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.     

旋转型单分子机器

分子机器是一种分子水平上的机器,它是一类通过外部刺激（如化学能、电能、光照等）将能量转化为可控运动的分子器件。由于人工分子机器在纳米科技领域的应用越来越普遍,已经引起人们的广泛关注。人工合成的分子机器在模拟机器运动时主要有线性运动和旋转运动两种基本运动方式,本文重点介绍了几种旋转型的单分子机器,包括分子齿轮、分子转门、分子闸和分子棘轮、分子马达等。这类分子机器的结构特点是由轴、转子和定子三部分组成,其运动特点是转子通过轴围绕定子进行双向或单向旋转。本文在介绍这类分子转子的同时,简单讨论了其设计理念和在溶液状态下所表现出的动力学行为,同时还展望了分子转子和分子马达的发展前景和面临的挑战。     

基于24-冠-8大环化合物构筑的人工分子器件和分子机器

简要阐述了分子器件和分子机器的相关概念,按照调控方式分类综述了基于24冠8的准轮烷、轮烷和索烃大环化合物构筑的分子器件和分子机器等在超分子领域的研究进展并对研究前景作了展望.     

具有分子机器、分子开关功能的自组装超分子体系

本文介绍了具有分子梭或分子开关性质的新型轮烷和索烃超分子以及具有分子机器功能的其它类型化学和生物分子的国际研究最新动态。     

溶液酸碱度调控的分子机器与分子开关

人工分子机器按其能量驱动方式可以分为化学驱动、电化学驱动和光驱动三类.溶液酸碱度调控(p H调控)驱动属于化学驱动的一种,其基本原理是通过加入酸碱性化合物调节溶液的酸碱度从而改变体系中各种组分的化学性质,实现分子机器的运动.利用溶液酸碱度调控已成为人工组装分子机器最常用的能量供应方式之一.对溶液酸碱度调控的分子机器和分子开关进行了详细综述,分别总结了基于冠醚和其他大环主体的溶液酸碱度调控分子机器与分子开关的制备及酸碱调控方法,并展望了它们在信息存储、电子器件及药物传递等领域中的应用.     

分子机器的回顾与展望——2016年诺贝尔化学奖简介

1983年,让-皮埃尔·索瓦日将2个环形分子连接在一起形成链,并将其命名为索烃。2个互锁的环可以彼此相对移动,这是第一个分子机器的雏形。1991年,詹姆斯·弗雷泽·斯托达特制备了一种轮烷,并展示了分子轴上的分子环能够沿着轴移动。基于轮烷,他设计研发了分子电梯和分子肌肉等分子机器。1999年,伯纳德·费林加成为第一个开发分子马达的人,并且根据它设计制造出分子汽车。基于上述3位科学家在分子机器研究领域的杰出贡献,他们分享了2016年诺贝尔化学奖。     

基于环糊精和富勒烯偶联体系的新型分子机器*

超分子化学是当前研究热点领域之一,利用超分子体系来模拟宏观过程,进而将宏观机器纳米尺寸化更是备受瞩目。环糊精与富勒烯各自具有非常优良的性质,而基于环糊精和富勒烯偶联体系的新型“加工型”分子机器,与传统的“运动型”分子机器不同,不是强调分子间与分子内的位置变化,而是强调对特定客体分子“识别-捕捉-加工-释放”的过程。这种新型的分子机器将为包括生物酶模拟、生物过程研究、光能固定等领域的研究提供新思路。本文综述了环糊精和富勒烯偶联体系的研究进展：首先介绍了不同种类的环糊精和富勒烯偶联体系的合成,包括合成思路、步骤方法及表征;然后叙述了此体系的应用领域,包括分子识别、DNA裂解、电子传输等方面;最后结合现阶段的研究状况,对其发展前景进行了展望。     

分子机器的设计与合成——2016年诺贝尔化学奖解读

法国斯特拉斯堡大学的让-皮埃尔·索维奇（Jean-Pierre Sauvage）和美国西北大学的弗雷泽·斯托达特（J.Fraser Stoddart）利用机械键设计了锁链分子机器--索烃和轮烷,荷兰格罗宁根大学的伯纳德·费林加（Bernard L.Feringa）基于不饱和键合成分子马达实现了分子机器的单向旋转,3位科学家因“设计、合成分子机器”而被授予2016年诺贝尔化学奖。     

功能分子体系的设计与构建

功能分子在外界刺激(酸、碱、光等)的诱导下能发生分子构型、构象变化,并引起相应的物理化学性质变化,或能实现特定的功能,例如具有方向性的电子、能量转移,对分子/离子的识别能力的调控,以及光/电开关功能.功能分子的设计是分子材料科学研究的基础.作者将就我们在分子机器,化学传感器等功能分子的设计合成与性质研究领域取得的进展作一总结,并对未来的发展进行了描述.     

酸碱驱动的分子机器研究与应用

酸碱驱动的分子机器是化学驱动的分子机器的重要组成部分,是构筑分子机器的研究热点。近年来,酸碱驱动的分子机器理论研究水平不断提高。在此基础上,围绕构筑功能性、实用型的分子机器的研究成果也不断出现。目前,酸碱度驱动的分子机器在超分子凝胶、超分子催化、药物载体、超分子阀门、超分子聚合物等方面表现出很好的应用价值。本文以分子机器的酸碱驱动力为主题,分别从准轮烷、轮烷及索烃等角度,综述了近年来分子机器在合成方面的研究进展,并对酸碱度驱动的分子机器的应用实例进行总结,最后对酸碱驱动的分子机器的完善空间和发展趋势进行了展望。     

Development of photoresponsive supramolecular machines inspired by biological molecular systems

In the growing research area on molecular machinery, light is one of the attractive and useful stimuli source to operate synthetic molecular machines, since light allows selective operation of photoresponsive moieties without additives. We have proposed a new approach to design of photoresponsive molecular machines by interlocking mechanical motions between photoresponsive and movable units through covalent and non-covalent bonds. This approach is inspired by biological molecular machines consisting of multiple protein subunits, and potentially useful for construction of giant mechanical systems. In this review, we will introduce our concepts of the molecular design with several successful examples as well as their applications for controlling chemical events, and also glance at a semi-biological molecular machine controllable by light, which reveals a potential of biological systems for development of elaborate molecular devices.     

分子组装机器：纳米工厂

Molecular machines have attracted significant attentions as one of the most promising aspects of chemistry for their potential applications ever since receiving the 2016 Nobel Prize in Chemistry. The molecular assembler, also called the nanofactory, is a novel type of molecular machines that are capable of controlling the chemical reactions precisely at the microscopic level. As an analog to the macroscopic factories, nanofactories are comprised of a "transporting" part, the molecular walkers, and an "assembling" part, the molecular robotic arms. In this review, we provide a brief introduction of the research progress in recent years together with analysis on the principles of designing, constructing and operating molecular assemblers. We also summarize the prospects and challenges in the research area of molecular assemblers.     

Nano Trek Beyond: Driving Nanocars/Molecular Machines at Interfaces

In 2016, the Nobel Prize in Chemistry was awarded for pioneering work on molecular machines. Half a year later, in Toulouse, the first molecular car race, a “nanocar race”, was held by using the tip of a scanning tunneling microscope as an electrical remote control. In this Focus Review, we discuss the current state‐of‐the‐art in research on molecular machines at interfaces. In the first section, we briefly explain the science behind the nanocar race, followed by a selection of recent examples of controlling molecules on surfaces. Finally, motion synchronization and the functions of molecular machines at liquid interfaces are discussed. This new concept of molecular tuning at interfaces is also introduced as a method for the continuous modification and optimization of molecular structure for target functions.     

Molecular machines as a driving force of progress in modern post-industrial society

The review considers main advances achieved in recent years in a fairly old and simultaneously modern field of research, controlled motion at the molecular level and its practical transformation in the form of synthetic molecular machines and devices. The basic principles of the design and controlled linear and rotational motion in such molecular systems and various useful functions potentially inherent in synthetic molecular machines have been discussed. Examples of already implemented molecular rotors, shuttles, switches, transporters, and muscles are given. Finally, immediate and more distant prospects for the development of this fascinating and very important field of nanotechnology are presented.     

功能大分子金属轮烷和索烃的研究进展

金属轮烷和金属索烃是通过在轮烷和索烃中引入金属离子或金属配合物而制得的,它们不仅结构特殊,而且具有许多特殊的性质,因此受到化学家们的广泛关注。本文综述了近几年来金属轮烷和金属索烃在分子机器、分子开关、仿生物质、分子材料等方面的应用及研究进展,并对该领域的前景进行了展望。     

Artificial Molecular Machines

The miniaturization of components used in the construction of working devices is being pursued currently by the large-downward (top-down) fabrication. This approach, however, which obliges solid-state physicists and electronic engineers to manipulate progressively smaller and smaller pieces of matter, has its intrinsic limitations. An alternative approach is a small-upward (bottom-up) one, starting from the smallest compositions of matter that have distinct shapes and unique properties-namely molecules. In the context of this particular challenge, chemists have been extending the concept of a macroscopic machine to the molecular level. A molecular-level machine can be defined as an assembly of a distinct number of molecular components that are designed to perform machinelike movements (output) as a result of an appropriate external stimulation (input). In common with their macroscopic counterparts, a molecular machine is characterized by 1) the kind of energy input supplied to make it work, 2) the nature of the movements of its component parts, 3) the way in which its operation can be monitored and controlled, 4) the ability to make it repeat its operation in a cyclic fashion, 5) the timescale needed to complete a full cycle of movements, and 6) the purpose of its operation. Undoubtedly, the best energy inputs to make molecular machines work are photons or electrons. Indeed, with appropriately chosen photochemically and electrochemically driven reactions, it is possible to design and synthesize molecular machines that do work. Moreover, the dramatic increase in our fundamental understanding of self-assembly and self-organizational processes in chemical synthesis has aided and abetted the construction of artificial molecular machines through the development of new methods of noncovalent synthesis and the emergence of supramolecular assistance to covalent synthesis as a uniquely powerful synthetic tool. The aim of this review is to present a unified view of the field of molecular machines by focusing on past achievements, present limitations, and future perspectives. After analyzing a few important examples of natural molecular machines, the most significant developments in the field of artificial molecular machines are highlighted. The systems reviewed include 1) chemical rotors, 2) photochemically and electrochemically induced molecular (conformational) rearrangements, and 3) chemically, photochemically, and electrochemically controllable (co-conformational) motions in interlocked molecules (catenanes and rotaxanes), as well as in coordination and supramolecular complexes, including pseudorotaxanes. Artificial molecular machines based on biomolecules and interfacing artificial molecular machines with surfaces and solid supports are amongst some of the cutting-edge topics featured in this review. The extension of the concept of a machine to the molecular level is of interest not only for the sake of basic research, but also for the growth of nanoscience and the subsequent development of nanotechnology.     

Molecular machines operated by light

The bottom-up construction and operation of machines and motors of molecular size is a topic of great interest in nanoscience, and a fascinating challenge of nanotechnology. Researchers in this field are stimulated and inspired by the outstanding progress of molecular biology that has begun to reveal the secrets of the natural nanomachines which constitute the material base of life. Like their macroscopic counterparts, nanoscale machines need energy to operate. Most molecular motors of the biological world are fueled by chemical reactions, but research in the last fifteen years has demonstrated that light energy can be used to power nanomachines by exploiting photochemical processes in appropriately designed artificial systems. As a matter of fact, light excitation exhibits several advantages with regard to the operation of the machine, and can also be used to monitor its state through spectroscopic methods. In this review we will illustrate the design principles at the basis of photochemically driven molecular machines, and we will describe a few examples based on rotaxane-type structures investigated in our laboratories.      

Applied Aspects of Organic Photochemistry

The results of applied studies on organic photochemistry in the basic areas of research: solar energy storage and conversion, atmospheric photochemistry, medicine photochemistry and biophotochemistry, photoprocessing, light-sensitive recording media, photoswitches, and photocontrolled molecular machines, are summarized.     

Operation of micro and molecular machines: a new concept with its origins in interface science

A landmark accomplishment of nanotechnology would be successful fabrication of ultrasmall machines that can work like tweezers, motors, or even computing devices. Now we must consider how operation of micro- and molecular machines might be implemented for a wide range of applications. If these machines function only under limited conditions and/or require specialized apparatus then they are useless for practical applications. Therefore, it is important to carefully consider the access of functionality of the molecular or nanoscale systems by conventional stimuli at the macroscopic level. In this perspective, we will outline the position of micro- and molecular machines in current science and technology. Most of these machines are operated by light irradiation, application of electrical or magnetic fields, chemical reactions, and thermal fluctuations, which cannot always be applied in remote machine operation. We also propose strategies for molecular machine operation using the most conventional of stimuli, that of macroscopic mechanical force, achieved through mechanical operation of molecular machines located at an air-water interface. The crucial roles of the characteristics of an interfacial environment, i.e. connection between macroscopic dimension and nanoscopic function, and contact of media with different dielectric natures, are also described.