多体相互作用体系中的弛豫与扩散:一个尚未解决的问题

文章目的在于引起国内研究团体对一系列复杂相互作用体系中的弛豫和扩散的普适性进行关注.研究发现,无论是不同的化学结构(如无机物、有机物、聚合物、生物分子、胶体、金属和离子导电材料),还是不同的物理状态(如晶态、玻璃态、液体、熔体、混合体系和含水系统),以及不同的尺度(如从块体至纳米),这种普适性无处不在[K.L.Ngai.Relaxation and Diffusion in Complex Systems.NewYork:Springer,2011].该现象起源于多体系统的不可逆过程,取决于一些基本物理定律,与非简谐势引发的经典混沌有关.重新认识这种普适性不仅对众多不同领域的发展有利,而且能进一步弄清楚多体系统中的弛豫与扩散问题——一个重要而又未解决的物理问题.作者提出的耦合模型尽管不是一个严格而完整的答案,但却能够预测多体系统的弛豫和扩散特征,而且与实验结果吻合.基于该模型,绝大多数多体系统中的弛豫与扩散行为是相似的.该模型有望为这一难题的彻底解决奠定基石.     

C−H?Pd interactions and cyano-bridged heteronuclear polymeric complexes

Three new heterometallic complexes, [Cu(N-Meim)₄Pd(μ-CN)₂(CN)₂]_n (1), [Zn(N-Meim)₃Pd(μ-CN)₂(CN)₂]_n (2) and [Cd(N-Meim)₂Pd(μ-CN)₄]_n (3), have been isolated from the reactions of M[Pd(CN)₄] (M = Cu(II), Zn(II) or Cd(II)) and N-Meim (N-methylimidazole) with in different molar ratios. All complexes have been characterized by X-ray analyses, vibrational (FT-IR and Raman) spectra, thermal and elemental analyses. The crystallographic analysis reveals that the crystal structures of 1 and 2 are 1D coordination polymer, while 3 presents a 2D network. In the Cu(II) and Zn(II) complexes, two cyanide groups of [Pd(CN)₄]²⁻ coordinated to the adjacent M(II) ions and distorted octahedral and square pyramidal geometries of complexes are completed by four and three nitrogen atoms of N-Meim ligands, respectively. The Cd(II) ion is six-coordinate, completed with the two nitrogen atoms of N-Meim ligands in the axial positions and the four nitrogen atoms from bridging cyano groups in the equatorial plane. The most striking features of complexes 1-3 are the presence of obvious C-H?Pd hydrogen-bonding interactions between the Pd(II) and hydrogen atoms of N-Meim ligand. This weak hydrogen bonding plays a crucial role in the architecture of the network polymers. The adjacent chains are held together by C-H?Pd, C-H?π or π?π interactions, forming three-dimensional network.     

双带频率选择表面设计

为了实现频率选择表面(FSS)的双带特性,设计了由矩形栅格和三圆环组合单元FSS。对FSS的谱域求解方法进行了详细的描述。采用谱域法分析了不同角度和极化入射波下FSS的频率响应性能。结果表明,所设计的FSS对于不同入射角度和极化电磁波具有稳定的双带、平顶传输及陡峭下降边缘特性。双带特性大致表现为1.8～5.4GHz的阻带和5.4～20.0GHz的通带。阻带谐振频率稳定在3.1GHz左右,而通带在-4dB的平顶传输带宽达14.3GHz以上。其陡峭下降边缘特性表现为S波段信号强烈反射,而其他波段信号通过,从而实现多波段通讯。该结构FSS可应用于卫星通信、雷达罩及其他相关领域。     

多晶硅不同晶面陷阱坑形貌与陷光效应的关系

提出了多晶硅表面陷阱坑内表面高次绒面的陷光模型。利用测不准原理,分析了光子散射方向与绒面上凸点大小的关系,利用光学傅里叶变换推导了光子逃逸陷阱坑概率与绒面陷阱坑形貌的关系。理论分析结果表明内表面布满凹凸点的U字形陷阱坑反射率比V字形的低;而内表面光滑的U字形陷阱坑的反射率比V字形的高。利用扫描电子显微镜拍摄了碱液刻蚀的多晶硅样品表面图像,分析了碱液刻蚀的不同晶面陷阱坑的形貌。[100]晶面呈峡谷状的陷阱坑,[111]晶面呈扭曲的U字形凹坑,[110]晶面则显示混合结构。实验测量了样品不同晶面的反射率曲线,证实了U字形陷阱坑的绒面具有相对低的反射率,与理论分析结果基本吻合。     

NbB2（0001）表面性质的第一性原理研究

应用密度泛函理论的第一性原理的方法分析了两种不同终端的NbB2(0001)表面的几何结构和电子结构。结果表明:两种不同终端的(0001)表面结构弛豫主要发生在前三层,并且硼终端的表面弛豫程度小于铌终端表面的弛豫。表面能分析结果表明,终止于硼终端的(0001)表面结构在更宽的范围内具有较低的表面能,即硼终端的(0001)表面比铌终端的表面更稳定。进一步分析NbB2(0001)两种终端表面的电子结构表明:在金属铌和硼之间发生了电子转移,加强了化学键的相互作用,导致第一间层向内弛豫。对于铌终端的表面第一层铌转移到第二层的电子数比硼终端表面第二层铌转移到第一层的电子数多,这是导致铌终端表面弛豫程度大于硼终端表面的主要原因。     

Selective response of antigen‐antibody reactions on chiral surfaces modified with 1,2‐diphenylethylenediamine enantiomers

This work reported a comparative analysis of the amperometric responses of antigen‐antibody reactions on two stable chiral surfaces which were modified with 1,2‐diphenylethylenediamine enantiomers. Alpha‐fetoprotein antibody and antigen (anti‐AFP and AFP) were selected as model systems. First, (1R,2R)‐1,2‐diphenylethylenediamine or (1S,2S)‐1,2‐diphenylethylenediamine was modified on the gold surface of the electrode through amide linkage to construct chiral surfaces. Then, anti‐AFP was immobilized on the chiral electrode surface by electrostatic and hydrogen bonding interactions. The electrochemical characteristics of the modified electrodes were studied via cyclic voltammetry. The selective current responses of antigen‐antibody reactions on chiral electrode surfaces for different incubation time and varying AFP concentrations were monitored. The antigen‐antibody reactions were greatly influenced by the chirality of 1,2‐diphenylethylenediamine enantiomers, and the amperometric responses obtained from the (1S,2S)‐1,2‐diphenylethylenediamine modified electrode was obviously stronger than that from the (1R,2R)‐1,2‐diphenylethylenediamine modified electrode. Such work may not only offer valuable reference to the research of chiral drugs, but also help to comprehend the high selectivity of chiral molecular species in biosystems. Copyright © 2011 John Wiley & Sons, Ltd.     

Self‐Assembly Studies of a Chiral Bisurea‐Based Superhydrogelator

A chiral bisurea‐based superhydrogelator that is capable of forming supramolecular hydrogels at concentrations as low as 0.2 mM is reported. This soft material has been characterized by thermal studies, rheology, X‐ray diffraction analysis, transmission electron microscopy (TEM), and by various spectroscopic techniques (electronic and vibrational circular dichroism and by FTIR and Raman spectroscopy). The expression of chirality on the molecular and supramolecular levels has been studied and a clear amplification of its chirality into the achiral analogue has been observed. Furthermore, thermal analysis showed that the hydrogelation of compound 1 has a high response to temperature, which corresponds to an enthalpy‐driven self‐assembly process. These particular thermal characteristics make these materials easy to handle for soft‐application technologies.     

The reduction of rotational ambiguity in soft-modeling by introducing hard models

Rotational ambiguity is a major problem in the application of soft-modeling analysis to a variety of multivariate mixture resolution problems and particularly important in the analysis of kinetic data. Soft-modeling analyses rely on constraints that restrict the concentration profiles and/or the spectral responses of all components. The main goal of this work is to demonstrate how a hard-modeling constraint on concentration profiles drastically decreases the extent of the rotational ambiguity. Therefore, in the present paper the discussion is focused on systems in which hard-modeling information is available. The results of simulated examples reveal that the utilized hard constraint decreases the rotational ambiguity in estimated concentration profile even components that do not take part in the explicit model. In addition, the rate constant of known reaction is determined in this method.     

Electrocatalytic Reduction and Flow Injection Analysis of Organic Peroxides at Polymeric Tetra-Amino Iron Phthalocyanine Modified Electrode

Abstract

It has been demonstrated that tetra-amino iron phthalocyanine can be polymerized onto a glassy carbon electrode by electrooxidation of the monomer in solution. Organic peroxides can be catalytically reduced at such polymeric film modified electrode. While on a bare glassy carbon electrode, none of the peroxides can be reduced within the potential range studied. When used in flow injection analysis, the modified electrode permits the detection of these compounds by reduction mechanism at higher potentials without the interference from oxygen. The response is stable and has a wide dynamic range.