速差动力学分析及其应用进展

速差动力学分析是不经分离同时或连续测定混合物中性质密切相关的多组份的重要方法。本文综述了该法在１９８９－１９９２年间国内外新进展，尤着重其在有机，生物混合物中多组份分析的应用及新的计算方法，化学计量学的引入。引用最新文献６７篇。     

Synthesis and thermal decomposition of ditetrazol-5-ylamine

Ditetrazol-5-ylamine (DTA) was synthesized from cyanuric chloride in four steps. The thermal decomposition of DTA in the solid state was studied by thermogravimetry, volumetry, mass spectrometry, IR spectroscopy, and calorimetry. Under isothermal conditions at 200–242 °C, thermal decomposition obeys the first order autocatalytic kinetics. The kinetic and activation parameters of DTA decomposition were determined. The composition of gaseous reaction products and the structure of condensed residue were studied. The thermal effect of thermal DTA decomposition is 281.4 kJ mol⁻¹. The nitrogen content in a mixture of gaseous products formed by the reaction in a temperature interval of 200–242 °C exceeds 97 vol.%. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1660–1664, July, 2005.     

Electrochemical Impedance Analysis of Thermogalvanic Cells

Thermogalvanic cells(also known as thermo-electrochemical cells) that convert waste heat energy to electricity are a new type of energy conversion device. However, the electron transfer kinetics and mass transfer of redox couples have not been thoroughly studied. Here, the ion reaction and charge transport in thermogalvanic cells are investigated by electrochemical impedance analysis. We first propose the detailed impedance model followed experimental verification on three types of electrode materials. Parameters including kinetic rate constants and ion diffusion coefficients for the electrodes are obtained by fitting the impedance data. Our study shows explicitly that impedance analysis can provide useful information on selecting suitable electrode materials for thermogalvanic cells.     

The structure of arylmercury derivatives of alizarin and their interaction with anions

The structure of mono- and di-ArHg-derivatives of alizarin (1,2-dihydroxy-9,10-anthraquinone) and their interactions with halide- and oxygen-containing salts are examined by vibrational and electronic spectroscopy. The interaction of solid mono- and di-ArHg-derivatives of alizarin with bromides results only in the formation of the monoanion or the ion pair, depending on the nature of the counterion. Dianions are formed in a DMSO solution with very great excess of the bromide.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2019–2023, November, 1994.The work is performed within the framework of the Direction No 02-05-01 of the Ministry of Science and Technical Policy of Russian Federation. The authors are grateful to the International Science Foundation (grant MHW000) and the Russian Foundation for Basic Research (Project No. 94-03-08873) for financial support.     

Chiral resolution of diphenylalanine by high-performance liquid chromatography on a crown-ether-based chiral stationary phase and by NMR spectroscopy

Summary The enantiomers of diphenylalanine (DPA) were well separated by chiral HPLC and NMR spectroscopy on the chiral stationary phase (CSP) derived from (18-crown-6)-2,3,11,12-tetracarboxylic acid (18-C-6-TA). The chromatographic parameters such as separation factors and retention times were greatly influenced by the mobile phase conditions. The (+)-18-C-6-TA used in the CSP was also employed as a chiral solvating agent for the enantiodiscrimination of the DPA enantiomers by NMR spectroscopy. The proton of the DPA analyte showing the chemical shift nonequivalences was used in determining the enantiomeric composition of the analyte.     

A Background and noise elimination method for quantitative calibration of near infrared spectra

A new hybrid algorithm is proposed to eliminate the varying background and noise simultaneously for multivariate calibration of near infrared (NIR) spectral signals. The method is based on the use of multi-resolution, which is one of the main advantages provided by wavelet transform. The signals are firstly split into different frequency components, which keep the same data points of the original signals. In conjunction with a modified uninformative variable elimination (mUVE) criterion, the new method can be used to remove the low-frequency varying background and the high-frequency noise simultaneously. The method is successfully applied to simulated spectral data set and experimental NIR spectral data, resulting in more parsimonious multivariate models with higher precision. In addition, the proposed strategy can be applied to other spectral signals as well.     

Time-resolved ultraviolet laser-induced breakdown spectroscopy for organic material analysis

Ultraviolet pulses (266 nm) delivered by a quadrupled Nd:YAG laser were used to analyze organic samples with laser-induced breakdown spectroscopy (LIBS). We present characteristics of the spectra obtained from organic samples with special attentions on the emissions of organic elements, O and N, and molecular bonds CN. The choice of these atomic or molecular species is justified on one hand, by the importance of these species to specify organic or biological materials; and on the other hand by the possible interferences with ambient air when laser ablation takes place in the atmosphere. Time-resolved LIBS was used to determine the time-evolution of line intensity emitted from these species. We demonstrate different kinetic behaviors corresponding to different origins of emitters: native atomic or molecular species directly vaporized from the sample or those generated through dissociation or recombination due to interaction between laser-induced plasma and air molecules. Our results show the ability of time-resolved UV-LIBS for detection and identification of native atomic or molecular species from an organic sample.     

[3,4]-annulated pyrroles 1. Polynuclear heterocyclic systems based on pyrrolo[3,4-d]pyrimidine-2,4-dione

The intramolecular electrophilic substitution in 6-functionalized 1,3-dimethyl-1H-pyrrolo[3,4-d]pyrimidine-2,4(3H,6H)-diones was used for the synthesis of pyrimido[4′,5′:3,4]-pyrrolo[1,2-a]quinoxaline-8,10(7H,9H)-dione, pyrimido[4′,5′:3,4]pyrrolo[2,1-c][1,2,4]benzo-triazine-8,10(7H,9H)-dione, and 2H-pyrimido[4′,5′:3,4]pyrrolo[1,2-a]indole-2,4,11(1H, 3H)-trione derivatives. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2180–2185, December, 2006.     

Reversible Immobilization of Peptides: Surface Modification and In Situ Detection by Attenuated Total Reflection FTIR Spectroscopy

A generic method is described for the reversible immobilization of polyhistidine‐bearing polypeptides and proteins on attenuated total reflecting (ATR) sensor surfaces for the detection of biomolecular interactions by FTIR spectroscopy. Nitrilotriacetic acid (NTA) groups are covalently attached to self‐assembled monolayers of either thioalkanes on gold films or mercaptosilanes on silicon dioxide films deposited on germanium internal reflection elements. Complex formation between Ni²⁺ ions and NTA groups activates the ATR sensor surface for the selective binding of polyhistidine sequences. This approach not only allows a stable and reversible immobilization of histidine‐tagged peptides (His–peptides) but also simultaneously allows the direct in situ quantification of surface‐adsorbed molecules from their specific FTIR spectral bands. The surface concentrations of both NTA and His–peptide on silanized surfaces were determined to be 1.1 and 0.4 molecules nm^?2, respectively, which means that the surface is densely covered. A comparison of experimental FTIR spectra with simulated spectra reveals a surface‐enhancement effect of one order of magnitude for the gold surfaces. With the presented sensor surfaces, new ways are opened up to investigate, in situ and with high sensitivity and reproducibility, protein–ligand, protein–protein, protein–DNA interactions, and DNA hybridization by ATR–FTIR spectroscopy.