Web service infrastructure for chemoinformatics

The vast increase of pertinent information available to drug discovery scientists means that there is a strong demand for tools and techniques for organizing and intelligently mining this information for manageable human consumption. At Indiana University, we have developed an infrastructure of chemoinformatics Web services that simplifies the access to this information and the computational techniques that can be applied to it. In this paper, we describe this infrastructure, give some examples of its use, and then discuss our plans to use it as a platform for chemoinformatics application development in the future.     

μ-氧-双四苯基卟吩合铁(Ⅲ)在CH_2Cl_2-氧化剂体系中的转化反应研究

本文报道了以CH_2Cl_2为溶剂,μ-氧-双四苯基卟吩合铁(Ⅲ)[(TPPFe)_2O]分别在亚碘酰苯(PhIO),H_2O_2和空气氧存在下转化为氯合、四苯基卟吩合铁(Ⅲ)(TPPFeCl)的反应.动力学初步研究表明在H_2O_2或PhIO存在下对(TPPFe)_2O为一级反应,而在空气氧中则为零级反应.反应速率常数与反应温度的关系符合Arrhenius方程式.根据动力学数据提出了该反应的可能机理.     

Emerging pollutants, and communicating the science of environmental chemistry and mass spectrometry: pharmaceuticals in the environment

While this paper is to a large degree targeted for those not familiar with mass spectrometry, [for an overview of mass spectrometry, a number of excellent websites are available, including http://base-peak.wiley.com/links/Resources/Educational_Resources/], the primary focus is on the importance of mass spectrometry in ultimately protecting public health and minimizing risks of chemical exposure. Its other audience is those who practice in this specialized field. Should this subject not interest you, by reading this article you can discover among other things, why elevator rides can be important for your career and for your discipline. Why acetaminophen is used for brown tree snakes, or lipid-lowering drugs for pigeons.     

全盘自动化气相色谱仪单纯形寻优

自行研制的全盘自动化气相色谱仪在通用计算机的支持下,通过单纯形自动寻优,在色谱专家水平上建立了分析样品的最佳气相色谱分析方法。     

The three-dimensional model for helical columns on type-J synchronous counter-current chromatography

Unlike the existing 2-D pseudo-ring model for helical columns undergoing synchronous type-J planetary motion of counter-current chromatograph (CCC), the 3-D "helix" model developed in this work shows that there is a second normal force (i.e. the binormal force) applied virtually in the axial direction of the helical column. This force alternates in the two opposite directions and intensifies phase mixing with increasing the helix angle. On the contrary, the 2-D spiral column operated on the same CCC device lacks this third-dimensional mixing force. The (principal) normal force quantified by this "helix" model has been the same as that by the pseudo-ring model. With β>0.25, this normal centrifugal force has been one-directional and fluctuates cyclically. Different to the spiral column, this "helix" model shows that the centrifugal force (i.e. the hydrostatic force) does not contribute to stationary phase retention in the helical column. Between the popular helical columns and the emerging spiral columns for type-J synchronous CCC, this work has thus illustrated that the former is associated with better phase mixing yet poor retention for the stationary phase whereas the latter has potential for better retention for the stationary phase yet poor phase mixing. The methodology developed in this work may be regarded as a new platform for designing optimised CCC columns for analytical and engineering applications.     

A method for the consistent production of high quality antisera to small peptide hormones

Conclusion The high success ratio of this method for production of high quality antisera against several small peptides, suggests that this method may be useful for other small antigens. Successful preliminary results with prostaglandine E and thyroxine support this assumption.Supported by the Deutsche Forschungsgemeinschaft (grant We608/3 and SFB 51)     

Catalytic,Mild, and Selective Oxyfunctionalization of Linear Alkanes: Current Challenges

Selective catalysts for sustainable oxidation of alkanes are highly demanded because of the abundance of these molecules in the environment, the possibility to transform them into higher‐value compounds, such as chemicals or synthetic fuels, and the fact that, kinetically speaking, this is a difficult reaction. Numerous chemical and biological catalysts have been developed in the lasts decades for this purpose, rendering the overview over this field of chemistry difficult. After giving a definition of the ideal catalyst for alkane oxyfunctionalization, this review aims to present the catalysts available today that are closest to ideal.     

Adsorption of xenon on purified HiPco single walled carbon nanotubes

We have measured adsorption of xenon on purified HiPco single-walled carbon nanotubes (SWNTs) for coverages in the first layer. We compare the results on this substrate to those our group obtained in earlier measurements on lower purity arc-discharge produced nanotubes. To obtain an estimate for the binding energy of Xe, we measured five low-coverage isotherms for temperatures between 220 and 260 K. We determined a value of 256 meV for the binding energy; this value is 9% lower than the value we found for arc discharge nanotubes and is 1.59 times the value found for this quantity on planar graphite. We have measured five full monolayer isotherms between 150 and 175 K. We have used these data to obtain the coverage dependence of the isosteric heat. The experimental values obtained are compared with previously published computer simulation results for this quantity.     

Oxonol 染料的稳态光物理行为研究

对oxonol——一种带负电荷类菁染料化合物溶液的光谱和光物理问题进行了研究.发现它和一般分子内共轭的电荷转移化合物相比，无论在吸收光谱或荧光发射光谱上，都表现出不同的光物理和光化学行为.对出现的这种差异，特别是负的溶致变色行为和在不同pH条件下分子的互变异构等对吸收光谱的影响进行了讨论.     

Non-linear optics in liquid crystals: basic ideas and perspectives

In this paper the 'unconventional' optical non-linearities of liquid crystals are considered. The basic ideas for the interpretation of collective thermal origin are reviewed. After reporting the which are the major challenges for scentists in this field are recalled. reorientation and of other phenomena of main results of this approach, the issues     

Conductive Organic Complex Salt TTF‐TCNQ as a Mediator for Biosensors. An Overview

Preparation and application of a conductive organic salt complex of tetrathiafulvalene‐tetracyanoquinodimethane (TTF‐TCNQ) for analytical bioelectrochemistry as a mediator is overviewed in this work. The third‐generation biosensors based on this charge transfer salt are very promising for biosensors applied in vivo. Such mediated biosensors have been studied mainly for glucose determination, but at present other substrates are being applied in this system more and more often.     

简化柱切换技术在高浓度基体存在下测定痕量离子的研究

 建立了适用于高浓度基体存在下测定痕量离子的简化柱切换技术。通过分析淋洗液浓度对待测离子色谱峰保留时间的影响 ,指出可使用高浓度淋洗液抑制色谱峰漂移 ,并通过实验案例提出了针对不同样品采取的不同策略。     

Metal ion directed self-assembly of sensors for ions, molecules and biomolecules

Recent years have seen a surge of interest in the metal-ion directed construction of discrete molecular assemblies. Once the versatility of this approach for the construction of hitherto inaccessible molecular architectures was demonstrated, work towards fully functional systems rapidly developed. Since these architectures have a wide range of possible applications, this perspective review will focus on one important aspect of this research: the construction of hosts with optical or electrochemical sensing outputs. As this overview will illustrate, research in this area is now producing working examples of sensors for variety of ionic, molecular, and biomolecular guests.     

A unique rhodium-catalyzed rearrangement process: isomerization of an alkyne to a 1,3-diene with concomitant migration of a formyl group. An expeditious route to dienals from readily available 4-alkynals

In CH2Cl2, [Rh(BINAP)]BF4 catalyzes the isomerization of 4-alkynals to dienals with excellent regio- and stereoselectivity; this new process compares favorably with previously reported methods for the synthesis of this class of compounds; a possible pathway for this unusual rearrangement is provided.     

Use of the hexane-2,2,2-trifluoroethanol system in partition chromatography

The use of the hexane-2,2,2-trifluoroethanol heterophase system of solvents in partition chromatography is characterized. Gas-chromatographic retention indices and partition coefficients are used for the identification of organic compounds in this technique. The partition coefficients of compounds from 12 homologous series were measured in this heterophase system, and parameters for their group identification were calculated. The examples of the use of this system for solving different analytical problems are considered.     

The ‘Temperature Integral’ — Its use and abuse

This paper first reviews the history of the temperature dependence of reaction rate in reaction kinetics. The various equations which are in use today for expressing this dependence were delineated by van't Hoff almost one hundred years ago. Since an exponential form best describes this dependence for most thermal analysis reactions and, due to the fact that the simple Arrhenius equation (with a temperature-independent preexponential factor) has traditionally been used for this purpose, the mathematically intractable temperature integral often has become a necessary evil in the analysis of thermal analysis kinetics. Methods which avoid the temperature integral in kinetics analysis are discussed. The merits of various evaluations and approximations for the temperature integral are described and assessed in this paper.     

A highly performing electrochemical sensor for NADH based on graphite/poly(methylmethacrylate) composite electrode

A fabrication strategy for developing new electrochemical interface based on graphite/poly(methylmethacrylate) (PMMA) composite electrode for some biological molecules was proposed. The results indicated that this electrochemical sensing interface has the advantages, such as quick electron-transfer rate, avoidance of electrode fouling, highly sensitive and stable amperometric sensing for some biomolecules. Compared with carbon paste electrode, this interface would effectively minimize the over-potential and enhance the electrochemical response to some biomolecules. In order to further evaluate the high performance of this interface, the electrochemical behaviors of NADH at this sensing interface were investigated in detail.     

Pyrolysis of 1-iodopropane by the variable encounter method

The pyrolysis of 1-iodopropane has been studied by the variable encounter method (VEM) at temperatures from 625 to 840 K. Deactivating wall collisions are found to be stronger for this molecule than for the hydrocarbons previously studied in this temperature range. The results of this study are compared with earlier steady-state work.     

Metal Complexes of Click‐Derived Triazoles and Mesoionic Carbenes: Electron Transfer,Photochemistry, Magnetic Bistability,and Catalysis

Even though the existence of 1,2,3‐triazoles has been known for more than a century, the recent discovery of a copper(I) catalyzed version of this reaction has attributed unprecedented importance to these compounds. Coordination and organometallic chemists have benefited from this modular synthetic route, and have accessed ligands based on both the triazoles as well as the triazolylidenes. The wide variation of steric and electronic properties that can be achieved for this ligand class has made them useful for generating metal complexes with various applications. Examples include, among others: magnetically switchable molecules, electro‐ and photo‐active molecules, molecules for light‐emitting electrochemical cells, dyes for dye‐sensitized solar cells and a host of homogeneous catalytic processes. In this contribution, we present recent developments in this field with examples of some selected ligands. The focus is on systems developed in our group over the past few years.