具有纳米孔洞的金属-有机超分子聚合物与功能材料

本文介绍了近几年来一个热门的研究领域－纳米超分子笼和具有纳米孔洞的金属－有机聚合物的研究现状和发展趋势。目前该领域的研究主要集中在：设计合成有机桥联配体并与金属离子自组装成各类具有纳米孔洞的超分子化合物和一维、二维或三维的金属－有机聚合物,应用结构化学研究手段,研究它们的自组装规律、空间结构、电子结构及其物理化学性能,寻找这两类化合物在生物工程与功能材料等领域中的应用。     

具有纳米孔洞的金属-有机超分子聚合物与功能材料

本文介绍了近几年来一个热门的研究领域-纳米超分子笼和具有纳米孔洞的金属-有机聚合物的研究现状和发展趋势。目前该领域的研究主要集中在:设计合成有机桥联配体并与金属离子自组装成各类具有纳米孔洞的超分子化合物和一维、二维或三维的金属-有机聚合物,应用结构化学研究手段,研究它们的自组装规律、空间结构、电子结构及其物理化学性能,寻找这两类化合物在生物工程与功能材料等领域中的应用。     

超两亲分子:可控组装与解组装

与基于共价键的两亲性分子相对照,超两亲分子系指基于非共价键构筑的两亲分子.基于超分子体系的分子工程学的思想,本文总结了超两亲分子的各种类型,包括小分子型、聚合物型和响应性超两亲分子等,以及组装超两亲分子的各种推动力,如主客体相互作用、基于电荷转移作用和不同分子间的协同作用等.研究表明,超两亲分子的研究既可丰富传统的胶体界面化学,又为高级结构的可控组装提供了新的构筑基元,并为制备功能超分子材料开拓了新的途径.     

表面分子纳米结构构筑的分子工程学

以分子工程学的基本思想为指导,基于对表面分子自组装过程基本原理及规律的深入理解,以功能为导向开展表界面分子纳米结构的定向设计与构筑,发展其在分子器件、单分子科学等领域的应用,是纳米科学与技术研究的一个重要方向。本文结合近年来国内外的工作,概述了表面分子工程学中的研究进展,展望了该领域的研究方向。     

[60]富勒烯的超分子自组装研究进展

超分子自组装是发展超分子电子学的重要途径。随着纳米科学和技术的迅速发展,自组装技术已成功地应用于纳米尺度物质的维数、形貌和功能等的调控。作为构筑分子水平上一维、二维、三维有序功能结构和高有序分子聚集态结构的关键技术,超分子自组装技术有力地推动了具有优良光、电、磁性能的分子材料和纳米功能材料更深层次的研究。本文综述了超分子自组装在富勒烯科学领域的基础研究和应用,特别是对有利于自组织和自组装功能的富勒烯基衍生物的设计与合成、超分子作用力引导的具有特定结构的分子体系的可控自组装、以及富勒烯分子聚集态结构材料的光物理过程、超分子中电子转移和能量转移现象进行了描述;并对卟啉、四硫富瓦烯、碗烯和杯芳烃等一系列富π电子化合物和大环主体分子等包含[60]富勒烯的主体化合物的超分子作用和超分自组装体以及通过氢键、π-π作用、静电力和范德华力和金属配位作用形成的[60]富勒烯超分子自组装体进行了总结,对未来发展进行了展望。     

基于分子纳米粒子的巨型分子

本文聚焦于一类非传统的高分子结构,也即基于分子纳米粒子(或称纳米原子,nano-atoms)的巨型分子(giant molecules)。分子纳米粒子是具有确定化学组成、分子对称性和表面官能团的三维刚性笼状骨架结构。巨型分子是利用分子纳米粒子基元构筑的具有精确结构的高分子。受到蛋白质中结构域概念的启发,我们提出经过表面官能化修饰的分子纳米粒子可以作为合成高分子的结构域和功能域,通过逆功能分析,结合包括点击化学在内的高效化学反应,来实现巨型分子的快速模块化合成、可控组装和功能评估,并利用其中得到的构效关系,更为系统地理解材料的性质和指导材料的进一步优化设计。同时,这种新型高分子也可被看成是尺寸放大的小分子。它的许多有趣的自组装行为和相应小分子既有相似之处,又有截然不同之处。比如,巨型表面活性剂在溶液中能像小分子表面活性剂一样组装成为尾链被拉伸的胶束,在本体中则像嵌段聚合物一样形成纳米相分离的结构。这些组装展现出对于一级化学结构不同寻常的敏感性,并容易形成一些非传统的罕见相态,包括Frank-Kasper相态、在低分子量层状晶体PEO中出现的非整数折叠以及在溶液组装中出现的多级结构。因此,我们认为巨型分子作为功能材料在将来的技术领域中将具有广阔的应用前景。     

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.     

分子纳米技术与金属有机分子纳米体系

基于超分子自组装的分子纳米技术是一种新兴的高新技术。本文从金属矢量操纵的自组装分子纳米体系、自组装的纳米微反应器与超分子催化和自组装金属超分子高分子纳米材料等三个方面评述了分子纳米技术及其在构筑金属有机分子纳米体系中的发展现状 ,进一步阐述了“金属矢量”的概念 ,并首次提出建立“自组装子工具箱” ,探讨了分子纳米技术的发展方向。     

氢键识别超分子聚合物的新进展*

近年来,由于氢键作用对聚合物的热力学性质、微观自组装、结晶及液晶行为的重要影响,氢键识别在超分子聚合物的分子设计与结构控制方面的应用受到广泛关注。本文系统介绍了氢键识别体系的类型与性质,以及分子结构、分子内氢键对氢键识别强度的影响,讨论了羧酸与吡啶间氢键识别体系、与核苷相关的氢键识别体系以及四重氢键识别体系在超分子聚合物中的最新应用,主要介绍了氢键识别超分子聚合物的合成、结构、性质及功能。     

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。     

Crystal engineering: a holistic view

Crystal engineering, the design of molecular solids, is the synthesis of functional solid-state structures from neutral or ionic building blocks, using intermolecular interactions in the design strategy. Hydrogen bonds, coordination bonds, and other less directed interactions define substructural patterns, referred to in the literature as supramolecular synthons and secondary building units. Crystal engineering has considerable overlap with supramolecular chemistry, X-ray crystallography, materials science, and solid-state chemistry and yet it is a distinct discipline in itself. The subject goes beyond the traditional divisions of organic, inorganic, and physical chemistry, and this makes for a very eclectic blend of ideas and techniques. The purpose of this Review is to highlight some current challenges in this rapidly evolving subject. Among the topics discussed are the nature of intermolecular interactions and their role in crystal design, the sometimes diverging perceptions of the geometrical and chemical models for a molecular crystal, the relationship of these models to polymorphism, knowledge-based computational prediction of crystal structures, and efforts at mapping the pathway of the crystallization reaction.     

多孔晶体材料的分子工程学研究

功能无机晶体材料的定向设计与合成是化学及材料科学领域中一项重要的前沿课题。本文介绍了近十几年来我们在多孔晶体材料,主要包括分子筛和金属有机骨架晶体材料的分子工程学研究方面所取得的一些进展。其中包括提出了定向设计具有特殊孔道结构和特殊计量比分子筛多孔骨架结构的计算机方法;在国际上率先建立了分子筛多孔晶体材料合成与结构数据...     

合成生物学展望

近年来,合成生物学快速发展成为一个新兴交叉学科领域,研究重点逐渐由基因线路、简单元件和模块的设计构建转向设计与构建复杂的人工生物系统.本文阐述了合成生物学与化学工程学科的内在联系,并从基因组的人工设计合成与编辑、人工细胞的设计合成、人工合成多细胞体系及其应用等方面展望了未来合成生物学的发展趋势.     

浅谈2016年诺贝尔化学奖:分子机器

2016年诺贝尔化学奖颁给了Jean-Pierre Sauvage、Fraser Stoddart和Ben Feringa,以表彰他们在设计与合成分子机器领域的卓越贡献.分子机器是模拟自然界的生物大分子机器或宏观机器的分子,科学家通过精巧的设计,利用有机合成反应构建这些内部能相对运动的分子,实现从分子层面的精确控制.本次诺贝尔化学奖颁给了尚无实际应用的分子机器,给未来带来了无限可能.     

Toward rational and modular molecular design in soft matter engineering

This essay discusses some preliminary thoughts on the development of a rational and modular approach for molecular design in soft matter engineering and proposes ideas of structural and functional synthons for advanced functional materials. It echoes the Materials Genome Initiative by practicing a tentative retro-functional analysis(RFA) scheme. The importance of hierarchical structures in transferring and amplifying molecular functions into macroscopic properties is recognized and emphasized. According to the role of molecular segments in final materials, there are two types of building blocks: structural synthon and functional synthon. Guided by a specific structure for a desired function, these synthons can be modularly combined in various ways to construct molecular scaffolds. Detailed molecular structures are then deduced, designed and synthesized precisely and modularly. While the assembled structure and property may deviate from the original design, the study may allow further refinement of the molecular design toward the target function. The strategy has been used in the development of soft fullerene materials and other giant molecules. There are a few aspects that are not yet well addressed:(1) function and structure are not fully decoupled and(2) the assembled hierarchical structures are sensitive to secondary interactions and molecular geometries across different length scales. Nevertheless, the RFA approach provides a starting point and an alternative thinking pathway by provoking creativity with considerations from both chemistry and physics. This is particularly useful for engineering soft matters with supramolecular lattice formation, as in giant molecules, where the synthons are relatively independent of each other.     

Molecular Architectonics-guided Design of Biomaterials

The quest for mastering the controlled engineering of dynamic molecular assemblies is the basis of molecular architectonics. The rational use of noncovalent interactions to programme the molecular assemblies allow the construction of diverse molecular and material architectures with novel functional properties and applications. Understanding and controlling the assembly of molecular systems are daunting tasks owing to the complex factors that govern at the molecular level. Molecular architectures depend on the design of functional molecular modules through the judicious selection of functional core and auxiliary units to guide the precise molecular assembly and co-assembly patterns. Biomolecules with built-in information for molecular recognition are the ultimate examples of evolutionary guided molecular recognition systems that define the structure and functions of living organisms. Explicit use of biomolecules as auxiliary units to command the molecular assemblies of functional molecules is an intriguing exercise in the scheme of molecular architectonics. In this minireview, we discuss the implementation of the principles of molecular architectonics for the development of novel biomaterials with functional properties and applications ranging from sensing, drug delivery to neurogeneration and tissue engineering. We present the molecular designs pioneered by our group owing to the requirement and scope of the article while acknowledging the designs pursued by several research groups that befit the concept.     

Molecular and Crystal Magnetic Engineering of Polymetallic Coupling System: From Magnetic Molecules to Molecular Magnets

One of the main challenges in the field of molecular materials is the design of molecular ferromagnets. General design strategy includes two steps, that is molecular magnetic engineering and crystal magnetic engineering. The first step is the synthesis of ferromagnetically coupled polymetallic systems. The second step is the assembly of polymetallic systems with muti‐dimensional structure and exhibiting a ferromagnetic transition. This paper summarized the strategies of molecular design and crystal engineering allowed to obtain such systems and our efforts in the fields of molecular magnetism and molecular‐based magnets.     

Metabolic engineering--a genetic toolbox for small molecule organic synthesis

Metabolic engineering is an emerging field that exploits biosynthetic machinery as a means to genetically design small molecule production within heterologous host organisms. Molecular design and synthesis with biological tools has lagged behind total synthesis technology for about seventy-five years and owes its existence to relatively new molecular biology techniques. Here the field of metabolic engineering is explained as a comparison to total organic synthesis, including the sequence of scientific events leading up to successful implementation and future goals in the field. It is expected that metabolic engineering will take a place alongside traditional organic synthesis as a powerful means to design and create small organic molecules.     

Frontier Molecular Orbital Engineering: Constructing Highly Efficient Narrowband Organic Electroluminescent Materials

It is of great strategic significance to develop highly efficient narrowband organic electroluminescent materials that can be utilized to manufacture ultra-high-definition (UHD) displays and meet or approach the requirements of Broadcast Television 2020 (B.T.2020) color gamut standards. This motif poses challenges for molecular design and synthesis, especially for developing generality, diversity, scalability, and robustness of molecular structures. The emergence of multiple resonance thermally activated delayed fluorescence (MR-TADF) emitters has ingeniously solved the problems and demonstrated bright application prospects in the field of UHD displays, sparking a research boom. This Minireview summarizes the research endeavors of narrowband organic electroluminescent materials, with emphasis on the tremendous contribution of frontier molecular orbital engineering (FMOE) strategy. It combines the outstanding advantages of MR framework and donor-acceptor (D−A) structure, and can achieve red-shift and narrowband emission simultaneously, which is of great significance in the development of long-wavelength narrowband emitters with emission maxima especially exceeding 500 nm. We hope that this Minireview would provide some inspiration for what could transpire in the future.     

Molecular Engineering of Metal Alkoxides for Solution Phase Synthesis of High-Tech Metal Oxide Nanomaterials

The ‘bottom-up’ synthesis of inorganic nanomaterials with precision at the atomic/molecular level offers many opportunities for the design and improvement of the nanomaterials for various applications. Molecular engineering during soft chemical processing for the synthesis of functional nanomaterials enables the desired chemical and physical properties of the precursors, such as solubility or volatility, clean decomposition, control of stoichiometry for multimetallic species to name a few, and leads to easy control of uniform particle size distribution, stoichiometry…. This Minireview illustrates some important aspects of the molecular engineering in light of some recent developments from the molecular synthesis of nanomaterials involving non-silicon metal alkoxide systems for high-tech applications.