建立在群对称轨道（SMO）及特征组态（CD）基础上的线性分子 …

定义和讨论了线性分子的群以称轨道（ＳＭＯ）及特征组态函数（ＣＤ）它能够在线性分子的分子轨道与组态函数进行简单而完全的对称分类，ＳＭＯ－ＣＤＣＩ方法是一种高效的计算方法，大大节省了线性分子ＣＩ计算的机时与内存。     

双核金属酞菁类化合物催化脱硫机理研究Ⅳ──中心金属离子对MPc－PcM催化活性的影响

实验研究结果表明双核金属酞菁类化合物ＭＰｃ－ＰｃＭ（Ｍ＝Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ）是催化Ｈ＿２Ｓ液相氧化反应的良好催化剂，且其催化活性顺序为Ｃｏ＞Ｎｉ＞Ｖ＞Ｆｅ＞Ｃｕ＞Ｃｒ＞Ｍｎ．采用量子化学理论计算方法（ＩＮＤＯ／Ｓ）分析了其前线分子轨道的构成特征，结果表明这几种ＭＰｃ－ＰｃＭ的ＬＵＭＯ轨道皆为有金属离子参与形成的π轨道，但ＨＯＭＯ轨道间的差异却很大．Ｍ＝Ｃｏ、Ｎｉ、Ｃｕ、Ｃｒ时，其ＨＯＭＯ为π轨道；而Ｍ＝Ｆｅ、Ｍｎ时，其ＨＯＭＯ却为σ轨道．正是在前线分子轨道的轨道类型、共轭程度及金属轨道贡献三方面因素的协同作用下，才导致ＭＰｃ－ＰｃＭ的催化活性顺序并非按中心金属离子价电子层ｄ电子数的递变而呈现出规律性的变化．     

S_2N_2环夹心配合物的MO研究

根据ＭＡＤ－ＳＣＣ－ＥＨＭＯ法的计算结果,用衡量相对稳定性的三个指标：稳定化能、ＨＯＭＯ－ＬＵＭＯ能隙和重迭集居比较了无机环Ｓ２Ｎ２与有机环的夹心和半夹心配合物的相对稳定性,并用碎片分子轨道法讨论了Ｓ２Ｎ２环分子轨道与过渡金属ｄ轨道间的相互作用以及配合物的成键情况和电子结构．     

双核锰化合物的定域分子轨道研究

利用ＩＮＤＯ和Ｅｄｍｉｓｔｏｎ－Ｒｕｅｄｅｎｂｅｒｇ定域化方法，计算了Ｍｎ２（μ－Ｃｌ）２（ＣＯ）８和Ｍｎ２（ＣＯ）１０的正则和定域分子轨道，给出了它们的成键图象，讨论了Ｍｎ－Ｍｎ原子间相互作用以及不同方式配位的ＣＯ化学键和几何结构的关系。     

钌(Ⅱ)联吡啶配合物cis-[Ru~Ⅱ(bpy)_2(L)_2]的配体取代效应(CNDO/2)

用ＣＮＤＯ／２方法经ＳＣＦ计算获得了钌（Ⅱ）联吡啶配合物ｃｉｓ－［ＲｕⅡ（ｂｐｙ）２（Ｌ）２］的电子结构（其中ｂｐｙ＝２，２′－二联吡啶；Ｌ＝Ｃｌ－，ＮＣＳ－，ＣＮ－，ＮＨ３，ＮＣＣＨ３）．计算结果表明，这些钌（Ⅱ）联吡啶配合物的ＬＵＭＯ均定域于配体ｂｐｙ的最低能π轨道，而其ＨＯＭＯ均定域于中心钌（Ⅱ）原子的ｄπ轨道．随着配体Ｌ的σ电子给予能力的增强，对应配合物的ＨＯＭＯ能级相应增大，ＬＵＭＯ能级亦有所增大，两者之差值则降低．这些钌（Ⅱ）联吡啶配合物的ＨＯＭＯ和ＬＵＭＯ能级变化趋势分别与相应的第一氧化和第一还原电势变化趋势相同，并且ＨＯＭＯ和ＬＵＭＯ能级与其光谱最低吸收能和第一氧化还原电势呈现出很好的线性相关性．计算结果与实验数据相吻合．     

ESTLMATION OF THE pH VALUES OF ACIDIC SURFACE WATERS BY CHEMICAL EQUILIBRIUM CALCULATION

ＥＳＴＬＭＡＴＩＯＮＯＦＴＨＥｐＨＶＡＬＵＥＳＯＦＡＣＩＤＩＣＳＵＲＦＡＣＥＷＡＴＥＲＳＢＹＣＨＥＭＩＣＡＬＥＱＵＩＬＩＢＲＩＵＭＣＡＬＣＵＬＡＴＩＯＮ￥ＳｈｕＰｉｎｇＢＩ（ＣｈｅｍｉｓｔｒｙＤｅｐａｒｔｍｏｎｔ．ＮａｎｊｉｎｇＵｎｉｖｅｒｓｉｔｙ，...     

STUDIES ON THE ANIONIC SPECIES OF SODIUM ALUMINATE SOLUTIONS OF LOW CAUSTIC RATIOS

ＳＴＵＤＩＥＳＯＮＴＨＥＡＮＩＯＮＩＣＳＰＥＣＩＥＳＯＦＳＯＤＩＵＭＡＬＵＭＩＮＡＴＥＳＯＬＵＴＩＯＮＳＯＦＬＯＷＣＡＵＳＴＩＣＲＡＴＩＯＳ￥ＹｉＬｉｎＣＡＯ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ，ＨｅｎａｎＮｏｒｍａｌＵｎｉｖｅｒｓｉｔｙ，Ｘ...     

STUDIES ON THE CRINUM ALKALOIDS PART I: SYNTHESIS OF ANHYDROLYCORINE-7-ONE

ＳＴＵＤＩＥＳＯＮＴＨＥＣＲＩＮＵＭＡＬＫＡＬＯＩＤＳＰＡＲＴＩ：ＳＹＮＴＨＥＳＩＳＯＦＡＮＨＹＤＲＯＬＹＣＯＲＩＮＥ－７－ＯＮＥＨｕａＷｕＳＨＡＯ；ＪｕｎＣｈａｏＣＡＩ（ＳｈａｎｇｈａｉＩｎｓｔｉｔｕｔｅｏｆＭａｔｅｒｉａＭｅｄｉｃａ，Ｃｈｉｎｅｓ...     

C_(19)-DITERPENOID ALKALOIDS OF DELPHINIUM MOLLIPILUM

Ｃ_（１９）－ＤＩＴＥＲＰＥＮＯＩＤＡＬＫＡＬＯＩＤＳＯＦＤＥＬＰＨＩＮＩＵＭＭＯＬＬＩＰＩＬＵＭ￥ＳｕｏＭｉｎｇＺＨＡＮＧ；ＱｉｎｇＹｕＯｕ（ＬａｎｚｈｏｕＩｎｓｔｉｔｕｔｅｏｆＣｈｅｍｉｃａｌＰｈｙｓｉｃｓ，ＣｈｉｎｅｓｅＡｃａｄｅｍｙｏｆＳｃｉ?..     

CO_2 HYDROGENATION OVER SiO_2－SUPPORTED HETEROBINUCLEAR METAL COMPLEX CATALYSTS

ＣＯ_２　ＨＹＤＲＯＧＥＮＡＴＩＯＮ　ＯＶＥＲ　ＳｉＯ_２－ＳＵＰＰＯＲＴＥＤ　ＨＥＴＥＲＯＢＩＮＵＣＬＥＡＲ　ＭＥＴＡＬ　ＣＯＭＰＬＥＸ　ＣＡＴＡＬＹＳＴＳＣｈａｎｇＰｉｎｇＳＨＡＯ（ＤａｌｉａｎＩｎｓｔｉｔｕｔｅｏｆＣｈｅｍｉｃａｌＰｈｙｓｉｃｓ，...     

Optimal group symmetric localized molecular orbitals

Summary The concept and generating method of optimum group symmetric localized molecular orbitals (OSLMOs) are proposed. The OSLMOs have strong points of orthogonality, equivalence and symmetry, and they are simultaneously as close to the classical VB structure as possible. By using the OSLMOs as one-electron orbitals the multiconfigurational correlation calculations are reduced. The scheme is also a valuable popularization and development to hybridization theory.     

大体系多电子相关研究中应用群对称定域轨道的构想

大体系多电子相关研究中应用群对称定域轨道的构想周泰锦，刘爱民（厦门大学化学系，厦门３６１００５）关键词：组态相关，多构型自治叠代，多中心积分，群对称定域轨道，对称约化有关原子簇化合物及化学吸附、过渡态、激发态、催化反应等大体系的量子化学研究，对于探讨...     

Review of Analytical Methods for Atmospheric Oxidants Measurements

Abstract

Instrumental and manual methods currently available for the measurement of atmospheric oxidants are surveyed. Techniques used in the United States are emphasized and their advantages and disadvantages are discussed. Commercial systems are evaluated in terms of general operating principles rather than of specific instruments. The ability of these techniques to meet the measurement requirements defined by U.S. Federal air quality oxidant criteria are discussed. Alternative chemical techniques that may have some advantages over the neutral, buffered KI procedure are discussed. Also some attractive, alternative instrumental procedures that are ozone-specific are presented. These systems are based on chemiluminescence and ultraviolet absorption photometry. Electrochemical and colorimetric methods for total oxidant measurements are compared. Finally, some data are presented on relationships of ozone and total oxidants.     

The Application of NMR Spectroscopy and Chemometrics in Authentication of Spices

Spices and herbs are among the most commonly adulterated food types. This is because spices are widely used to process food. Spices not only enhance the flavor and taste of food, but they are also sources of numerous bioactive compounds that are significantly beneficial for health. The healing effects of spices are connected with their antimicrobial, anti-inflammatory and carminative properties. However, regular consumption of adulterated spices may cause fatal damage to our system because adulterants in most cases are unhealthy. For that reason, the appropriate analytical methods are necessary for quality assurance and to ensure the authenticity of spices. Spectroscopic methods are gaining interest as they are fast, require little or no sample preparation, and provide rich structural information. This review provides an overview of the application of NMR spectroscopy combined with chemometric analysis to determine the quality and adulteration of spices.     

Densities,speeds of sound,excess volumes and viscosities of binary mixtures of mtbe with tetralin and decalin at 303.15 k

Measurements of densities, speeds of sound, excess volumes and viscosities of binary mixture of methyl tert-butyl ether with tetralin and decalin are reported at 303.15?K over the entire range of composition. Excess volumes are measured using batch dilatometer technique. Sound speeds are obtained using ultrasonic interferometer. Densities are computed from excess volume data. Isentropic compressibilities are derived from density and sound speed data. Speeds of sound are evaluated on the basis of Jacobson's free length theory and Schaff's collision factor theory. The predicted values are in good agreement with the experimental results. The viscosity data are analysed on the basis of corresponding states approach. Excess volumes and deviation in isentropic compressibilities are negative and deviation in viscosities are positive over the entire composition range. The experimental results are discussed in terms of possible molecular interactions between unlike molecules.     

钼、钨系过氧化物在Sharpless烯烃环氧化反应中的应用*

钼、钨系过氧化物是非常重要的Sharpless烯烃环氧化催化剂,有着非常广泛的工业发展前景。本文综述了钼、钨系过氧化物的种类,结构,合成方法及催化活性,分析了各种钼、钨系过氧化物的特点以及在催化环氧化领域的发展现状。同时,本文还讨论了钼、钨系过氧化物催化烯烃环氧化反应的机理。评述了在催化环氧化领域中两种主要理论——Mimoun机理与Sharpless机理的争论焦点及发展现状,以及计算化学对两种理论中间过渡态的研究进展,并且重点分析了Sharpless机理的过渡态结构。此外,本文还综述了影响钼、钨系过氧化物催化剂反应活性的各种因素以及质子所产生的副反应。最后,本文对应用于催化环氧化领域的钼、钨系过氧化物未来的研究方向提出了建议。     

Contactless conductivity detection for microfluidics: designs and applications

Different methods for construction of contactless conductivity detectors (CCD) for microchip electrophoresis device are described in this review. This includes three main schemes of CCD for microchips, such as (i) the detection electrodes are placed along the microchannel from outside of the microchip and they are insulated from the channel by the cover lid of microchip device; (ii) the electrodes are placed across of the microchannel in the same plane and they are insulated by thin separation channel walls and (iii) electrodes are buried in widened part of microchannel and they are insulated from solution by ultrathin layer of silicon carbide. Specific issues related to the CCD on microfluidics are discussed, such as an influence of shape and magnitude of ac voltage and placement of electrodes and their insulation. Various applications for security, pharmacological, bioassays and food analysis purposes are described.     

Surface Reconstruction by a Coassembly Approach

Materials with switchable surfaces, capable of changing surface properties under external stimuli, are playing a pivotal role in many applications, such as tissue engineering, biosensors, and drug/protein delivery. In this research silica particles with patterned and switchable surfaces are fabricated. Surface micelles on silica particles are formed by coassembly of polymer brushes and “free” block copolymer chains in a selective solvent. The cores of the surface micelles are crosslinked by anthracene photodimerization. After quaternization of the coronae, amphiphilic surface micelles are prepared. The surface micelles are able to rearrange in different media. After treatment with an organic solvent, the surfaces of silica particles are occupied by hydrophobic polymer components; in aqueous solution, the positively charged polymer chains are on the surfaces. The switching of the surface micelles results in changes in surface composition and wetting behaviors.     

Structure and growth of self-assembling monolayers

The structural phases and the growth of self-assembled monolayers (SAMs) are reviewed from a surface science perspective, with emphasis on simple model systems. The concept of self-assembly is explained, and different self-assembling materials are briefly discussed. A summary of the techniques used for the study of SAMs is given. Different general scenarios for structures obtained by self-assembly are described. Thiols on Au(1 1 1) surfaces are used as an archetypal system to investigate in detail the structural phase diagram as a function of temperature and coverage, the specific structural features on a molecular level, and the effect of changes of the molecular backbone and the end group on the structure of the SAM. Temperature effects including phase transitions are discussed. Concepts for the preparation of more complex structures such as multi-component SAMs, laterally structured SAMs, and heterostructures, also with inorganic materials, are outlined. The growth and ways to control it are discussed in detail. Solution and gas phase deposition and the impact of various parameters such as temperature, concentration (in solution) or partial pressure (in the gas phase) are described. The kinetics and the energetics of self-assembly are analyzed. Several more complex issues of the film formation process including non-equilibrium issues are discussed. Some general conclusions are drawn concerning the impact of various molecular features on the growth behavior and concerning the relationship between growth and structural phase diagram. Finally, the potential of self-assembly as a route for the preparation of monolayers with pre-designed properties and SAMs as building blocks in heterostructures as well as application strategies are discussed.