Design and DNA binding of an extended triple-stranded metallo-supramolecular cylinder

A new tetracationic triple-stranded supramolecular cylinder is prepared from a bis(pyridylimine) ligand containing a diphenylmethane and two ketimine groups in the spacer. The cylinder is longer and slightly wider than the corresponding cylinder containing just diphenylmethane spacers. Inter-strand CH...pi interactions are not observed and this affects the relay of the chiral information within the cylinder; a mixture of rac and meso isomers results, with the meso isomer being the dominant solution species and characterised in the solid state by crystallography. This new cylinder does bind to DNA as confirmed by induced circular dichroism signals in both the metal-to-ligand charge transfer (MLCT) and in-ligand bands of the cylinder. Flow linear dichroism demonstrates that the cylinder binds to DNA in a specific orientation(s) and is consistent with (major) groove-binding as seen for the shorter cylinder. Some DNA bending/coiling is observed but the effect is much less dramatic than observed for the cylinder with diphenylmethane spacers confirming that coiling is not solely a consequence of the tetracationic charge, but rather is related to the precise size and shape of the cylinder.     

A DNA-binding copper(I) metallosupramolecular cylinder that acts as an artificial nuclease

The DNA binding of a dicationic pyridylimine-based dicopper(I) metallosupramolecular cylinder is reported together with its ability to act as an artificial nuclease. The cylinder binds strongly to DNA; more strongly than the spherical dication [Ru(phen)(3)](2+) (phen=1,10-phenanthroline), but more weakly than the corresponding tetracationic cylinders. DNA coiling effects are not observed with this dication, in contrast to the situation with the previously reported tetracationic cylinder involving a similar ligand. Linear dichroism (LD) data suggests that the dicopper cylinder binds in a different orientation from that of the tetracationic iron cylinder. Furthermore, the dicopper cylinder shows DNA-cleavage activity in the presence of peroxide. Of particular note is that the cylinder displays a marked and unusual ability to cleave both DNA strands at the same site, probably reflecting its dinuclear nature and possibly its mode of binding to the DNA.     

Analytical calculation of the solid angle defined by a cylindrical detector and a point cosine source with orthogonal axes

We derive analytical expressions for the solid angle subtended by a right circular cylinder at a point source with cosine angular distribution in the case where the source and the cylinder axes are mutually orthogonal.     

Simulations of DNA coiling around a synthetic supramolecular cylinder that binds in the DNA major groove

In this work we present the results of a molecular simulation study of the interaction between a tetracationic bis iron(II) supramolecular cylinder, [Fe2(C25H20N4)3]4+, and DNA. This supramolecular cylinder has been shown to bind in the major groove of DNA and to induce dramatic coiling of the DNA. The simulations have been designed to elucidate the interactions that lead the cylinder to target the major groove and that drive the subsequent DNA conformational changes. Three sets of multi-nanosecond simulations have been performed: one of the uncomplexed d(CCCCCTTTTTCC) d(GGAAAAAGGGGG) dodecamer; one of this DNA complexed with the cylinder molecule; and one of this DNA complexed with a neutralised version of the cylinder. Coiling of the DNA was observed in the DNA-cylinder simulations, giving insight into the molecular level nature of the supramolecular coiling observed experimentally. The cylinder charge was found not to be essential for the DNA coiling, which implies that the DNA response is moderated by the short range interactions that define the molecular shape. Cylinder charge did, however, affect the integrity of the DNA duplex, to the extent that, under some circumstances, the tetracationic cylinder induced defects in the DNA base pairing at locations adjacent to the cylinder binding site.     

Floating objects with finite resistance to bending

We consider the equilibrium flotation of a thin, flexible cylinder at the interface between a liquid and a gas. In particular, we determine the maximum load that such a cylinder can support without sinking. We find that as the length of such a cylinder increases the maximum load at first increases. However, the maximum load reaches a plateau when the length of the cylinder is comparable to the elastocapillary length, which is determined by a balance between the bending of the cylinder and surface tension. We then consider the implications of our analysis for the walking on water of both arthropods and man-made robots. In particular, we show that the legs of water striders are typically slightly shorter than this 'optimal' length, suggesting that elastocapillary effects may act as a selection pressure.     

The lateral electric force on an off-axis sphere in a circular cylinder

The electrophoretic velocity of a sphere within a liquid-filled circular cylinder in a direction parallel to the cylinder axis has been studied by Yariv and Brenner (Phys. Fluids 2002, 14, 3354–3357; SIAM J. Appl. Math. 2003, 64, 423–441). We use their analyses of the electric field in order to determine the electrical force on the sphere along the cylinder radius (i.e., perpendicular to its axis) when either the radius of the sphere is small compared to that of the cylinder, or when the radius of the sphere is only slightly smaller than that of the cylinder. In both cases the force acts towards the centreline of the cylinder, and hence this force tends to stabilize electrophoresis of the sphere along the cylinder axis.     

Electrokinetic-vortex formation near a two-part cylinder with same-sign zeta potentials in a straight microchannel

Vortex formation near a two-part cylinder with zeta potentials of different values but the same sign under an external DC electric field is numerically investigated in this paper. The cylinder, inserted in a straight microchannel filled with an aqueous solution, is composed of an upstream part and a downstream part. When a DC electric field is applied in the channel, under certain conditions, the vortex will form near the cylinder due to the different velocities of electroosmotic flow generated on the cylinder surface. The numerical results reveal that the larger the velocity difference of electroosmotic flow generated on the two-part cylinder and the smaller the channel width, the more conducive to vortex formation in the channel. In addition, if the zeta potential ratios of cylinder downstream part to upstream part and channel wall to cylinder upstream part are unchanged, the DC electric field strength and the zeta potential value do not affect the pattern of vortices formed in the channel. This study provides a way for vortex formation in microchannels and has the potential application in microfluidic devices.     

Analytical Dispersion Force Calculations for Nontraditional Geometries

Presented in this paper are first-principle-based approximate macroscopic models of the van der Waals adhesion force for a variety of particle shapes interacting with an infinite cylinder. In particular, expressions for the van der Waals adhesion force and interaction energy are developed for a (1) spherical particle/infinite cylinder, (2) disk-like particle/infinite cylinder, (3) disk-like particle oriented edgewise to an infinite cylinder, and (4) a deformed slice/infinite cylinder. The models presented depict expected trends in the behavior of both the force of adhesion and the interaction energy between different geometric configurations. These results are also used to demonstrate the impact of contact time on the adhesion force for cylindrical fibers in contact with a disk-shaped particle. After long time intervals where the disk-like particles have remained in contact with the cylinder, the adhesion force may lead to significant deformation of the attached particle. Hence, the adhesion force for a fourth geometric set which represents the most likely scenario for attached particles with long contact times is developed. As will be shown, this scenario results in the highest values of adhesion force and interaction energy. Copyright 2000 Academic Press.     

乙醇气体标准物质包装容器的选择及分析条件的优化

采用不同分装方法考察了低含量乙醇气体在国内现有气瓶中的吸附情况,通过对比选择出最适合的乙醇气体的气瓶,然后使用高浓度乙醇气体对其进行预饱和,最后再次通过分装实验来验证其吸附情况.此外,通过选择不同的色谱柱、柱温、柱流速和分流比等条件,对乙醇分析的色谱条件进行了优化.     

Boundary effects on the electrophoretic motion of cylindrical particles: concentrically and eccentrically-positioned particles in a capillary

The bounded electrophoretic motion of a cylindrical particle in a circular cylindrical microchannel is explored for two cases: (1) the particle is located on the centerline of a channel (concentrically), with a symmetric wall boundary condition since gap width is constant throughout; and (2) the particle is at an eccentric location in the channel, with an asymmetric boundary condition set by the walls. The objective is to determine the effect of different boundary conditions, geometries, and physical properties on the velocity and orientation of the cylinder with respect to the boundary. A theoretical model for the motion of the cylinder is presented and the problem is solved numerically. The steady-state simulations show that the velocity of the cylinder is reduced at small gap widths for the concentric case, but the velocity is increased at small gap widths for the eccentric case. When the cylinder is angled with respect to the horizontal in the symmetric case or is near the boundary in the asymmetric case, vertical and rotational components of velocity are predicted. In such cases, transient simulations are appropriate for most accurately representing particle motion. Two such simulations are included herein and show both horizontal and vertical translation plus rotation of the particle as a function of time.     

Analytical calculation of the solid angle defined by a cylindrical detector and a point cosine source with parallel axes

We derive analytical expressions for the solid angle subtended by a right finite circular cylinder at a point source with cosine angular distribution in the case where the source direction is parallel to the cylinder axis. As a subsidiary result, an expression for the solid angle subtended by a disc detector at a spread disc source is also provided, in the case where the two discs have a common symmetry axis which is also coincident with the source direction.     

重量法配气的称量数学模型及其不确定度评定

对重量法制备气体标准物质中充入气体质量的计算方法进行了研究,建立了基于单盘电子天平的钢瓶称量方法,并建立了系统的数学模型和不确定度评价方法。为重量法制备气体标准物质提供一种简单、实用和精确的钢瓶称量方法和气体加入质量的计算方法。     

The viscous drag of three-dimensional model fibrous filters

Dependences of the viscous drag of the model filter consisting of two parallel cylinder rows arranged perpendicular to the Stokes flow and to each other, on a step and a distance between rows are found. The approximation formula for the drag force of a cylinder in contacting rows is obtained. The drag was calculated for the three-dimensional model filter where two hexagonal grids of cylinders are inserted into each other at a right angle. The drag force of a cylinder for this model is close to that for the fan model filter.     

The Electrical Double-Layer Interaction between a Spherical Particle and a Cylinder

Based on the well-known Debye-Hückel approximation and the Derjaguin's integration method, this paper presents an integral solution for the electrical double-layer (EDL) interaction between a spherical particle and a cylinder. The effects of the relative dimensions of the cylinder to the sphere on the EDL interaction are studied using this numerical solution. The detailed numerical results indicate that, in general, the curvature effect on the EDL interaction cannot be neglected at small separation distances. The widely used sphere-flat plate approximation will considerably overestimate the actual EDL interaction between a spherical particle and a cylinder. The ratio of the radius of the particle to the EDL thickness, tau=kappaa(p), also plays an important role in determining the EDL interaction at small dimensionless separation distances (相似文献   

Entropic selectivity of binary mixtures in cylindrical pores

We show that a simple model consisting of a binary hard-sphere mixture in a narrow cylindrical pore can lead to strong size selectivity by considering a situation where each species of the mixture sees a different radius of the cylinder. Two mechanisms are proposed to explain the observed results depending on the radius of the cylinder: for large radii the selectivity is driven by an enhancement of the depletion forces at the cylinder walls whereas for the narrowest cylinders excluded-volume effects lead to a shift of the effective chemical potential of the particles in the pore.     

Polarized absorption and anomalous temperature dependence of fluorescence depolarization in cylindrical J-aggregates

We study chiral J-aggregates of the amphiphilic dye 1A that are spontaneously and asymmetrically generated from achiral dye monomers. These aggregates occur in two types. One type possesses a threefold split J-absorption band and forms micrometer-sized superhelices. The other type has a twofold split J-absorption band and forms smaller nanoparticles. We show that the analysis of optical experiments with polarized light in terms of an exciton model yields strong indications that the smaller aggregates have a cylindrical structure as well; the lower exciton band is polarized along the cylinder axis, while the higher band is polarized perpendicular to it. Our analysis allows for an estimate of the number of molecules around the circumference of the cylinder. Fluorescence–polarization excitation spectra at room temperature confirm the cylinder model. At low temperature, these spectra reveal a surprising loss of fluorescence polarization upon excitation in the higher exciton band. Possible explanations for this observation are discussed.     

Capillary impregnation into cylinder banks

The capillary rise of liquid in a cylinder bank is examined in order to study the capillary pressure variation perpendicular to the direction of the cylinders. The calculations consider the local geometric variation of the flow channel and the position-dependent capillary pressure. The capillary flow around each cylinder is calculated by balancing the capillary pressure and the viscous drag along the flow path. The rate of filling for several layers of cylinders is used to estimate the equivalent capillary pressure. The method is also applied to the underfill of a flip chip system, which is modeled as a cylinder bank between parallel plates.     

Long flexible polymers interacting with ellipsoids, cylinders, and needles

The depletion interactions of ellipsoidal colloidal particles in a solution of long polymer chains are analyzed. Of primary concern are the limiting cases in which the ellipsoid reduces to a cylinder of infinite length and finite radius and a "needle" of finite length and vanishing radius. Relations are obtained between the polymer effects induced by a needle that is much shorter than the polymer size and by a cylinder with radius much smaller than the polymer size. These imply exact quantitative results for the orientation-dependent depletion interaction between a short needle and a wall. Qualitative differences between the needle and thin disk are discussed.     

Influence of electric field on the phase transitions of the hexagonal cylinder phase of diblock copolymers.

We have used the cell dynamic simulations (CDS) method to study the evolution of asymmetric and symmetric diblock copolymers under electric fields. For symmetric diblock copolymers, long-range-ordered lamellar phases form readily under electric fields. For asymmetric diblock copolymers, sphere-to-cylinder phase transitions occur rapidly when strong electric fields are applied, but it takes longer for the system to form hexagonal cylinder structures. The results of these simulations suggest that the sphere phase is stable under weak electric fields, but a threshold electric intensity exists for the sphere-to-cylinder phase transition. In addition, we also studied the kinetic pathways of the transition of the lamellar phase to the hexagonal cylinder phase of the asymmetric diblock copolymers under electric fields. Hexagonal cylinder structures form when the lamellar phase is subjected to a sudden temperature jump. The scattering functions suggest that the hexagonal cylinder structures are very regular and possess very few flaws.     

一种新型半导体气体传感器

气体传感器的结构形式通常有接触燃烧型、陶瓷烧结型和气敏感场效应晶体管型等。陶瓷烧结型的传感方式是基于金属氧化物半导体(如SnO₂、ZnO和γ-Fe₂O₃)吸附气体分子后表面电阻发生变化的原理来实现的^(1-3)。