Insulated Molecular Wires: Dendritic Encapsulation of Poly(triacetylene) Oligomers,Attempted Dendritic Stabilization of Novel Poly(pentaacetylene) Oligomers,and an Organometallic Approach to Dendritic Rods

Multinanometer‐long end‐capped poly(triacetylene) (PTA) and poly(pentaacetylene) (PPA) oligomers with dendritic side chains were synthesized as insulated molecular wires. PTA Oligomers with laterally appended Fréchet‐type dendrons of first to third generation were prepared by attaching the dendrons ( 8 , 13 , and 17 , respectively, Scheme 1) to (E)‐enediyne 18 by a Mitsunobu reaction and subsequent Glaser‐Hay oligomerization under end‐capping conditions (Scheme 2). Whereas first‐generation oligomers up to the pentamer were isolated ( 1a – e ), for reasons of steric overcrowding, only oligomers up to the trimer ( 2a – c ) were formed at the second‐generation level, and only the end‐capped monomer and dimer ( 3a , b ) were isolated at the third‐generation level. By repetitive sequences of hydrosilylation (with the Karstedt catalyst), followed by allylation or vinylation, a series of carbosilane dendrons were also prepared (Schemes 3 and 4). Attachment of the second‐generation wedge 40 to (E)‐enediyne 18 , followed by deprotection and subsequent end‐capping Hay oligomerization, provided PTA oligomers 4a – d with lateral carbosilane dendrons (Scheme 5). UV/VIS Studies (Figs. 5 – 10) demonstrated that the insulating dendritic layers did not alter the electronic characteristics of the PTA backbone, even at the higher‐generation levels. Despite distortion from planarity due to the bulky dendritic wedges, no loss of π‐electron conjugation along the PTA backbone was detected. A surprising (E)→(Z) isomerization of the diethynylethene (DEE) core in the third generation derivative 3a was observed, possibly photosensitized by the bulky Fréchet‐type dendritic wedge. Electrochemical investigations by steady‐state voltammetry and cyclic voltammetry showed that the first reduction potential of the PTA oligomer with Fréchet‐type dendrons is shifted to more negative values as the dendritic coverage increases. With compounds 5a – c , the first oligomers with a poly(pentaacetylene) backbone were obtained by oxidative Hay oligomerization under end‐capping conditions (Scheme 6). The synthesis of dendritic PPA oligomers by oxidative coupling of (E)‐enetetrayne 60 under end‐capping conditions provided oligomers 61a – d , which were formed as mixtures of stereoisomers due to unexpected thermal (E)→(Z) isomerization (Scheme 8). In another novel approach towards dendritic encapsulation of molecular wires with a Pt‐bridged tetraethynylethene (TEE) oligomeric backbone, the trans‐dichloroplatinum(II) complex trans‐ 67 with dendritic phosphane ligands (Fig. 14) was coupled under Hagihara conditions to mono‐deprotected 69 under formation of the extended monomer 65 (Scheme 12). Again, an unexpected thermal (E)→(Z) isomerization, possibly induced by steric strain between TEE moieties and dendritic phosphane ligands in the unstable complex, led to the isolation of 65 as an isomeric mixture only.     

Proteins in Countryclub-Like Jails:Encapsulation of Enzymes in Nanoporous Materials

A popular method for enzyme immobilization is formation of covalent bonds between enzymes and a solid support, which often alters the enzymatic activities. Recently, various enzymes have been entrapped in inorganic oxides such as silica for biocatalysis and biosensor applications through conventional sol-gel process. However, because of the microporous nature (i.e. pore diameter of 1.5-2 nm or less) of conventional sol-gels, the activities of enzymes are hindered by low diffusion rates of substrate molecules and poor accessibility of enzymes inside the materials.     

Sol–Gel Encapsulation of Molecules to Generate Functional Optical Materials: A Molecular Programming Approach

The extraordinary opportunities offered by integrating solution chemistry of molecular entities with the solid-state nature of the gel provide the basis for designing a number of novel molecular materials. Herein, we present a strategy based on encapsulation of suitable response active species to impart useful optical properties to sol–gel glasses. The basic concept of this molecular programming approach is based on deliberate incorporation of response-active species in the silica gel framework to elicit specific optical responses. Design of molecular materials for device applications depends on selection of molecules which exhibit well-defined electronic or optical response, and assembly of these molecular components into a geometric structure that retains the rigidity, addressability, and stability necessary for practical applications. The approach is based on using molecules as active species and sol–gel glass as structural matrix in which the molecules are selectively integrated. A designer approach that employs specific molecules for generating optical signals is described. As such the properties of these silica-based glasses can be tuned by varying the composition of encapsulated species. These modified glasses exhibit substantially altered optical properties as compared to pristine silica sol–gels. The optical response of these materials provide initial examples toward designing novel materials whose optical and/or photonic responses can be modulated by structural integration of specific dopant entities.     

Dendritic polymers: from efficient catalysis to drug delivery

Dendritic polymers constitute an intriguing class of macromolecules that offer tremendous potential in designing new materaisl for applications in areas such as catalysis and small molecule loading and delivery. Synthesis of a variety of dendritic polymers using a simple and highly versatile synthetic methodology has enabled us to carry out a detailed investigation of dendritic effects in transition metal catalyzed organic transformations. Small dye molecules such as p-nitroaninline and DR1 could be loaded into the intrinsic cavities of the backbone of 3,5-dihydroxybenzyl alcohol based dendrimers, leading to a change in physical properties of both the dye and the dendrimer. We are also exploring the use of dendrimers as templates to prepare network carriers containing cavities of predetermined size and disposition.     

Molecular Encapsulation of Half-Sandwich Complexes of Iron with Cyclodextrins: New Laminar Materials

The treatment of - and -cyclodextrins with the half-sandwich complexes of iron afford the inclusion compounds CpFe(L₂)XCD ( and ) (X = Cl, I; L = CO; L₂ = dppe, dppe = (Ph)₂P(CH₂)₂P(Ph)₂), [CpFe(L₂)L-]PF₆CD ( and ) L- neutral donor ligands and[(Cp(dppe)Fe)₂-µ-CN]PF₆2CD ( and ). The inclusion compounds [Cp(dppe)Fe-NCCH₃]PF₆-CD and [Cp(dppe)Fe-(¹-dppm)]PF₆-CD have a laminar structure. The - and -cyclodextrin encapsulation effect on the electro-oxidation of the binuclear complex was studied using cyclic voltammetry.The electron-transfer reactions associated with the oxidation of the two different N-bonded and C-bonded organometallic fragments are substantially affected by and encapsulation.     

应用研究式学习提高理论课程教学的质量——以高分子材料课程为例

高分子材料课程是高分子材料与工程专业的核心骨干课程,但其庞杂的知识体系给课程讲述带来了诸多困难。为了更好地完成课程教学目标,实现学生思维能力与科研素质的全面培养,在教学过程中大量采用了互动式、讨论式和研究式教学方法。其中,研究式学习方式是将4~5 人分为一个学习小组,由学生自主遴选生活中常见的高分子材料品类,再与教师沟通协商后确定材料品类和分组,并进行一系列探究的教学模式。在完成该学习任务时,应先通过课程知识、产品说明、外观等初步分析判断材料的主要化学成分;进而结合现代检测分析方法或自制研究方法,鉴定材料的化学结构;再针对材料的应用领域,检测分析材料的物理结构、性能和功能;最后,整理所得数据,并结合文献对结果进行分析和讨论。通过目标驱动的方式引导学生去自主完成课题研究,极大地调动了学生参与的积极性,提高了全体学生参与课程讨论和学习的热情,进一步拓展了学生的知识面,取得了较好的教学效果。     

新型石墨烯基LED器件：从生长机理到器件特性

III族氮化物因具有禁带宽度大、击穿电压高、电子饱和漂移速度大、稳定性高等优异特性而广泛应用在发光二极管(LED)、激光器以及高频器件中。目前III族氮化物薄膜通常是异质外延生长在蓝宝石衬底表面,但是由于蓝宝石与III族氮化物之间存在较大的晶格失配与热失配,使得外延生长的III族氮化物内部存在较大的应力与较高的位错密度,严重影响了器件性能;与此同时,蓝宝石衬底热导率差,限制了其在大功率器件方面的应用。近年来研究发现,石墨烯作为外延生长缓冲层,能够有效解决蓝宝石衬底与外延III族氮化物薄膜之间由于晶格失配和热失配导致的高应力与高位错密度等问题,进而获得了高品质薄膜,并提升了器件的性能。本文综述了石墨烯/蓝宝石衬底上III族氮化物生长与LED器件构筑的研究现状,着重介绍了本课题组提出的一种新型外延衬底—石墨烯/蓝宝石衬底的特点,阐明了III族氮化物在该新型衬底上的生长机理,总结了其对III族氮化物质量提升的作用,并对其发展前景进行了展望。     

有机电致磷光材料的分子设计：从主体材料到客体材料

有机电致磷光器件的设计和利用，可以突破由三线态激子跃迁自旋禁阻引起的有机电致荧光器件量子效率的限制。本文综述了有机电致磷光器件和材料的研究进展，主要介绍了主体材料和客体材料的研究现状，特别是蓝光磷光器件主客体材料的研究情况。     

Prospects of Materials Science. From crystalline to amorphous solids

A survey of materials science through our experiences shows that our knowledge of amorphous solids is quite poor compared with that of crystalline solids. Most pure substances can be obtained, in principle, as crystalline as well as non-crystalline states by physical and chemical methods. Destruction of the three-dimensional periodicity in crystalline substances will produce novel properties which cannot be anticipated from knowledge of crystal sciences. One direction of materials science in the coming century will surely be a new realm of amorphous condensed matter science. This revised version was published online in August 2006 with corrections to the Cover Date.     

学史明理 学史增信*——以“奇妙的二氧化碳”教学中的科学史实情境应用为例

以人类认识二氧化碳知识的形成与发展史实为问题线索和教学主线,进行教学情境设计,探索利用科学史知识,从宏观认识上提升学生对二氧化碳性质的理解,促进学生初步建立学习常见物质的基本思路和方法的有效路径,为初中化学教师教学提供参考借鉴。     

碳基介熵材料:理论与实验

富碳型材料,包括纯碳材料的各种同素异形体、碳基骨架的稠环芳香分子、聚合物、框架材料等,已成为当今材料领域最重要的研究领域之一.在这些研究当中,很大一部分工作都是研究材料本身的结构与性质,而忽略了这些材料之间的内在联系.课本中的很多概念,如同分异构体、同素异形体和拓扑缺陷,已经无法用于深入理解种类和数量繁多的富碳型材料之间的构效关系.这就使得通过改变已知材料的有限结构来调控材料的性质变得工作重复而繁重,且基础理解受限于研究个体上.作者将从材料"熵"的概念入手,尝试理解富碳型材料之间熵的相对高低,并建议基于"介熵"的认识开发新型富碳型材料、开发新型介熵富碳型材料的全新性质.基于对具体的不同的新型富碳型材料的讨论,将"介熵"这一概念引入到同素异形体、同分异构体以及广泛存在于碳材料中的拓扑缺陷的理解上.类似富碳型材料的关系不再模糊地停留在几何结构层面上,为今后介熵富碳型材料及其他介熵材料的开发提供参考.     

二维半导体材料与器件——从传统二维光电材料到石墨炔

近年来,二维半导体材料由于其独特的材料结构和电子输运特性得到了科学界的广泛关注,被应用于光电器件、催化和生物传感器等领域。本文系统概述了传统二维材料以及新兴二维材料石墨炔的发现和发展历程。重点聚焦在二维材料在光探测器领域中的应用,探讨了不同二维材料体系及器件结构对光探测器性能的影响;并详细介绍了新兴二维材料——石墨炔,及其合成和应用。展望了传统二维材料及石墨炔在光电转换器件应用中所面临的机遇和挑战。     

二维半导体材料与器件——从传统二维光电材料到石墨炔

近年来,二维半导体材料由于其独特的材料结构和电子输运特性得到了科学界的广泛关注,被应用于光电器件、催化和生物传感器等领域。本文系统概述了传统二维材料以及新兴二维材料石墨炔的发现和发展历程。重点聚焦在二维材料在光探测器领域中的应用,探讨了不同二维材料体系及器件结构对光探测器性能的影响;并详细介绍了新兴二维材料——石墨炔,及其合成和应用。展望了传统二维材料及石墨炔在光电转换器件的应用中所面临的机遇和挑战。     

Natural products synthesis: enabling tools to penetrate Nature's secrets of biogenesis and biomechanism

Selected examples from our laboratory of how synthetic technology platforms developed for the total synthesis of several disparate families of natural products was harnessed to penetrate biomechanistic and/or biosynthetic queries is discussed. Unexpected discoveries of biomechanistic reactivity and/or penetrating the biogenesis of naturally occurring substances were made possible through access to substances available only through chemical synthesis. Hypothesis-driven total synthesis programs are emerging as very useful conceptual templates for penetrating and exploiting the inherent reactivity of biologically active natural substances. In many instances, new enabling synthetic technologies were required to be developed. The examples demonstrate the often untapped richness of complex molecule synthesis to provide powerful tools to understand, manipulate and exploit Nature's vast and creative palette of secondary metabolites.     

Self‐Assembled Selenium Monolayers: From Nanotechnology to Materials Science and Adaptive Catalysis

Self‐assembled monolayers (SAMs) of selenium have emerged into a rapidly developing field of nanotechnology with several promising opportunities in materials chemistry and catalysis. Comparison between sulfur‐based self‐assembled monolayers and newly developed selenium‐based monolayers reveal outstanding complimentary features on surface chemistry and highlighted the key role of the headgroup element. Diverse structural properties and reactivity of organosulfur and organoselenium groups on the surface provide flexible frameworks to create new generations of materials and adaptive catalysts with unprecedented selectivity. Important practical utility of adaptive catalytic systems deals with development of sustainable technologies and industrial processes based on natural resources. Independent development of nanotechnology, materials science and catalysis has led to the discovery of common fundamental principles of the surface chemistry of chalcogen compounds.     

小实验大道理 ——从热缩片小制品DIY看高分子材料的熵致形变

A little experiment concerning the pyrocondensation materials was introduced in this paper. The aim was to help the public understand the principles of entropy induced deformation of polymer materials.