Reaction of sulphate radical anion (SO<Superscript>.</Superscript><Subscript>4</Subscript><Superscript>-</Superscript>) with hydroxy-and methyl-substituted pyrimidines: a pulse radiolysis study

Reactions of sulphate radical anion (SO·₄ ^-) with 4,6-dihydroxy-2-methyl pyrimidine (DHMP), 2,4-dimethyl-6-hydroxy pyrimidine (DMHP), 6-methyl uracil (MU) and 5,6-dimethyl uracil (DMU) have been studied by pulse radiolysis at pH 3 and at pH 10. The transient intermediate spectra were compared with those from the reaction of hydroxyl radical (·OH). It is proposed that SO·₄ ^- produces radical cations of these pyrimidines in the initial stage. These radical cations are short-lived except in the case of DMHP where a relatively longer lived radical cation is proposed to be formed. When there is a hydrogen atom attached to the N(1) or N(3) position, a deprotonation from these sites is highly favored. When there is no hydrogen attached to these sites, deprotonation from a substituted methyl group is favored. At acidic pH, deprotonation from nitrogen is observed for DHMP, MU and DMU. At basic pH, the radical cation reacts with OH^- leading to the formation of OH adducts.     

Direct Identification of the Carbon Skeleton of Organic Compounds using Double Quantum Coherence 13C-NMR Spectroscopy. The INADEQUATE Pulse Sequence

NMR spectroscopy plays an important part in the determination of the structures of organic compounds. The parameters of importance here are the chemical shifts of the ¹H and ¹³C nuclei and the spin-spin interactions both between ¹H nuclei and between ¹H and ¹³C nuclei. Couplings between ¹³C nuclei were almost completely neglected until a few years ago, since they were extremely difficult to observe because of the low natural abundance of ¹³C. However, it is these couplings which afford information directly on the carbon-carbon connectivities in the molecule. It is now possible to use a special NMR pulse sequence to make these couplings more readily visible: the result of using this sequence is a ¹³C-NMR spectrum from which the carbon skeleton concerned can be directly read off. Two-dimensional spectra in particular are very easy to evaluate. The pulse sequence involved, which bears the somewhat puzzling name INADEQUATE, produces double-quantum coherences from which the NMR signals of the coupled carbon nuclei can be obtained. In this article the principle of double-quantum coherence is described and a number of examples for the application of the INADEQUATE pulse sequences to problems in synthetic organic chemistry, biosynthesis and natural products chemistry are presented; in addition, the possibility of applying the INADEQUATE method to other nuclei is considered.     

甲烷氧化偶联催化剂La2O3／SrCO3—BaCO3的催化活性与表征

在甲烷氧化偶联制Ｃ２烃的研究中，人们发现碱土金属与稀土金属组成的复合氧化物催化剂具有高的催化活性［１，２］．稀土化合物作为有希望的工业催化剂之一，已受到广泛的关注．一般认为，它们含有的氧空位对活化甲烷的有效氧物种有利．Ｄｅｂｅｙ等在１％Ｓｒ／Ｌａ２Ｏ...     

Electroreduction of the antifouling agent TCMTB and its electroanalytical determination in tannery wastewaters

The electrochemical reduction of antifouling agent 2-thiocyanomethylthiobenzothiazole (TCMTB) was investigated by cyclic and pulse differential voltammetry. The irreversible electrode reduction of TCMTB proceeded by ECEC reaction mechanism by two electrons transfer with one irreversible wave. Upon the basis of electrochemical evidence, the electrodic reaction mechanism was suggested to formation of mercaptobenzothiazole (MTB) in solution.Subsequently, a pulse differential method is described for the formation of TCMTB based on this electroreduction. Having been obtained a detection limit of 1.0 × 10⁻⁷ mol L⁻¹ and recovery to 98% to concentration of 2.0 × 10⁻⁶ mol L⁻¹. Therefore, the proposed method in this study is practical, sensitive and accurate for the analysis of TCMTB in tannery wastewater samples.     

Synthesis of SBA-15/carbon composite with an ink-bottle-like pore structure by a novel pulse CVD technique

A novel and easy post modification method, pulse chemical vapor deposition (pulse CVD), was developed to tailor the pore-opening of SBA-15 while largely keeping its surface area and pore volume. By using acetylene as carbon precursor and nitrogen as carrier gas, the pore-mouth of SBA-15 was effectively reduced from 8.1 nm to 5.1 nm within 5 min while maintaining the pore body at 8.1 nm. This ink-bottle-structured SBA-15/carbon composite only losses 12% BET specific surface area and 16% total pore volume, respectively. The SBA-15/carbon composite is highly hexagonally ordered and has similar particle morphology as the original SBA-15. The effect of three pore modification factors—the number of cycles of pulse CVD, the ratio of acetylene/nitrogen and the feeding time of carbon precursor, on the final pore structure of the SBA-15/carbon composite is also studied.     

Thermodynamic properties of peptide solutions: 7. Partial molar isentropic pressure coefficients of some dipeptides in aqueous solution

The partial molar isentropic pressure coefficients at infinite dilution, K _S,2 ^o , have been determined for a number of dipeptides in aqueous solution at 25°C. For a series of dipeptides of sequence gly-X, where X is an amino acid with a neutral side chain, the K _S,2 ^o values are all more negative than that for diglycine. The results are discussed in terms of the hydration of the side chains. There are significant differences in the K _S,2 ^o values for sequence isomeric dipeptides. These differences can be rationalized in terms of the mutual interactions between the side chain and the ionic end groups in the dipeptides. Possible relationships between K _S,2 ^o and V ₂ ^o , the partial molar volume at infinite dilution, were investigated. For the dipeptides of sequence gly-X there is an interesting linear relationship between K _S,2 ^o /V ₂ ^o and V ₂ ^o .     

Stochastic resonance is applied to quantitative analysis for weak chromatographic signal of glyburide in plasma

Based on the theory of stochastic resonance, a new method carried on the quantitive analysis to weak chromatographic signal of glyburide in plasma, which was embedded in the noise background and the signal-to-noise ratio (SNR) of HPLC-UV is enhanced remarkably. This method enhances the quantification limit to 1 ng ml⁻¹, which is the same as HPLC-MS, and makes it possible to detect the weak signal accurately by HPLC-UV, which was not suitable before. The results showed good recovery and linear range from 1 to 50 ng ml⁻¹ of glyburide in plasma and the method can be used for quantitative analysis of glyburide.     

Synthesis,characterization, and application of griseofulvin surface molecularly imprinted polymers as the selective solid phase extraction sorbent in rat plasma samples

In present study, an investigation was carried out to develop and validate an analytical method for the selective extraction and determination of griseofulvin (GSF) from plasma samples. For this purpose, a rational approach was made to synthesize and characterize the surface molecularly imprinted polymers (SMIPs). The SMIPs were utilized as solid phase extraction (SPE) sorbents. The SMIPs were prepared by using GSF as template molecule on the surface of modified silica particles through a non-covalent technique. The particles demonstrated high adsorption capacity (119.1 µg/mL), fast adsorption equilibrium time (30 min) and good recognition selectivity for the template drug. The scanning electron microscopy and infrared spectroscopy were used to explain the structural and morphological characteristics of the SMIPs and surface non-imprinted polymers. The SPE method was combined with HPLC for plasma analysis. The method validation results demonstrated that the established method possessed good linearity for GSF ranging from 0.1 to 50 µg/mL (R² = 0.997). The limit of detection for this method was 0.02 µg/mL for rat plasma samples. The recoveries of GSF from spiked plasma samples were (90.7–97.7%) and relative standard deviations were (0.9–4.5%). Moreover, the SMIPs as selective SPE sorbent can be reused more than 8 times which is a clear advantage over commercial SPE sorbents. Finally, the usefulness of the proposed strategy was assessed by extraction and detection of GSF in real rat plasma samples.     

电爆炸箔断路开关的理论和实验研究

 采用金属箔电爆炸过程的二维数值计算模型，对含电爆炸金属箔断路开关的电感储能脉冲功率调节系统进行了数值计算。以此为基础，研制出了一种低电感型的电爆炸箔断路开关，并以4μF/75kV脉冲电容器组作为初级能源，13Ω电阻作为负载进行实验研究。研究结果表明：在负载上可获得约250kV，脉宽大于400ns的脉冲电压。     

S-5N全固态重复频率脉冲发生器

 主要介绍S-5N的结构及测试实验结果。S-5N型全固态重复频率脉冲发生器是目前国际上同类源中峰值功率和平均功率均为最大的一台。随负载大小的变化，S-5N脉冲发生器的输出电压为400～600kV，输出电流2～3kA，输出脉冲半高宽40～50ns，单脉冲输出能量40～65J。 S-5N脉冲发生器在300Hz重复频率条件下可连续工作，500Hz重复频率条件下可连续工作3min，平均输出功率高达30kW。