Self-assembly in aqueous solution of wheel-shaped Mo154 oxide clusters into vesicles

Surfactants and membrane lipids readily assemble into complex structures such as micelles, liposomes or hollow vesicles owing to their amphiphilic character-the fact that part of their structure is attracted to polar environments while another part is attracted to non-polar environments. The self-assembly of complex structures also occurs in polyoxometallate chemistry, as exemplified by the molybdenum blue solutions known for centuries. But while the presence of nanometre-sized metal oxide aggregates in these solutions has long been recognized, unravelling the composition and formation process of these aggregates proved difficult. Recent work has indicated that discrete, wheel-shaped mixed-valence polyoxomolybdate clusters of the type [Mo154] (refs 2-4) assemble into well-defined nanometre-sized aggregates, including spherical structures. Here we report light-scattering data and transmission electron microscopy images of hollow spherical structures with an average, almost monodisperse radius of about 45 nm and composed of approximately 1,165 [Mo154] wheel-shaped clusters. The clusters appear to lie flat and homogeneously distributed on the vesicle surface. Unlike conventional lipid vesicles, the structures we observe are not stabilized by hydrophobic interactions. Instead, we believe the polyoxomolybdate-based vesicles form owing to a subtle interplay between short-range van der Waals attraction and long-range electrostatic repulsion, with important further stabilization arising from hydrogen bonding involving water molecules encapsulated between the wheel-shaped clusters and in the vesicles' interior.     

Coherent transfer of Cooper pairs by a movable grain

Superconducting circuits that incorporate Josephson junctions are of considerable experimental and theoretical interest, particularly in the context of quantum computing. A nanometre-sized superconducting grain (commonly referred to as a Cooper-pair box) connected to a reservoir by a Josephson junction is an important example of such a system. Although the grain contains a large number of electrons, it has been experimentally demonstrated that its states are given by a superposition of only two charge states (differing by 2e, where e is the electronic charge). Coupling between charge transfer and mechanical motion in nanometre-sized structures has also received considerable attention. Here we demonstrate theoretically that a movable Cooper-pair box oscillating periodically between two remote superconducting electrodes can serve as a mediator of Josephson coupling, leading to coherent transfer of Cooper pairs between the electrodes. Both the magnitude and the direction of the resulting Josephson current can be controlled by externally applied electrostatic fields.     

Stepwise radial complexation of imine groups in phenylazomethine dendrimers

Dendrimers are highly branched organic macromolecules with successive layers or 'generations' of branch units surrounding a central core. Organic-inorganic hybrid versions have also been produced, by trapping metal ions or metal clusters within the voids of the dendrimers. The unusual, tree-like topology endows these nanometre-sized macromolecules with a gradient in branch density from the interior to the exterior, which can give rise to an energy gradient that directs the transfer of charge and energy from the dendrimer periphery to its core. Here we show that tin ions, Sn(2+), complex to the imine groups of a spherical polyphenylazomethine dendrimer in a stepwise fashion. This behaviour reflects a gradient in the electron density associated with the imine groups, with complexation in a more peripheral generation proceeding only after complexation in generations closer to the core has been completed. By attaching an electron-withdrawing group to the dendrimer core, we are able to change the complexation pattern, so that the core imines are complexed last. By further extending this strategy, it should be possible to control the number and location of metal ions incorporated into dendrimer structures, which might find uses as tailored catalysts or building blocks for advanced materials.     

四种光阱刚度测量法的实验研究与比较

通过对光阱刚度的测量原理、方法及其特点进行分析,对多种光镊刚度标定方法进行了比较,分析了不同方法的精度和适用范围,总结了各种方法的优缺点.其中,流体力学法简单易行,但是误差较大;外加周期驱动力法精度较高,不需要测量绝对位移,但是适用的微粒的直径范围有限;热运动分析法所需要的参数少,但是受到系统噪声影响较大;功率谱方法精度较高,且不需要测量出绝对位移,但是测量结果受到系统噪声影响较大.     

应用ABEEMσπ模型快速计算分子静电势

分子静电势是量子化学的理论指标,可以用来判断分子的某些性质,尤其是分子的反应活性.由于静电势由分子本身的性质决定,不同分子在其周围空间各点产生的静电势不同,因此可以采用静电势来描述分子本身的性质.建立了一种新的快速计算分子静电势的方法,并以HF、H2O、NH3和CH4小分子为例计算了他们的静电势.其中的电荷采用原子-键电负性均衡方法σπ模型（ABEEMσπ）计算的结果,结构由MP2/6-311＋＋G（d,p）方法优化所得.基于杨等人建立的内禀特征轮廓理论,绘制了相应的分子静电势分布图.结果与从头算符合得很好,为大分子静电势的计算打下基础.     

A prototype storage ring for neutral molecules

The ability to cool and manipulate atoms with light has yielded atom interferometry, precision spectroscopy, Bose-Einstein condensates and atom lasers. The extension of controlled manipulation to molecules is expected to be similarly rewarding, but molecules are not as amenable to manipulation by light owing to a far more complex energy-level spectrum. However, time-varying electric and magnetic fields have been successfully used to control the position and velocity of ions, suggesting that these schemes can also be used to manipulate neutral particles having an electric or magnetic dipole moment. Although the forces exerted on neutral species are many orders of magnitude smaller than those exerted on ions, beams of neutral dipolar molecules have been successfully slowed down in a series of pulsed electric fields and subsequently loaded into an electrostatic trap. Here we extend the scheme to include a prototype electrostatic storage ring made of a hexapole torus with a circumference of 80 cm. After injection, decelerated bunches of deuterated ammonia molecules, each containing about 106 molecules in a single quantum state and with a translational temperature of 10 mK, travel up to six times around the ring. Stochastic cooling might provide a means to increase the phase-space density of the stored molecules in the storage ring, and we expect this to open up new opportunities for molecular spectroscopy and studies of cold molecular collisions.     

具有模糊弹性连接的杆系结构有限元方法

杆系结构各单元在节点处的连接状态往往是介于刚接和铰接之间的某种弹性连接状态。作者推导了具有转动弹性连接的杆单元刚度矩阵和荷载转移矩阵,其中考虑了横向切效应。     

Visual categorization shapes feature selectivity in the primate temporal cortex.

The way that we perceive and interact with objects depends on our previous experience with them. For example, a bird expert is more likely to recognize a bird as a sparrow, a sandpiper or a cockatiel than a non-expert. Neurons in the inferior temporal cortex have been shown to be important in the representation of visual objects; however, it is unknown which object features are represented and how these representations are affected by categorization training. Here we show that feature selectivity in the macaque inferior temporal cortex is shaped by categorization of objects on the basis of their visual features. Specifically, we recorded from single neurons while monkeys performed a categorization task with two sets of parametric stimuli. Each stimulus set consisted of four varying features, but only two of the four were important for the categorization task (diagnostic features). We found enhanced neuronal representation of the diagnostic features relative to the non-diagnostic ones. These findings demonstrate that stimulus features important for categorization are instantiated in the activity of single units (neurons) in the primate inferior temporal cortex.     

Electrically erodible polymer gel for controlled release of drugs

New controlled drug-delivery systems are being explored to overcome the disadvantages of conventional dosage forms. For example, stimulated drug-delivery has been used to overcome the tolerance problems that occur with a constant delivery rate, to mimic the physiological pattern of hormonal concentration and to supply drugs on demand. Stimuli-sensitive polymers, which are potentially useful for pulsed drug delivery, experience changes in either their structure or their chemical properties in response to changes in environmental conditions. Environmental stimuli include temperature, pH, light (ultraviolet or visible), electric field or certain chemicals. Volume changes of stimuli-sensitive gel networks are particularly responsive to external stimuli, but swelling is slow to occur. As well as being useful in the controlled release of drugs, such systems also provide insight into intermolecular interactions. Here we report on a novel polymeric system, which rapidly changes from a solid state to solution in response to small electric currents, by disintegration of the solid polymer complex into two water-soluble polymers. We show that the modulated release of insulin, and by extension other macromolecules, can be achieved with this polymeric system.     

Electrostatic trapping of ammonia molecules

The ability to cool and slow atoms with light for subsequent trapping allows investigations of the properties and interactions of the trapped atoms in unprecedented detail. By contrast, the complex structure of molecules prohibits this type of manipulation, but magnetic trapping of calcium hydride molecules thermalized in ultra-cold buffer gas and optical trapping of caesium dimers generated from ultra-cold caesium atoms have been reported. However, these methods depend on the target molecules being paramagnetic or able to form through the association of atoms amenable to laser cooling, respectively, thus restricting the range of species that can be studied. Here we describe the slowing of an adiabatically cooled beam of deuterated ammonia molecules by time-varying inhomogeneous electric fields and subsequent loading into an electrostatic trap. We are able to trap state-selected ammonia molecules with a density of 10(6) cm(-3) in a volume of 0.25 cm3 at temperatures below 0.35 K. We observe pronounced density oscillations caused by the rapid switching of the electric fields during loading of the trap. Our findings illustrate that polar molecules can be efficiently cooled and trapped, thus providing an opportunity to study collisions and collective quantum effects in a wide range of ultra-cold molecular systems.     

Chemically tailorable colloidal particles from infinite coordination polymers

Micrometre- and nanometre-sized particles play important roles in many applications, including catalysis, optics, biosensing and data storage. Organic particles are usually prepared through polymerization of suitable monomers or precipitation methods. In the case of inorganic materials, particle fabrication tends to involve the reduction of a metal salt, or the controlled mixing of salt solutions supplying a metal cation and an elemental anion (for example, S2-, Se2-, O2-), respectively; in some instances, these methods even afford direct control over the shape of the particles produced. Another class of materials are metal-organic coordination polymers, which are based on metal ions coordinated by polydentate organic ligands and explored for potential use in catalysis, gas storage, nonlinear optics and molecular recognition and separations. In a subset of these materials, the use of organometallic complexes as ligands (so-called metalloligands) provides an additional level of tailorability, but these materials have so far not yet been fashioned into nano- or microparticles. Here we show that simple addition of an initiation solvent to a precursor solution of metal ions and metalloligands results in the spontaneous and fully reversible formation of a new class of metal-metalloligand particles. We observe initial formation of particles with diameters of a few hundred nanometres, which then coalesce and anneal into uniform and smooth microparticles. The ease with which these particles can be fabricated, and the ability to tailor their chemical and physical properties through the choice of metal and organic ligand used, should facilitate investigations of their scope for practical applications.     

糖苷合成酶及应用的研究进展

糖基化修饰不仅能改善生物大分子和化合物的理化性质如水溶性和稳定性,且有可能增强其原生物活性或赋予新活性。目前,提取分离、化学合成和酶法合成是糖基化修饰产物的主要来源,但前两种方法通常存在产物多样性不足、得率低或糖基化位点特异性差等难题。基于糖基转移酶和糖苷合成酶的酶法糖基化修饰技术则能够较好地解决上述两种方法存在的问题,并展现出一定优势。由于糖基转移酶已被多次综述,本文将概述糖苷合成酶的研究进展,为多功能新型糖苷合成酶的开发和应用提供参考和借鉴。     

偶极激子的静电俘获

考虑设计偶极间接激子的2维静电俘获.可以看到,与由于陷阱几何增加的平面电场结合的激子偶极-偶极相互作用约束所俘获的最大密度和寿命.导出这些值的解析估算,并确定它们与陷阱几何的关系,提出观察激子的Bose-Einstein凝聚方法中的高密度陷俘的最佳设计.     

Adsorption-induced scission of carbon-carbon bonds

Covalent carbon-carbon bonds are hard to break. Their strength is evident in the hardness of diamonds and tensile strength of polymeric fibres; on the single-molecule level, it manifests itself in the need for forces of several nanonewtons to extend and mechanically rupture one bond. Such forces have been generated using extensional flow, ultrasonic irradiation, receding meniscus and by directly stretching a single molecule with nanoprobes. Here we show that simple adsorption of brush-like macromolecules with long side chains on a substrate can induce not only conformational deformations, but also spontaneous rupture of covalent bonds in the macromolecular backbone. We attribute this behaviour to the fact that the attractive interaction between the side chains and the substrate is maximized by the spreading of the side chains, which in turn induces tension along the polymer backbone. Provided the side-chain densities and substrate interaction are sufficiently high, the tension generated will be strong enough to rupture covalent carbon-carbon bonds. We expect similar adsorption-induced backbone scission to occur for all macromolecules with highly branched architectures, such as brushes and dendrimers. This behaviour needs to be considered when designing surface-targeted macromolecules of this type-either to avoid undesired degradation, or to ensure rupture at predetermined macromolecular sites.     

Folding-driven synthesis of oligomers.

The biological function of biomacromolecules such as DNA and enzymes depends on their ability to perform and control molecular association, catalysis, self-replication or other chemical processes. In the case of proteins in particular, the dependence of these functions on the three-dimensional protein conformation is long known and has inspired the development of synthetic oligomers and polymers with the capacity to fold in a controlled manner, but it remains challenging to design these so-called 'foldamers' so that they are capable of inducing or controlling chemical processes and interactions. Here we show that the stability gained from folding can be used to control the synthesis of oligomers from short chain segments reversibly ligated through an imine metathesis reaction. That is, folding shifts the ligation equilibrium in favour of conformationally ordered sequences, so that oligomers having the most stable solution structures form preferentially. Crystallization has previously been used to shift an equilibrium in order to indirectly influence the synthesis of small molecules, but the present approach to selectively prepare macromolecules with stable conformations directly connects folding and synthesis, emphasizing molecular function rather than structure in polymer synthesis.     

Optical emission from a charge-tunable quantum ring

Quantum dots or rings are artificial nanometre-sized clusters that confine electrons in all three directions. They can be fabricated in a semiconductor system by embedding an island of low-bandgap material in a sea of material with a higher bandgap. Quantum dots are often referred to as artificial atoms because, when filled sequentially with electrons, the charging energies are pronounced for particular electron numbers; this is analogous to Hund's rules in atomic physics. But semiconductors also have a valence band with strong optical transitions to the conduction band. These transitions are the basis for the application of quantum dots as laser emitters, storage devices and fluorescence markers. Here we report how the optical emission (photoluminescence) of a single quantum ring changes as electrons are added one-by-one. We find that the emission energy changes abruptly whenever an electron is added to the artificial atom, and that the sizes of the jumps reveal a shell structure.     

Imaging of localized electronic states in the quantum Hall regime

The concept of electron localization has long been accepted to be essential to the physics of the quantum Hall effect in a two-dimensional electron gas. The exact quantization of the Hall resistance and the zero of the diagonal resistance over a range of filling factors close to integral are attributed to the localization of electronic states at the Fermi level in the interior of the gas. As the electron density is changed, charging of the individual localized states may occur by single-electron jumps, causing associated oscillations in the local electrostatic potential. Here we search for such a manifestation of localized states in the quantum Hall regime, using a scanning electrometer probe. We observe localized potential signals, at numerous locations, that oscillate with changing electron density. In general, the corresponding spatial patterns are complex, but well-defined objects are often seen which evidently arise from individual localized states. These objects interact, and at times form a lattice-like arrangement.     

Extreme damping in composite materials with negative-stiffness inclusions

When a force deforms an elastic object, practical experience suggests that the resulting displacement will be in the same direction as the force. This property is known as positive stiffness. Less familiar is the concept of negative stiffness, where the deforming force and the resulting displacement are in opposite directions. (Negative stiffness is distinct from negative Poisson's ratio, which refers to the occurrence of lateral expansion upon stretching an object.) Negative stiffness can occur, for example, when the deforming object has stored (or is supplied with) energy. This property is usually unstable, but it has been shown theoretically that inclusions of negative stiffness can be stabilized within a positive-stiffness matrix. Here we describe the experimental realization of this composite approach by embedding negative-stiffness inclusions of ferroelastic vanadium dioxide in a pure tin matrix. The resulting composites exhibit extreme mechanical damping and large anomalies in stiffness, as a consequence of the high local strains that result from the inclusions deforming more than the composite as a whole. Moreover, for certain temperature ranges, the negative-stiffness inclusions are more effective than diamond inclusions for increasing the overall composite stiffness. We expect that such composites could be useful as high damping materials, as stiff structural elements or for actuator-type applications.     

Bandgap modulation of carbon nanotubes by encapsulated metallofullerenes

Motivated by the technical and economic difficulties in further miniaturizing silicon-based transistors with the present fabrication technologies, there is a strong effort to develop alternative electronic devices, based, for example, on single molecules. Recently, carbon nanotubes have been successfully used for nanometre-sized devices such as diodes, transistors, and random access memory cells. Such nanotube devices are usually very long compared to silicon-based transistors. Here we report a method for dividing a semiconductor nanotube into multiple quantum dots with lengths of about 10nm by inserting Gd@C82 endohedral fullerenes. The spatial modulation of the nanotube electronic bandgap is observed with a low-temperature scanning tunnelling microscope. We find that a bandgap of approximately 0.5eV is narrowed down to approximately 0.1eV at sites where endohedral metallofullerenes are inserted. This change in bandgap can be explained by local elastic strain and charge transfer at metallofullerene sites. This technique for fabricating an array of quantum dots could be used for nano-electronics and nano-optoelectronics.