Control of four stereocentres in a triple cascade organocatalytic reaction

Efficient and elegant syntheses of complex organic molecules with multiple stereogenic centres continue to be important in both academic and industrial laboratories. In particular, catalytic asymmetric multi-component 'domino' reactions, used during total syntheses of natural products and synthetic building blocks, are highly desirable. These reactions avoid time-consuming and costly processes, including the purification of intermediates and steps involving the protection and deprotection of functional groups, and they are environmentally friendly and often proceed with excellent stereoselectivities. Therefore, the design of new catalytic and stereoselective cascade reactions is a continuing challenge at the forefront of synthetic chemistry. In addition, catalytic cascade reactions can be described as biomimetic, as they are reminiscent of tandem reactions that may occur during biosyntheses of complex natural products. Here we report the development of an asymmetric organocatalytic triple cascade reaction for the synthesis of tetra-substituted cyclohexene carbaldehydes. This three-component domino reaction proceeds by way of a catalysed Michael/Michael/aldol condensation sequence affording the products with good to moderate yields (25-58 per cent). During this sequence, four stereogenic centres are formed with high diastereoselectivity and complete enantioselectivity. In addition, variation of the starting materials can be used to obtain diverse polyfunctional cyclohexene derivatives, which can be used as building blocks in organic synthesis.     

基因块编码的并行遗传算法及其在TSP中的应用

针对简单遗传算法在较大规模组合优化问题上搜索效率不高的现象,提出了一种用基因块编码的并行遗传算法(Building-block Coded Parallel GA,BCPGA).该方法以粗粒度并行遗传算法为基本框架,在染色体群体中识别出可能的基因块,然后用基因块作为新的基因单位对染色体重新编码,产生长度较短的染色体,再用重新编码的染色体群体作为下一轮以相同方式演化的初始群体.将BCPGA应用于一个100城市的旅行商问题(TSP)中,结果表明本方法可以提高遗传算法的搜索效率,并且在相同条件下,BCPGA明显优于单纯的粗粒度并行遗传算法.     

超细层状钛酸钾的制备及性质研究

采用纳米级TiO2为原料，通过固相反应法成功制备了超细层状钛酸钾(K2Ti4O9)，并与微米级TiO2为原料制备所得产物相比较，以XRD、TEM、TG等表征手段考察了超细层状钛酸钾的酸交换、烷基胺嵌入特性．发现超细层状钛酸钾有利于酸交换和嵌入反应的进行，同时发现了超细层状钛酸钾的剥离特性，剥离所得纳米级片层可以制备静电组装纳米TiO2多层膜．     

Indium phosphide nanowires as building blocks for nanoscale electronic and optoelectronic devices

Nanowires and nanotubes carry charge and excitons efficiently, and are therefore potentially ideal building blocks for nanoscale electronics and optoelectronics. Carbon nanotubes have already been exploited in devices such as field-effect and single-electron transistors, but the practical utility of nanotube components for building electronic circuits is limited, as it is not yet possible to selectively grow semiconducting or metallic nanotubes. Here we report the assembly of functional nanoscale devices from indium phosphide nanowires, the electrical properties of which are controlled by selective doping. Gate-voltage-dependent transport measurements demonstrate that the nanowires can be predictably synthesized as either n- or p-type. These doped nanowires function as nanoscale field-effect transistors, and can be assembled into crossed-wire p-n junctions that exhibit rectifying behaviour. Significantly, the p-n junctions emit light strongly and are perhaps the smallest light-emitting diodes that have yet been made. Finally, we show that electric-field-directed assembly can be used to create highly integrated device arrays from nanowire building blocks.     

Directed self-assembly of a colloidal kagome lattice

A challenging goal in materials chemistry and physics is spontaneously to form intended superstructures from designed building blocks. In fields such as crystal engineering and the design of porous materials, this typically involves building blocks of organic molecules, sometimes operating together with metallic ions or clusters. The translation of such ideas to nanoparticles and colloidal-sized building blocks would potentially open doors to new materials and new properties, but the pathways to achieve this goal are still undetermined. Here we show how colloidal spheres can be induced to self-assemble into a complex predetermined colloidal crystal-in this case a colloidal kagome lattice-through decoration of their surfaces with a simple pattern of hydrophobic domains. The building blocks are simple micrometre-sized spheres with interactions (electrostatic repulsion in the middle, hydrophobic attraction at the poles, which we call 'triblock Janus') that are also simple, but the self-assembly of the spheres into an open kagome structure contrasts with previously known close-packed periodic arrangements of spheres. This open network is of interest for several theoretical reasons. With a view to possible enhanced functionality, the resulting lattice structure possesses two families of pores, one that is hydrophobic on the rims of the pores and another that is hydrophilic. This strategy of 'convergent' self-assembly from easily fabricated colloidal building blocks encodes the target supracolloidal architecture, not in localized attractive spots but instead in large redundantly attractive regions, and can be extended to form other supracolloidal networks.     

SIP协议组合模型的研究

在传统的会话发起协议的实现中,实现软件可重用度低、不易于SIP(会话发起协议)的功能扩展,文中采用基于CSP(通信顺序进程)理论的协议组合模型将SIP协议分解成协议构件,准确地描述了SIP协议实体之间的交互,在此基础上建立了一个可以方便地、灵活地进行SIP功能扩展的SIP协议组合模型。这个组合模型首先将SIP协议分解为具有独立功能的构件协议,然后通过这些构件协议的组合来实现更多的SIP功能。这个模型解决了传统的SIP协议实现软件可重用度低、不易于进行功能扩展等缺点。同时,采用CSP对该模型进行形式化描述,从而说明通过构件协议的组合可以实现SIP的功能。     

A homochiral metal-organic porous material for enantioselective separation and catalysis

Inorganic zeolites are used for many practical applications that exploit the microporosity intrinsic to their crystal structures. Organic analogues, which are assembled from modular organic building blocks linked through non-covalent interactions, are of interest for similar applications. These range from catalysis, separation and sensor technology to optoelectronics, with enantioselective separation and catalysis being especially important for the chemical and pharmaceutical industries. The modular construction of these analogues allows flexible and rational design, as both the architecture and chemical functionality of the micropores can, in principle, be precisely controlled. Porous organic solids with large voids and high framework stability have been produced, and investigations into the range of accessible pore functionalities have been initiated. For example, catalytically active organic zeolite analogues are known, as are chiral metal-organic open-framework materials. However, the latter are only available as racemic mixtures, or lack the degree of framework stability or void space that is required for practical applications. Here we report the synthesis of a homochiral metal-organic porous material that allows the enantioselective inclusion of metal complexes in its pores and catalyses a transesterification reaction in an enantioselective manner. Our synthesis strategy, which uses enantiopure metal-organic clusters as secondary building blocks, should be readily applicable to chemically modified cluster components and thus provide access to a wide range of porous organic materials suitable for enantioselective separation and catalysis.     

Selection of peptides with semiconductor binding specificity for directed nanocrystal assembly

In biological systems, organic molecules exert a remarkable level of control over the nucleation and mineral phase of inorganic materials such as calcium carbonate and silica, and over the assembly of crystallites and other nanoscale building blocks into complex structures required for biological function. This ability to direct the assembly of nanoscale components into controlled and sophisticated structures has motivated intense efforts to develop assembly methods that mimic or exploit the recognition capabilities and interactions found in biological systems. Of particular value would be methods that could be applied to materials with interesting electronic or optical properties, but natural evolution has not selected for interactions between biomolecules and such materials. However, peptides with limited selectivity for binding to metal surfaces and metal oxide surfaces have been successfully selected. Here we extend this approach and show that combinatorial phage-display libraries can be used to evolve peptides that bind to a range of semiconductor surfaces with high specificity, depending on the crystallographic orientation and composition of the structurally similar materials we have used. As electronic devices contain structurally related materials in close proximity, such peptides may find use for the controlled placement and assembly of a variety of practically important materials, thus broadening the scope for 'bottom-up' fabrication approaches.     

声表面波谐振滤波器中纵横向耦合模式的研究及其复合应用

在通常的声表面波谐振滤波器中,由于采用的模式不同,纵向耦合谐振器具带宽大和插损低,带外抑制较差的特点;而横向耦合谐振器则具有带外抑制高,低插损及通带较窄的特点．为了综合两种滤波器的优点,采用了一种改进的滤波器结构,可同时利用纵向与横向耦合模式,得到既有较大带宽又有高带外抑制的声表面波谐振滤波器．运用耦合膜理论对纵横向模式的复合进行了分析,并在计算机上对这种结构的滤波器特性作了模拟,实验结果与模拟结果得到了较好的吻合．     

遗传算法进化中积木块的识别和利用研究

提出了一种基于积木块识别的遗传算法，该算法通过对进化过程中的候选积木块进行识别与利用来加速搜索，从而避免遗传算法随机搜索的盲目性．利用经典的对称旅行商问题求解过程来测试各种识别方法，再利用积木块的识别结果改进原有遗传算法，包括改进积木块的识别率以及基于积木块的交叉、变异算子．与基本遗传算法的计算结果对比分析表明，所提算法可显著提高遗传算法的搜索效率，减小遗传算法随机搜索的波动性．     

Distributed biological computation with multicellular engineered networks

Ongoing efforts within synthetic and systems biology have been directed towards the building of artificial computational devices using engineered biological units as basic building blocks. Such efforts, inspired in the standard design of electronic circuits, are limited by the difficulties arising from wiring the basic computational units (logic gates) through the appropriate connections, each one to be implemented by a different molecule. Here, we show that there is a logically different form of implementing complex Boolean logic computations that reduces wiring constraints thanks to a redundant distribution of the desired output among engineered cells. A practical implementation is presented using a library of engineered yeast cells, which can be combined in multiple ways. Each construct defines a logic function and combining cells and their connections allow building more complex synthetic devices. As a proof of principle, we have implemented many logic functions by using just a few engineered cells. Of note, small modifications and combination of those cells allowed for implementing more complex circuits such as a multiplexer or a 1-bit adder with carry, showing the great potential for re-utilization of small parts of the circuit. Our results support the approach of using cellular consortia as an efficient way of engineering complex tasks not easily solvable using single-cell implementations.     

船舶坐墩墩反力的分析计算

剖析了传统的船舶坐墩墩反力计算方法，并用有限元法进行了对比分析计算，指出了前者存在着适应范围的局限性和计算结果不完整及不直观等问题。认为采用有限元法进行船舶坐墩墩反力分析计算较适宜。最后讨论了墩木刚性对船体结构安全性的影响，提出了墩木设置的一般原则。     

DNA-programmable nanoparticle crystallization

It was first shown more than ten years ago that DNA oligonucleotides can be attached to gold nanoparticles rationally to direct the formation of larger assemblies. Since then, oligonucleotide-functionalized nanoparticles have been developed into powerful diagnostic tools for nucleic acids and proteins, and into intracellular probes and gene regulators. In contrast, the conceptually simple yet powerful idea that functionalized nanoparticles might serve as basic building blocks that can be rationally assembled through programmable base-pairing interactions into highly ordered macroscopic materials remains poorly developed. So far, the approach has mainly resulted in polymerization, with modest control over the placement of, the periodicity in, and the distance between particles within the assembled material. That is, most of the materials obtained thus far are best classified as amorphous polymers, although a few examples of colloidal crystal formation exist. Here, we demonstrate that DNA can be used to control the crystallization of nanoparticle-oligonucleotide conjugates to the extent that different DNA sequences guide the assembly of the same type of inorganic nanoparticle into different crystalline states. We show that the choice of DNA sequences attached to the nanoparticle building blocks, the DNA linking molecules and the absence or presence of a non-bonding single-base flexor can be adjusted so that gold nanoparticles assemble into micrometre-sized face-centred-cubic or body-centred-cubic crystal structures. Our findings thus clearly demonstrate that synthetically programmable colloidal crystallization is possible, and that a single-component system can be directed to form different structures.     

Functionalizing hydrogen-bonded surface networks with self-assembled monolayers

One of the central challenges in nanotechnology is the development of flexible and efficient methods for creating ordered structures with nanometre precision over an extended length scale. Supramolecular self-assembly on surfaces offers attractive features in this regard: it is a 'bottom-up' approach and thus allows the simple and rapid creation of surface assemblies, which are readily tuned through the choice of molecular building blocks used and stabilized by hydrogen bonding, van der Waals interactions, pi-pi bonding or metal coordination between the blocks. Assemblies in the form of two-dimensional open networks are of particular interest for possible applications because well-defined pores can be used for the precise localization and confinement of guest entities such as molecules or clusters, which can add functionality to the supramolecular network. Another widely used method for producing surface structures involves self-assembled monolayers (SAMs), which have introduced unprecedented flexibility in our ability to tailor interfaces and generate patterned surfaces. But SAMs are part of a top-down technology that is limited in terms of the spatial resolution that can be achieved. We therefore rationalized that a particularly powerful fabrication platform might be realized by combining non-covalent self-assembly of porous networks and SAMs, with the former providing nanometre-scale precision and the latter allowing versatile functionalization. Here we show that the two strategies can indeed be combined to create integrated network-SAM hybrid systems that are sufficiently robust for further processing. We show that the supramolecular network and the SAM can both be deposited from solution, which should enable the widespread and flexible use of this combined fabrication method.     

一种通用的可编程双模分频器

提出了一种通用的可编程双模分频器,电路主要由3部分组成: 9/8预分频器,8位可编程计数器和ΣΔ调制器构成。通过打开或者关断ΣΔ调制器的输出来实现分数和整数分频两种工作模式,仅用一个可编程计数器实现吞脉冲分频器的功能。9/8预分频器采用提高的TSPC动态触发器实现,而可编程分频器和调制器采用数字综合后布局布线的方法实现。基于SMIC 0.18μm 1.8V 电源CMOS工艺的SpectreVerilog仿真表明：它能在分频比56-2 047范围内工作,最大工作频率大于2GHz,消耗的电流小于4mA,适合应用在高性能的频率综合器中。     

基于3DEC的边坡块体稳定性分析

为了解决节理化岩质边坡块体稳定性问题,利用3DEC在运动特征和变形分析方面的优势,探讨岩质边坡块体失稳动态过程,分析块体之间的相互关系,确定关键块体,然后利用块体理论评价其稳定性,为治理设计提供依据.实例应用表明:该方法可直观地模拟块体变形和运动特点,找出关键块体及其边界条件,正确地评价块体稳定性,也为边坡块体间稳定性相互影响问题的研究提供了一种新的更有效的方法,为制定合理的边坡支护措施及验证支护效果提供支撑.     

Efficient Synthesis of Optically Active Alcohols

1 Introduction Optically active secondary alcohols are versatile building blocks for synthesis of unnatural biological active compounds and functional materials. Therefore, study on efficient synthesis of optically active alcohols is becoming an important subject in synthetic organic chemistry. Catalytic asymmetric reduction of carbonyl compounds is a practical method to create chiral alcohols. For the past decades, a large number of catalytic methods have been developed to achieve this goal. …     

Subcellular localization of chitosan oligosaccharides in living cells

Chitosan oligosaccharides （COS） is derived from the chemical or enzymatic decomposition of chitosan. The exact mechanisms underlying many biological functions of COS have not been elucidated. Since subcellular localization is very important in determining biological activity in a number of molecules, we used fluorescein isothiocyanate-labeled chitosan oligosaccharides （FITC- COS） and investigated the localization of COS in living cells by laser scanning microscopy. We found that COS entered cells in a dose- and time-dependent manner, and we first showed that COS may enter cells by facilitated passive diffusion and was preferentially localized in the mitochondria. While in high concentration, it was also found in the cytoplasm and nucleus and was enriched in the nucleolus and karyotheca. The different subcellular localization of COS suggested that they played different effects. Determination of COS subcellular localization in cells is important to help us understand the potent mechanisms underlying its multiple functions.     

Robotics: self-replication from random parts

Autonomously self-replicating machines have long caught the imagination but have yet to acquire the sophistication of biological systems, which assemble structures from disordered building blocks. Here we describe the autonomous self-replication of a reconfigurable string of parts from randomly positioned input components. Such components, if suitably miniaturized and mass-produced, could constitute self-fabricating systems whose assembly is brought about by the parts themselves.     

Recent development of peptide self-assembly

Amino acids are the building blocks to build peptides and proteins. Recent development in peptide synthesis has however enabled us to mimic this natural process by preparing various long and short peptides possessing different conformations and biological functions. The self-assembly of short designed peptides into molecular nanostructures is becoming a growing interest in nanobiotechnology. Self-assembled peptides exhibit several attractive features for applications in tissue regeneration, drug delivery, biological surface engineering as well as in food science, cosmetic industry and antibiotics. The aim of this review is to introduce the readers to a number of representative studies on peptide self-assembly.