有机功能材料薄膜与器件

具有光、电、磁物理功能的有机材料的出现促进新思想、新概念、新材料的发展；有机功能材料的电子状态、导电机理以及杂质的影响完全有别于无机金属和半导体，因此，在深入探索结构与功能的关系的基础上，有可能开展分子、聚集态以及器件设计的研究。若与有机化合物的结构多样化，良好的加工性、成膜和成纤性等特点相结合，有可能实现无机电子材料所难兼具的电子行为。进而实现“分子电路”的设想。这里，我们对有机功能材料的基本概念、种类，功能材料薄膜的沉积、器件的构筑，分子电子学和分子器件的概念作了一个较为全面的介绍。     

固态表面的分子纳米构筑与功能器件

分子纳米构筑与功能器件研制是极有意义的研究课题。本文总结了利用分子自组装构筑多层异质纳米结构、有机金属卟啉络合物的隧道电子诱导分子发光和轨道媒介分离作用、生物分子DNA的创造设计和微观结构、光电材料的本征性集成与功能器件研制。重点介绍了作者在相关课题研究方面所做的工作和最新研究结果。     

介孔有机膦酸盐材料的合成及应用研究进展

介孔有机膦酸盐材料作为一类新型的有机-无机杂化材料，凭借其独特的结构可剪裁性和丰富的化学表面性质在催化、分离与吸附、生物分子的固定等诸多领域都具有巨大的潜在应用价值，因此近几年来越来越受到人们的关注。本文系统地概述了介孔有机膦酸盐材料的发展历程及其合成和应用研究的发展现状，并对这种新型杂化介孔材料的应用前景进行了展望。     

原位法制备无机纳米粒子/聚合物复合材料

纳米粒子的尺寸介于体相材料和分子之间, 具有许多独特的物理和化学性质, 近年来在催化、光电子以及生物等领域得到广泛的关注. 为了使纳米粒子更好的展现它们特有的功能, 将其与聚合物复合是行之有效的方法, 这不仅可以稳定纳米粒子, 还可以实现纳米粒子与聚合物之间功能的集成. 但是, 这一思想的实现在很大程度上依赖于纳米粒子与聚合物之间的相容性, 以及如何调节纳米粒子与聚合物之间的相互作用, 使我们得到预期的功能. 因此, 人们发展了许多将纳米粒子复合到聚合物中的方法. 本文主要阐述了近几年我们课题组把原位法和其他方法有机结合, 实现纳米粒子与聚合物的复合, 从而制备了具有不同功能的一维、二维乃至体相纳米粒子/聚合物复合材料. 我们所建立的这些方法最突出的特点是纳米粒子与聚合物之间具有很好的相容性, 可以确保其在聚合物中的均匀分散, 而且聚合物网络结构的存在使纳米粒子更加稳定, 对于更好的体现其功能具有重要意义.     

功能化石墨烯的应用研究新进展

石墨烯拥有独特的二维纳米结构,并显现出了超强的机械性能和优异的电学性能.尽管它的研究历史很短暂,但已经在很多领域内展现出了极高的应用价值.为了使石墨烯在应用过程中能够很好的分散,通常需要对其进行功能化.石墨烯功能化的方法大体可分为2种,即基于共价键的共价键功能化法和依靠分子间作用力的非共价键功能化法.本文综述了功能化石墨烯(FGs)在光电材料、传感和探测器、储能材料、催化、纳米增强复合物及其他一些领域内的最新应用研究进展,并展望了未来FGs应用研究的发展趋势.     

超临界流体技术制备纳米材料进展

目前,已经有多种与超临界流体有关的技术用于纳米材料的制备。在这些技术方法中,超临界流体可以作为介质,也可以直接作为反应物来参与制备过程。超临界流体技术广泛应用于制备无机材料、有机材料、高分子聚合物、医药、电子等方面纳米级材料。本文概述了超临界流体制备纳米材料的研究和应用情况。     

可见光驱动Methanosarcina barkeri-天然碳基半导体产甲烷性能及机制

利用半人工光合系统(非光合微生物-纳米半导体生物杂化体系)将二氧化碳转化为高热值的甲烷有助于缓解全球温室效应和能源危机.作为生物杂化体系的关键组分,纳米半导体颗粒的结构及性质显著影响生物杂化体系的性能.本研究以油菜花粉为原料,成功构建Methanosarcina barkeri-天然碳基半导体生物杂化体系(M. barkeriNCS),并将其应用于二氧化碳还原产甲烷过程.结果表明,所制备的天然碳基半导体具有可见光响应好、孔体积大等优势.在可见光(1.0±0.2 mW/cm2)照射下, M. barkeri-NCS生物杂化体系具有良好的光电性能,其甲烷产量最高可达51±4.5μmol/g.实时荧光定量多聚合酶链式反应结果进一步显示, M. barkeri膜结合氢酶和细胞色素相关基因表达显著上调,尤其是EchB(2.47±0.25倍)和VhtC(2.83±0.15倍),这表明这些基因在生物杂化体系光生电子传递-捕获-利用过程中起着关键作用.该研究结果有望为构建高效的半人工光合系统提供理论支撑.     

TiO_2纳米阵列的制备、表面修饰及其在钙钛矿太阳电池中的应用

一维TiO_2纳米阵列具有直接的电子传输通道,在太阳电池中作为电子传导材料引起了广泛的关注.以水热法制备的金红石相TiO_2纳米阵列作为有机无机杂化钙钛矿太阳电池电子传导支架,系统研究了TiO_2致密层引入对纳米阵列生长和组装器件光电性能的影响;考察了TiO_2纳米棒棒长和TiCl_4水浴处理等对纳米阵列微结构和组装电池光电性能的影响.致密层的引入有利于获得垂直取向TiO_2纳米阵列,纳米棒棒长的优化有利于光生载流子的快速分离和传导,而采用TiCl_4水浴处理TiO_2纳米阵列,不仅增大了纳米阵列的比表面积,有利于吸附更多的钙钛矿晶体和提升电池对光的俘获,同时TiCl_4水浴处理产生的小纳米颗粒有助于填补钙钛矿晶体与纳米阵列间的缝隙,促进更好的界面接触,从而抑制载流子传导过程中的复合,提升电池性能.在引入TiO_2致密层后,进一步采用0.1 mol/L TiCl_4处理的TiO_2纳米阵列组装的电池展现最优的光电性能,其短路电流密度、开路电压、填充因子分别达到22.88 mA/cm~2,1.04 V和63.58%,电池的能量转化效率达到15.11%.     

功能纳米材料-金属及其化合物纳米粒子功能化的胶体微球的合成

由于金属及其化合物纳米粒子具有独特的光学、电子、催化等性质，其成为了纳米材料领域研究的热点。但它们容易发生聚集、表面易被氧化等缺点也大大限制了其应用范围：而通过胶体粒子来稳定这些纳米粒子不仅可以大大提高金属及其化合物纳米粒子的分散性和稳定性，同时也可以利用胶体微球自组装的特性以及特殊的核壳结构来实现这些纳米粒子的规则排列和复合结构的构筑。本文介绍了国内外金属纳米粒子及其化合物功能化的胶体微球的制备的最新进展，并在最后就其发展作了展望。     

激光冲击复合强化机理及在航空发动机部件上的应用研究

针对激光冲击强化在航空发动机高温部件、薄叶片和叶片榫槽/榫齿等复杂部件(位)应用的问题,系统开展了激光冲击表面纳米化方面的研究.本文在总结多种航空发动机金属材料激光冲击表面纳米化表征、原理、热稳定性研究的基础上,提出了基于表面纳米化和残余压应力的激光冲击复合强化机理,进而提高了激光冲击强化在高温部件上使用温度,并介绍了薄壁结构、榫槽/榫齿等特殊部件(位)激光冲击强化工程应用的情况.激光冲击表面纳米化及其复合强化机理的研究工作,拓宽了激光冲击强化的研究领域和应用范围.     

Nicotinamide/nicotinic acid mononucleotide adenylyltransferase, new insights into an ancient enzyme

Nicotinamide/nicotinic acid mononucleotide adenylyltransferase (NMNAT) has long been known as the master enzyme in NAD biosynthesis in living organisms. A burst of investigations on NMNAT, going beyond enzymology, have paralleled increasing discoveries of key roles played by NAD homeostasis in a number or patho-physiological conditions. The availability of in-depth kinetics and structural enzymology analyses carried out on NMNATs from different organisms offer a powerful tool for uncovering fascinating evolutionary relationships. On the other hand, additional functions featuring NMNAT have emerged from investigations aimed at unraveling the molecular mechanisms responsible for complex biological phenomena such as neurodegeneration. NMNAT appears to be a multifunctional protein that sits both at the core of central metabolism and at a crossroads of multiple cellular processes. The resultant wealth of biochemical data has built a robust framework upon which design of NMNAT activators, inhibitors or enzyme variants of potential medical interest can be based.     

陶瓷颗粒(纤维)增强聚合物复合电子封装与基板材料

本文论述了陶瓷颗粒(纤维)增强聚合物基复合电子封装与基板材料体系和性能特点,介绍了复合基板材料的实验研究和理论研究进展情况,根据实验研究和文献报道并结合目前在微电子封装领域广泛应用的环氧塑封材料,对复合电子封装与基板材料的发展趋势进行了分析和评述。     

无机功能晶体材料的结晶过程研究

功能晶体材料作为光、声、电等转换的重要介质,已经被广泛应用于能源、信息、航空航天等高新技术领域,是目前国际材料科学与工程学科发展的热点和前沿课题.结晶过程是制备功能材料的核心环节,结晶习性直接影响材料的光、电、磁、催化等功能特性.在无机材料的结晶过程中,晶体组成在微观上经历了从自由态离子到结晶态固体的相变过程.可以借助晶体组成离子的电负性及基团微观对称性的变化,研究结晶过程中聚集体的形成和结构演变规律.利用分子振动光谱能够从分子尺度上揭示非线性光学晶体材料在水溶液结晶过程中结晶学结构的形成过程,克服了传统原位观测手段中缺乏对非长程有序结构的确定.利用结晶生长的化学键合理论从热力学和动力学两个方面指导大块晶体的生长实践,合理调控晶体的生长表/界面热力学和动力学.将结晶生长的化学键合理论应用到大尺寸晶体提拉生长参数的设计和优化,成功搭建了大尺寸晶体智能生长系统,并成功生长了φ2″蓝宝石晶体、φ3″YAG晶体和φ4″铌酸锂晶体.     

The polymerization of sickle hemoglobin in solutions and cells

The polymerization of sickle hemoglobin occurs by the same mechanisms in solutions and in cells, and involves the formation of 14 stranded fibers from hemoglobin molecules which have assumed a deoxy quaternary structure. The fibers form via two types of highly concentration-dependent nucleation processes: homogeneous nucleation in solutions with hemoglobin activity above a critical activity, and heterogeneous nucleation in similarly supersaturated solutions which also contain hemoglobin polymers. The latter pathway is dominant, and creates polymer arrays called domains. The individual polymers bend, but also cross-link, and the resulting mass behaves as a solid. The concentration of polymerized hemoglobin increases exponentially unless clamped by rate limiting effects such as oxygen delivery.     

Multiple catalytically active thioredoxin folds: a winning strategy for many functions

The Thioredoxin (Trx) fold is a versatile protein scaffold consisting of a four-stranded β-sheet surrounded by three α-helices. Various insertions are possible on this structural theme originating different proteins, which show a variety of functions and specificities. During evolution, the assembly of different Trx fold domains has been used many times to build new multi-domain proteins able to perform a large number of catalytic functions. To clarify the interaction mode of the different Trx domains within a multi-domain structure and how their combination can affect catalytic performances, in this review, we report on a structural and functional analysis of the most representative proteins containing more than one catalytically active Trx domain: the eukaryotic protein disulfide isomerases (PDIs), the thermophilic protein disulfide oxidoreductases (PDOs) and the hybrid peroxiredoxins (Prxs).     

Polyubiquitin chains: functions, structures, and mechanisms

Ubiquitin is a highly conserved 76-amino acid polypeptide that is found throughout the eukaryotic kingdom. The covalent conjugation of ubiquitin (often in the form of a polymer) to substrates governs a variety of biological processes ranging from proteolysis to DNA damage tolerance. The functional flexibility of this post-translational modification has its roots in the existence of a large number of ubiquitinating enzymes that catalyze the formation of distinct ubiquitin polymers, which in turn encode different signals. This review summarizes recent advances in the field with an emphasis on the non-canonical functions of polyubiquitination. We also discuss the potential mechanism of chain linkage specification as well as how structural disparity in ubiquitin polymers may be distinguished by ubiquitin receptors to translate the versatile ubiquitin signals into various cellular functions.     

A microvolume molecular filter

A microvolume polymer membrane filter based on Amicon hollow fibers in described which permits separation of low molecular weight compounds from proteins, and can be used for desalting volumes of 100 microliter or less, or to separate cellular protein debris from perfusates during release studies. The filter has the advantage of being reusable and having almost no void volume.     

Role played in man by myelinated fibers of different diameters for the evocation of a nociceptive flex reflex and the accompanying pain sensation]

Using simultaneous recordings we have made in Man a comparative study of: the sural nerve afferent volley, the nociceptive flexor reflex of a muscle of the lower limb and the associated painful sensation. Two types of stimulations were used, a single short duration electric stimulus, and a train of electric shocks (100/sec). With a single stimulus, the nociceptive flexor reflex and the painful sensation develop only when A delta fibers are recruited. On the other hand, when the stimulations are given by trains the nociceptive flexor reflex and the painful sensation can develop with a stimulus sub-liminar to the threshold of A delta fibers, when A alpha fibers are recruited. When the stimulus activate both A alpha and A delta fibers, the flexion reflex and the pain disappear when a selective blockade of the A delta group is exerted by means of Lidocain.     

Biomimetic actuators: where technology and cell biology merge

The structural and functional analysis of biological macromolecules has reached a level of resolution that allows mechanistic interpretations of molecular action, giving rise to the view of enzymes as molecular machines. This machine analogy is not merely metaphorical, as bio-analogous molecular machines actually are being used as motors in the fields of nanotechnology and robotics. As the borderline between molecular cell biology and technology blurs, developments in the engineering and material sciences become increasingly instructive sources of models and concepts for biologists. In this review, we provide a--necessarily selective--summary of recent progress in the usage of biological and biomimetic materials as actuators in artificial environments, focussing on motors built from DNA, classical cellular motor systems (tubulin/kinesin, actin/myosin), the rotary motor F1F0-ATPase and protein-based 'smart' materials.