Energy contribution of the solvent to the charge migration in DNA

The authors have investigated the interactions of the reaction centers, participating in the charge transfer reaction within the DNA molecule with the phosphate backbones and the solvent molecules, and have estimated the contribution of these interactions into the charge migration in DNA. They have determined the unequal shift of the energy surfaces of the initial and final transition states of the transfer reaction along the energy axis and the dependence of the magnitude of the energy shift on the nature of the reaction centers and the surrounding environment. The nonuniform distribution of the negative charge in the DNA phosphate backbones results in an increase of the positive shift of the energy surface of the DNA base pairs in the center of the structure, where the maximum density of the negative charge is concentrated. Localization of the positive charge on the guanine and the adenine in the DNA base pairs in the oxidized state results in a dependence of the free energy of reaction in the solvent on the pair sequences and their arrangement in the DNA chain. As an example, for the G-C/A-T configuration the positive charges are localized on the same strand that results in a decrease of the free energy of reaction in the solvent for charge migration from G-C to A-T pair by 0.125 eV.     

Molecular dynamics simulation studies of the conformation and lateral mobility of a charged adsorbate biomolecule: implications for estimating the critical value of the radius of a pore in porous media

The conformations, the values of the lateral transport coefficient of a charged biomolecule (desmopressin) in the adsorbed layer and in the liquid layers above the adsorbed layer, the potential energies of the interaction between the biomolecules located in different liquid layers with the charged solid surface and with the biomolecules in the adsorbed layer, the potential energies of the interaction between water molecules in the hydration layers surrounding the conformations of the biomolecules in different layers, as well as the structure and number of hydration layers between the different conformations of desmopressin, were determined by molecular dynamics simulation studies. The results show that the lateral mobility of the adsorbed desmopressin is approximately equal to zero and the value of the lateral transport coefficient of the biomolecule in the liquid layers located above the adsorbed layer increases as the distance of the liquid layer from the charged solid surface increases. But the values of the lateral transport coefficient of the biomolecule in the liquid layers above the adsorbed layer are lower in magnitude than the value of the transport coefficient of desmopressin along the direction normal to the charged solid surface in the liquid phase located above the vacant charged sites of the solid surface, and these differences in the values of the transport coefficients have important implications with respect to the replenishment of the biomolecules in the inner parts of a channel (pore), the overall rate of adsorption, and the form of the constitutive equations that would have to be used in macroscopic models to describe the mechanisms of mass transfer and adsorption in the pores of adsorbent media. Furthermore, a novel method is presented in this work that utilizes the information about the sizes of the conformations of the biomolecule in the adsorbed layer and in the liquid layers above the adsorbed layer along the direction that is normal to the charged solid surface, as well as the number and size of the hydration layers along the same direction, and could be used to estimate the value of the lower bound of the linear characteristic dimension of a pore (i.e., pore radius) in porous adsorbent media (e.g., porous adsorbent particles; skeletons of porous monoliths) in order to realize effective transport and overall adsorption rate.     

Dynamics of electric field induced deformations in flexoelectric nematic layers

The dynamics of deformations induced by DC electrical fields in homeotropically aligned layers containing a flexoelectric nematic material with negative dielectric anisotropy has been studied numerically. The rise time constants, characterising the development of deformations after switching on the external voltage, and the decay time constants, describing the decay of deformation after switching off the voltage, were calculated as a function of the parameters essential for the behaviour of the layer. In particular, the influence of flexoelectricity was studied. It was found that the stronger the flexoelectric properties of the nematic, the lower is its viscosity, the higher is the bias voltage, the weaker is the surface anchoring, the thinner is the layer and the higher is the ion concentration, the more rapid was the onset of deformation. Similarly, the lower the viscosity, the thinner is the layer, the stronger the anchoring and the larger the ion content, the more rapid was the decay of deformation. Neither the voltage previously applied nor the flexoelectric properties were found to affect the decay time.     

Modeling of the trajectories of the hydrogen bubbles evolving from the cathode in a fluorine production cell

The fluid velocity and temperature fields and the trajectories of the hydrogen bubbles evolving from the cathode in a fluorine production cell were studied by using the finite element method. It was examined the effect of the configuration of the slits formed on the cathode on the escape of the hydrogen bubbles toward the backside of the cathode to reduce the ohmic voltage loss between the electrodes. The results showed that the cathode configuration has a profound effect on both of the flow pattern near the cathode and the bubble trajectories. It was found that the cathode with the slits only on the upper half of the electrode is more effective in removing the bubbles to the backside of the cathode than the one with the slits over the entire electrode.     

高分子链在球内表面上的吸附/排空转变

应用自洽场理论(SCFT)研究了受限于球内的高分子溶液的结构,重点关注高分子链在受限壁附近的行为.根据自洽场理论数值计算结果,讨论了球半径、高分子与球限制壁的相互作用、高分子平均浓度等因素对球内高分子浓度分布的影响.从高分子浓度分布和吸附/排空层厚度可以发现,在一定的条件下,受限的高分子在受限壁上会发生吸附/排空转变.吸附/排空转变与受限球大小、高分子链长和平均浓度,以及高分子链与受限壁之间相互作用都有关系.理论预测发生吸附/排空转变时的高分子与球限制壁的临界相互作用参数与链长的倒数成线性关系,且斜率与球半径有关.限制球越小,要发生吸附/排空转变,需要高分子与球之间有更大的临界吸引能.     

The effect of spacer length on the polymerization of diacetylenes in sams on gold surfaces

The influence of the molecular architecture of diacetylene disulfides on the structure and polymerizability of self assembled monolayers on gold was investigated. The position of the diacetylene group was varied systematically by adjusting the length of the tail and the spacer. For the structures studied, the longer the tail, the higher the akyl chain crystallinity as sensed by IR spectroscopy, and the higher the polymerization efficiency as probed by resonance Raman spectroscopy. The influence of the spacer on the polymerizability is more complicated. It is conjectured that the spacer reduces the lattice strain due to the misfit of the arrangement of the anchor groups and the arrangement of the diacetylene units and the polydiacetylene backbone, respectively. Simple modeling reveals that the number of the methylene units (odd or even) and the overall length both influence the arrangement. The highest polymerization efficiency is found for the longest, odd numbered spacer.     

启动工况下质子交换膜燃料电池动态性能仿真分析

本文以等效电路模型为基础模型,结合动态气体压力模型和动态热传输模型建立了集总参数模型,在SIMULINK环境下,利用建立的模型模拟了电池启动过程,发现了电压的下冲现象,且电压的响应时间与电池温度的响应时间基本一致,说明启停过程中电池温度对电池的动态性能影响很大. 进一步从温度角度对模型中决定电池输出电压大小的热力学电动势、活化过电势、欧姆过电势和浓差过电势的动态响应情况进行了分析,发现启动过程电压的下冲现象主要由电池活化过电势和欧姆过电势的过冲引起;当以阶跃信号形式输入温度时,启动过程电池输出电压响应很快且未发生下冲现象,说明提高电池温度的响应速度能够改善电池的动态性能.     

Electrically driven motion of an air bubble on hemispherical oil/water interface by three-phase boundary reactions

Our electrochemical cell consisted of a ferrocene-included hemispherical nitrobenzene (NB) droplet on the glassy carbon (GC) electrode which was immersed in the aqueous solution including sodium sulfate and sodium dodecyl sulfate (SDS). When an air bubble was injected near the boundary between the oil and the aqueous phase, it stayed at the top of the hemisphere on the boundary so that the lower half of the bubble was put in oil and the other half was in water. From the force balance of surface tension and buoyancy of the bubble, the bubble took an energetic minimum at the interface. It sank into the oil phase when ferrocene in the oil was electrochemically oxidized through the GC electrode by the three-phase boundary reaction. The electrochemical reduction caused the bubble to move back toward the aqueous phase. The motion of the bubble was synchronized with the redox reaction of ferrocene. The potential step oxidation showed such a rapid response that the motion could not be attributed to diffusion of ferricenium ion from the three-phase boundary to the bubble. Our idea of explaining the rapidity was the translational motion of the SDS layer along the boundary, which was driven by the difference in the surface concentration of SDS caused by the electrochemical generation of the ferricenium ion. The motion of the SDS layer was demonstrated by the shrinkage of the oil layer spread on the water surface when SDS solution was dropped on the oil layer. The spreading velocity was close to the velocity of propagating the oxidation of ferrocene to the bubble.     

Release of lysozyme from the branched polyelectrolyte-lysozyme complexation

On the basis of the discretely charged sphere model of lysozyme, the release behavior of lysozyme from the branched polyelectrolyte-lysozyme complexation is investigated by adding salt and changing the pH values of the solution. It is found that, with the increase of the salt ionic strength of the solution, the lysozymes are gradually released from the oppositely charged polyelectrolyte as a result of the screening of electrostatic attraction between the two ionic species by adding the salt. Interestingly, there exists a critical salt ionic strength at which all proteins are released from the branched polyelectrolyte, and the polyelectrolyte-protein complexation is broken completely. Beyond the critical value, the increase of the salt ionic strength causes self-association of the proteins released from the branched polyelectrolyte-protein complexation. The self-association of the protein is detrimental in biological systems. By calculating the second virial coefficient, we found that the optimal salt content for the dispersion of proteins coincides with the critical ionic strength, because the second virial coefficient reaches its maximum at the critical ionic strength. Similarly, increasing the pH value of the solution can also release the lysozymes from the polyelectrolyte, because the increase of pH value of the solution changes the charge distribution and net charge of the lysozyme, weakens the attraction between lysozymes mediated by polyelectrolyte, and finally leads to the dissolution of the complexation of branched polyelectrolyte with lysozymes in strong alkaline solution. In addition, by exploring the effect of architecture of the polyelectrolyte on the release behavior of proteins, we found that it is more difficult to release proteins from the branched polyelectrolyte than from the linear polyelectrolyte.     

高压离子交换排代法富集锂同位素(Ⅰ)——精馏型平衡塔板理论在富集同位素中的应用

本文根据精馏型平衡塔板理论推导出富集系数很小和有限带长时的同位素稳定谱带理论方程组,并对某些具体情况进行了分析。     

Hydrogen bond and halogen bond inside the carbon nanotube

The hydrogen bond and halogen bond inside the open-ended single-walled carbon nanotubes have been investigated theoretically employing the newly developed density functional M06 with the suitable basis set and the natural bond orbital analysis. Comparing with the hydrogen or halogen bond in the gas phase, we find that the strength of the hydrogen or halogen bond inside the carbon nanotube will become weaker if there is a larger intramolecular electron-density transfer from the electron-rich region of the hydrogen or halogen atom donor to the antibonding orbital of the X-H or X-Hal bond involved in the formation of the hydrogen or halogen bond and will become stronger if there is a larger intermolecular electron-density transfer from the electron-rich region of the hydrogen or halogen atom acceptor to the antibonding orbital of the X-H or X-Hal bond. According to the analysis of the molecular electrostatic potential of the carbon nanotube, the driving force for the electron-density transfer is found to be the negative electric field formed in the carbon nanotube inner phase. Our results also show that the X-H bond involved in the formation of the hydrogen bond and the X-Hal bond involved in the formation of the halogen bond are all elongated when encapsulating the hydrogen bond and halogen bond within the carbon nanotube, so the carbon nanotube confinement may change the blue-shifting hydrogen bond and the blue-shifting halogen bond into the red-shifting hydrogen bond and the red-shifting halogen bond. The possibility to replace the all electron nanotube-confined calculation by the simple polarizable continuum model is also evaluated.     

Syntheses, structural properties, and charge-transfer complexes of pyrenophanes

Dithia[3.3](4,9)benzenopyrenophanes carrying various functional groups at the inner position or the outer position of the benzene ring have been prepared. The pyrenophanes with the substituent at the inner position of the opposite benzene ring exhibit the conformation in which the pyrene and the benzene components exist in the parallel manner (parallel conformation). On the contrary the conformation characterized by the perpendicular orientation of the pyrene and the benzene components has been confirmed for the pyrenophanes having the substituent at the outer position of the opposite benzene ring (perpendicular conformation). The NH-pi interaction between the inner amino group on the opposite benzene ring and the pyrene ring was observed. Formation of charge-transfer complexes of the pyrenophanes and tetracyanoethylene (TCNE) was performed. It has been found out that the orientation of two aromatic components and the NH-pi interaction as well as the electronic nature of the substituent on the opposite benzene ring significantly affect characteristics of the charge-transfer complexes in this pyrenophane system.     

脉冲激光溅射下固液界面生长的碳纳米管及其机理初探

以脉冲激光束直接溅射浸在水中的单质碳样品，发现在固液界而也能产生碳纳米管．实验还发现碳纳米管的形成与样品的结构有密切的关联：石墨的层状结构越完整，碳纳米管的形成越容易，而且石墨层而相对于激光束的取向也会显著地影响碳纳米管的生成．通过对实验结果的分析，探讨了激光液相溅射产生碳纳米管的机理，认为激光溅射产生的碳蒸气被水束缚在固液的界而内，而完整的晶而使碳蒸气在界而内的分布具有准二维的性质，为碳纳米管的生长提供了较为理想的环境．     

Direct observation of protein motion during the photochemical reaction cycle of bacteriorhodopsin

Platinum-coated, conductive atomic force microscope cantilevers were used to deposit electrophoretically purple membranes from Halobacterium salinarum on the bottom part of the cantilevers. By illuminating the bacteriorhodopsin-containing purple membranes, the protein goes through its photochemical reaction cycle, during which a conformational change happens in the protein, changing its shape and size. The size change of the protein acts upon the cantilever by causing its deflection, which can be monitored by the detection system of the atomic force microscope. The shape of the signal, the action spectrum of the deflection amplitude, and the blue light inhibition of the deflection all prove that the origin of the signal is the conformational change arising in the bacteriorhodopsin during the photocycle. From the size of the signal, the magnitude of the protein motion could be estimated. Using polarized light, the orientation of the motion was determined, relative to the transition moment of the retinal.     

Liquid drainage in single plateau borders of foam

This paper reports on an investigation of the influence of the interfacial shear viscosity on the liquid drainage in single Plateau borders of foam. The simplified Navier-Stokes equation governing the liquid flow is solved for the liquid velocity by the numerical computational method. The numerical results show significant influence of the interfacial shear viscosity on the liquid velocity in the Plateau border. Comparison of the numerical results for the average velocity over the cross-section area of the Plateau border to the available analytical solution shows that the available analytical solution underestimates the average velocity. New, simple yet accurate correlations for the dependence of the average velocity on the radius of the cross section of the Plateau border, the pressure gradient, and the interfacial shear viscosity are obtained using the asymptotic analysis and the numerical data.     

An ESR spin-label study on molecular mobility in the interface between microphases of a diblock copolymer: effects of admixture of homopolymers that are miscible with one of the blocks

Molecular mobility in the interfacial region of a microphase-separated structure was studied in binary mixtures of AB-type diblock copolymers and homopolymers (miscible with only A) by the spin-label technique. In this study, we prepared (a) binary blends of polystyrene-block-poly(methyl acrylate) (PS-block-PMA) and homopolymer poly(cyclohexyl acrylate)'s having the number-averaged molecular weight (Mn) of 1000 (PCHA-S) and (b) having the Mn of 17300 (PCHA-L), and (c) binary mixtures of the PS-block-PMA and homopolymer PS with the Mn of 900 (PS-1). Emphasis was placed on effects of the molecular weight and the miscibility of added homopolymers on the mobility in the interfacial region of the microphase separation. Selective incorporation of the added PCHA-S, PCHA-L, and PS-1 into the PS phase of the PS-block-PMA was confirmed by modulated-temperature differential scanning calorimetry (MDSC) measurement as a decrease in the glass transition temperature of the PS phase. Moreover, the MDSC and small-angle X-ray scattering (SAXS) measurements suggested that the spatial distributions of the PCHA-S and PS-1 in the PS phase were relatively uniform because of their small Mn. On the other hand, the distribution of the PCHA-L in the PS phase was somewhat heterogeneous because of the large Mn of the PCHA-L. The spin-label at the junction point of the PS-block-PMA allowed us to estimate the mobility in the interfacial region of the microphase separation. Influence of the PCHA-S and PCHA-L on the mobility in the interfacial region was negligible even though the relatively uniform distribution of the PCHA-S in the PS phase was suggested by the SAXS and MDSC. More uniform distribution of the PS-1 than that of the PCHA-S in the PS phase was suggested by the SAXS, and the mobility in the interfacial region was slightly enhanced by the addition of the PS-1. However, the mobility was almost constant against an increase in the PS-1. The PS-1 was considered to be penetrated into the interfacial region and activated the mobility, but the fraction of the PS-1 in the interfacial region was constant irrespective of the blended amount of the PS-1. These results suggest that effects of homopolymers on the mobility in the interface are significantly related to their spatial distribution in the host phase.     

3-D transient electrophoretic motion of a spherical particle in a T-shaped rectangular microchannel

This paper considers the electrophoretic motion of a spherical particle in an aqueous electrolyte solution in a T-shaped rectangular microchannel, where the size of the channel is close to that of the particle. This is a complicated transient process where the electric field, the flow field, and the particle motion are coupled together. A theoretical model was developed to investigate the influences of the applied electric potentials, the zeta potentials of the channel and the particle, and the size of the particle on the particle motion. A direct numerical simulation method using the finite element method is employed. This method employs a generalized Galerkin finite element formulation that incorporates both equations of the fluid flow and equations of the particle motion into a single variational equation where the hydrodynamic interactions are eliminated. The ALE method is used to track the surface of the particle at each time step. The numerical results show that the electric field in the T-shaped microchannel is influenced by the presence of the particle, and that the particle motion is influenced by the applied electric potentials and the zeta potentials of the channel and the particle. The path of the particle motion is dominated by the local electric field and the ratio of the zeta potential of the channel to that of the particle. The particle's velocity is also dependent on its size in a small channel.     

吸附剂性能和操作参数对液相色谱流出峰不对称性的影响

色谱流出峰的拖尾现象普遍存在于制备和大型色谱分离过程中,它直接影响分离的产率和回收率．本文提出采用色谱流出峰形的不对称偏差度来表征色谱流出峰的拖尾程度;并基于液相制备色谱分离过程FAD－SMT模型及吸附速率理论,通过计算机模拟,定量分析了吸附剂性能和操作参数对色谱流出峰形不对称性的影响。结果表明：不仅是吸附剂的热力学和动力学性能（包括吸附相平衡关系、液固两相间的传质阻力）;而且柱的设计和吸附剂的装填状况（包括轴向扩散系数）,以及色谱分离的操作条件（进料时间、浓度和流速等）都直接影响色谱流出峰形的不对称性。随着吸附相平衡等温线的非线性程度增大,或者总传质系数的减小,色谱流出峰形的不对称偏差度明显增大;吸附剂吸附容量的减小也将引起色谱流出峰形的不对称偏差度的增加;色谱流出峰形的不对称偏差度与进科体积、浓度和流体线速,以及轴向扩散系数的增大成正比。     

Orbital interpretation of kinetic energy density and a direct space comparison of chemical bonding in tetrahedral network solids

We present how the kinetic energy density (KED) can be interpreted on the basis of the orbital interactions within the Kohn-Sham theory and propose how to utilize a direct space function in chemical bonding analysis, the relative entropy density (RED), which is constructed from the KED, the Thomas-Fermi KED (TF-KED), and the electron density. From the detailed analysis of the KED of wave functions and the TF-KED from the free electron model, it is shown that the RED can reveal the nodal properties of individual wave functions and provide a variationally meaningful way of accumulating chemical bonding information from the wave functions, hence allowing quantitative bonding analysis in direct space. To substantiate the proposal, the RED function has been tested on the tetrahedral network solids, including the group 14 elements and the III-V binary compounds with the zinc blende structure. The direct space maps of the RED quantitatively reflect the trend in metallicity and the polarity of their two-center, two-electron bonds in terms of the absolute values of the RED, the location of the minimum values, and the behavior of the deformation from the spherical symmetry of the atomic RED.     

Aging properties and mechanism of the modified asphalt by packaging waste polyethylene and waste rubber powder

For the consideration of the environmental and economic issues, retrieved packaging waste polyethylene and waste rubber powder were selected as modifiers to modify the ordinary oil asphalt, and the rotating film oven test was adopted to study the aging process of the modified asphalt. The results showed that the performance of the modified asphalt deteriorated, as indicated by the increase in the softening point and the reduced ductility and penetration. However, compared with nonmodified asphalt, the rangeability of the performance indicators of the modified asphalt before and after aging became narrow, indicating that the aging properties of the modified asphalt were improved. In the modified asphalt system, the swelling of the polymer modifiers was caused by the absorption of the light components of the asphalt, thereby reducing the formation of asphaltenes in the aging process. The polymer modifiers absorb the light oil of the asphalt, which can reduce the content of free radicals and improve the aging properties of the asphalt. In addition, the waste rubber power containing antioxidants and anti‐ozone agents effectively improves the antiaging properties of the asphalt. Copyright © 2012 John Wiley & Sons, Ltd.