要合成带有不同功能基团的巯基化合物。广泛使用的是具有X( CH2 ) n SH结构的巯基化合物 [2 ] ( X为所感兴趣的官能团 )。文献 [3] 报道了含酰胺键、偶氮苯基的 SAM材料的合成。巯基烷氧基喹啉化合物是一类新型…     

有机阳离子-无机多阴离子复合物:高分子体系中的组装及其自组装

有机阳离子包覆多金属氧簇无机多阴离子形成的具有确定化学组成、两亲性核壳结构超分子复合物,具有易于调控和集成有机和无机组分结构与功能的特性.以此类复合物为预组装体的自组装和高分子功能杂化材料展现了一类具有多方面构筑超分子组装体的新型构筑基元体系.如何实现预组装体复合物在结构稳定、具有良好加工性基材中的组装和功能化成为这一领域的重要研究内容.本文系统地总结了基于此类超分子复合物的高分子纳米复合材料和溶液中组装方面的研究进展与发展趋势.     

静电自组装铁电超薄膜及其性能研究

利用静电自组装方法在石英玻璃表面交替沉积聚二烯丙基二甲基氯化铵(PDDA)和聚偏氟乙烯(PVDF)超薄膜,制得PDDA/PVDF铁电复合超薄膜.通过石英晶体微天平实时监测超薄膜的沉积,研究了超薄膜的表面形貌、结构及电性能.结果表明,自组装每层PVDF超薄膜的厚度为7.5 nm;PDDA/PVDF铁电复合超薄膜的表面平整、均匀,其中C1s的光电子能谱与极化处理后充负电荷的PVDF铁电聚合物一致,但F1s由于溶解再组装过程而降低了0.3 eV;静电自组装材料纳米级的薄膜厚度和聚合物的络合作用导致了铁电复合超薄膜的非晶结构和高的表面电阻率.     

智能响应与自修复的层层组装聚合物膜

具有刺激响应性和自修复功能的复合膜是重要的仿生功能膜材料.层层组装是一种基于物质交替沉积而制备复合膜的方法,可以实现膜的结构和组成的精确调控.通过结构与组成的精确调控,基于层层组装制备的微米厚度的聚电解质厚膜可以对外界刺激产生快速有效的响应,因而在制备智能仿生膜材料方面具有重要的价值.本文以作者的研究结果为基础,阐明了基于层层组装的聚电解质膜可以成功用于制备湿度和温度响应的双结构自支持膜和高效的促动器及行走机器,以及自修复超疏水和划痕修复聚电解质膜.     

非共价键自组装有机功能材料

分子自组装对于某些化学反应过程、生物化学过程及生命活动的模拟等方面具有重要的意义。本文对非共价键组装方式自组装的有机功能材料的分类，结构、性质、自组装机理以及研究进展进行了综述。     

Nanocomposites and macroscopic materials: assembly of chemically modified graphene sheets

Self-assembly of chemically modified graphenes (CMGs), including graphene oxide (GO), reduced graphene oxide (RGO) and their derivatives, has emerged as one of the most appealing strategies to develop unprecedented graphene-based functional materials. With the assistance of various non-covalent forces such as hydrogen bonding, ionic, amphiphilic and π-π interactions, CMGs decorated with multiple functional groups are favorable for assembly with different organic and inorganic components which can result in hierarchical composites possessing unique structures and functions. In this review, we will summarize the state-of-the-art self-assembly strategies that have been established to construct CMG based nanomaterials, including nanoparticles, nanospheres, nanofibers, nanorods, nanosheets, and macroscopic thin films, fibers and porous networks. The driving forces involved in the self-assembly process will be elucidated in the context. Further, we will also highlight several representative examples of applications regarding the self-assembled CMG based materials.     

几种自组装拉胀分子网络的分子模拟

报道了几种蜈蚣形、双足蜈蚣形聚合物 ,以及单箭头、双箭头形小分子通过氢键自组装形成拉胀分子网络的分子设计 .分子力学计算结果表明这些自组装分子网络靠氢键相互作用规则排列 ,具有类似倒插蜂窝网络结构 ,所设计的聚合物、小分子的合成较之以往报道的二维网络结构的合成简便易行 ,为真正分子水平意义上的拉胀结构的实现提供了新的思路和指导     

Adsorption of Cationic Laser Dye onto Polymer/Surfactant Complex Film

Fabrication of complex molecular films of organic materials is one of the most important issues in modern nanoscience and nanotechnology. Soft materials with flexible properties have been given much attention and can be obtained through bottom up processing from functional molecules, where self-assembly based on supramolecular chemistry and designed assembly have become crucial processes and technologies. In this work, we report the successful incorporation of cationic laser dye rhodamine 6G abbreviated as R6G into the pre-assembled polyelectrolyte/surfactant complex film onto quartz substrate by electrostatic adsorption technique. Poly(allylamine hydrochloride) (PAH) was used as polycation and sodium dodecyl sulphate (SDS) was used as anionic surfactant. UV-Vis absorption spec-troscopic characterization reveals the formation of only H-type aggregates of R6G in their aqueous solution and both H- and J-type aggregates in PAH/SDS/R6G complex layer-by-layber films as well as the adsorption kinetics of R6G onto the complex films. The ratio of the absorbance intensity of two aggregated bands in PAH/SDS/R6G complex films is merely independent of the concentration range of the SDS solution used to fabricate PAH/SDS com-plex self-assembled films. Atomic force microscopy reveals the formation of R6G aggregates in PAH/SDS/R6G complex films.     

Ordered patterns and structures via interfacial self-assembly: superlattices, honeycomb structures and coffee rings

Self-assembly is now being intensively studied in chemistry, physics, biology, and materials engineering and has become an important "bottom-up" approach to create intriguing structures for different applications. Self-assembly is not only a practical approach for creating a variety of nanostructures, but also shows great superiority in building hierarchical structures with orders on different length scales. The early work in self-assembly focused on molecular self-assembly in bulk solution, including the resultant dye aggregates, liposomes, vesicles, liquid crystals, gels and so on. Interfacial self-assembly has been a great concern over the last two decades, largely because of the unique and ingenious roles of this method for constructing materials at interfaces, such as self-assembled monolayers, Langmuir-Blodgett films, and capsules. Nanocrystal superlattices, honeycomb films and coffee rings are intriguing structural materials with more complex features and can be prepared by interfacial self-assembly on different length scales. In this critical review, we outline the recent development in the preparation and application of colloidal nanocrystal superlattices, honeycomb-patterned macroporous structures by the breath figure method, and coffee-ring-like patterns (247 references).     

纳米材料的概述、制备及其结构表征

纳米材料在电子、光学、化工、陶瓷、生物和医药等诸多方面的重要应用而引起人们的高度重视。本文从以下3个方面加以论述。 一、纳米材料的概述:从分子识别、分子自组装、吸附分子与基底的相互关系、分子操作与分子器件的构筑,并通过具体的例证加以阐述,包括在STM操作下单分子反应;有机小分子在半导体表面的自指导生长;多肽-半导体表面特异性选择结合;生物分子/无机纳米组装体;光驱动多组分三维结构组装体;DNA分子机器。 二、纳米材料的若干制备方法和结构表征方法:制备方法包括:物理的蒸发冷凝法,分子束外延法(MBE),机械球磨法,扫描探针显微镜法(SPM)。化学的气相沉淀法(VCD),液相沉淀法,溶胶-凝胶法(Sol-gel),L-B膜法,自组装单分子层和表面图案化法,水热/溶剂热法,喷雾热解法,样板合成法或化学环境限制法及自组装法。 三、若干结构表征方法包括:X-射线法(XRD),扩展X射线精细结构吸收谱(EXAFS),X-射线光电子能谱(XPS),光谱法,扫描隧道显微镜/原子力显微镜(STM/AFM)和有机质谱法(OMS)。     

分子识别指导下的有机分子设计、合成和组装——世纪交替时代的有机化学

在21世纪即将来临之际,有机化学将面临生命科学、环境科学和材料科学越来越多的挑战。本文回顾了在分子识别指导下的有机分子的设计、合成和组装这个新领域的诞生和发展,认为这个领域将成为新世纪有机化学发展的一个重要方向。它的发展和应用不仅使得有机化学可能较好地面对新挑战,同时能推动有机合成化学自身的发展。     

Programming supramolecular peptide materials by modulating the intermediate steps in the complex assembly pathway: Implications for biomedical applications

Self-assembling peptides form a prominent class of supramolecular materials with in general good biocompatibility. To afford better control over the material properties, tremendous progress has been made in studying the supramolecular organization of the peptide assemblies. This knowledge has helped us to understand the correlation between the molecular structure of the peptide building blocks and the properties of the supramolecular products. However, peptide self-assembly consists of a complex pathway rather than a spontaneous thermodynamic process. This implies that the outcome of the self-assembly is critically governed by the assembly pathway. Here, we are going to discuss how peptide self-assembly can be modulated at the intermediate steps in the self-assembly pathway. The focus will be to demonstrate this engineering approach on the example of zero-dimensional/one-dimensional nanostructure selectivity over the β-sheet assembly pathway. In addition, we provide examples of biomedical applications of such steered peptide assemblies in the field of drug delivery and tissue engineering.     

Self-assembled gelators for organic electronics

Nature excels at engineering materials by using the principles of chemical synthesis and molecular self-assembly with the help of noncovalent forces. Learning from these phenomena, scientists have been able to create a variety of self-assembled artificial materials of different size, shapes, and properties for wide ranging applications. An area of great interest in this regard is solvent-assisted gel formation with functional organic molecules, thus leading to one-dimensional fibers. Such fibers have improved electronic properties and are potential soft materials for organic electronic devices, particularly in bulk heterojunction solar cells. Described herein is how molecular self-assembly, which was originally proposed as a simple laboratory curiosity, has helped the evolution of a variety of soft functional materials useful for advanced electronic devices such as organic field-effect transistors and organic solar cells. Highlights on some of the recent developments are discussed.     

Manipulation of molecular transport into mesoporous silica thin films by the infiltration of polyelectrolytes

The design of hybrid mesoporous materials incorporating polymeric assemblies as versatile functional units has become a very fertile research area offering major opportunities for controlling molecular transport through interfaces. However, the creation of such functional materials depends critically on our ability to assemble polymeric units in a predictable manner within mesopores with dimensions comparable to the size of the macromolecular blocks themselves. In this work, we describe for the first time the manipulation of the molecular transport properties of mesoporous silica thin films by the direct infiltration of polyelectrolytes into the inner environment of the 3D porous framework. The hybrid architectures were built up through the infiltration-electrostatic assembly of polyallylamine (PAH) on the mesopore silica walls, and the resulting systems were studied by a combination of experimental techniques including ellipso-porosimetry, cyclic voltammetry and X-ray photoelectron spectroscopy, among others. Our results show that the infiltration-assembly of PAH alters the intrinsic cation-permselective properties of mesoporous silica films, rendering them ion-permeable mesochannels and enabling the unrestricted diffusion of cationic and anionic species through the hybrid interfacial architecture. Contrary to what happens during the electrostatic assembly of PAH on planar silica films (quantitative charge reversal), the surface charge of the mesoporous walls is completely neutralized upon assembling the cationic PAH layer (i.e., no charge reversal occurs). We consider this work to have profound implications not only on the molecular design of multifunctional mesoporous thin films but also on understanding the predominant role of nanoconfinement effects in dictating the functional properties of polymer-inorganic hybrid nanomaterials.     

Engineered hydrogen-bonded polymer multilayers: from assembly to biomedical applications

Over the last two decades the layer-by-layer (LbL) assembly technique has become a highly versatile platform for the synthesis of nanoengineered thin films and particles. The widespread need for highly functional and responsive materials for applications in biomedicine-such as drug and gene delivery-has recently led to considerable efforts in the assembly of LbL materials, particularly films that can be subsequently stabilised and functionalised through a range of chemistries. In this tutorial review, recent developments in hydrogen-bonded LbL-assembled materials will be discussed, focusing on the design of materials with enhanced stimuli-responsive characteristics. Emphasis will be given to materials engineered for biomedical applications, specifically films/capsules that afford controlled loading and release of therapeutic cargo for application in vitro and in vivo.