Broadband and band-selective IMPRESS-gHMBC: compensation of refocusing inefficiency with synchronized inversion sweep

Compensation of refocusing inefficiency in a gHMBC experiment by replacing the rectangular pi pulse with a pair of adiabatic pulses with synchronized inversion sweep (CRISIS) significantly improves the performance of the gHMBC experiment. The CRISIS-gHMBC experiment retains the pure absorptive shapes in F1 and hence results in better lineshape and higher resolution than the current versions of magnitude mode gHMBC spectra. When used as a broadband experiment, CRISIS-gHMBC, owing to better refocusing efficiency of the adiabatic pulse pairs, gives improved performance across the 13C spectral width. Moreover, it is shown that CRISIS-gHMBC is a robust and improved alternative and when used along with the IMPRESS (Improved Resolution using Symmetrically Shifted pulses) technique further increases the sensitivity and resolution without additional experimental time. The IMPRESS-CRISIS combination is demonstrated for broadband gHMBC and band-selective gHMBC experiments. The ICbs-gHMBC [IMPRESS-CRISIS-band-selective gHMBC] experiment is an attractive and better alternative to individual band-selective gHMBC.     

Pulse radiolysis study of I− oxidation with radical anions Cl2 ⋅− in an aqueous solution

Radiation-chemical transformations of chloride solutions in the presence of iodide additives were studied by pulse radiolysis. Radical anion Cl₂ ^⋅− oxidize I⁻ ion, while in the secondary reactions Cl₂ reacts with I⁻ to form a mixed trihalide ion ICl₂ ⁻. A reaction model that satisfactorily describes the experimental data was proposed. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1336–1340, June, 2005.     

盐酸吡哆辛及其制剂的二阶导数差示脉冲极谱法定量研究

建立盐酸吡哆辛及其制剂的二阶导数差示脉冲极谱定量分析方法。盐酸吡哆辛在0.1mol/L氢氧化钠溶液-0.1moL/L磷酸二氢钾溶液-水(体积比为1.2:8.8:990)的混合溶液中,于-0.140V(vs·Ag/AgCl)处出现一良好的二阶导数差示脉冲极谱峰,盐酸吡哆辛浓度在3.6×10~(-4)～9.6×10~(-4)mol/L范围内与其峰幅值呈显著的线性关系(P<0.01),线性相关系数r=0.9997,检出限为9.0nmol/L。     

Electrochemical Study of the Lipid‐Transfer Protein

Electrochemical study of barley grain lipid‐transfer protein (LTP) revealed that it may belong to the metal‐binding protein class. Using differential pulse polarography the presence of Cu(II) and Zn(II) ions in the native LTP structure was proved, as well as its affinity for binding Ni(II) ion. Application of a more sensitive electroanalytical technique, such as anodic stripping voltammetry with analyte preconcentration, revealed the presence of Pb(II) and Cd(II) ions and also enabled the following Hg(II) ion binding. Possible biological role of LTP in plant stress response and its contribution to barley phytoextraction potential are discussed.     

Highly conjugated p-quinonoid pi-extended tetrathiafulvalene derivatives: a class of highly distorted electron donors

A new class of pi-extended TTF-type electron donors (11 a-c) has been synthesized by Wittig-Horner olefination of bianthrone (9) with 1,3-dithiole phosphonate esters (10 a-c). In cyclic voltammetry experiments, donors 11 a-c reveal a single, electrochemically irreversible oxidation-yielding the corresponding dicationic products-at relatively low oxidation potentials (approximately 0.7-0.8 V). Theoretical calculations, performed at the DFT level (B3 P86/6-31 G*), predict a highly-folded C(2h) structure for 11 a. In the ground state, the molecule adopts a double saddle-like conformation to compensate the steric hindrance. The calculations suggest that the intramolecular charge transfer associated with the HOMO-->LUMO transition is responsible for an absorption band observed above 400 nm. While the radical cation 11 a*+ retains the folded C(2h) structure predicted for the neutral molecule as the most stable conformation, the dication 11 a(2+) has a fully aromatic D(2) structure, formed by an orthogonal 9,9'-bianthryl central unit to which two singly-charged dithiole rings are attached. The drastic conformational changes that compounds 11 undergo upon oxidation account for their electrochemical properties. By means of pulse radiolysis measurements, radical-induced one-electron oxidation of 11 a-c was shown to lead to the radical cation species (11 a-c*+), which were found to disproportionate with generation of the respective dication species (11 a-c(2+)) and the neutral molecules (11 a-c).     

铜膜差分脉冲阳极溶出伏安法测定药物中铋的含量

研究了铜膜电极代替汞膜电极测定重金属铋的差分脉冲溶出伏安法。实验了同位镀膜法测定铋的条件。在最佳实验条件下,Bi3+浓度在5×10-8~2×10-5mol/L范围内,其溶出峰峰高与浓度呈线性关系,检出限达到1×10-8mol/L。测定了一些药物中铋的含量,结果准确。     

Measurement of the sign and the magnitude of heteronuclear coupling constants from spin-state-edited J-cross-polarization NMR experiments

New spin-state-selective (S3) NMR pulse sequences exclusively applying cross-polarization schemes to achieve optimum homonuclear and heteronuclear 1H-X coherence transfer are reported for the simple and accurate measurement of the magnitude and sign of heteronuclear coupling constants for samples at natural abundance. The proposed spin-edited HCP-TOCSY experiments are based on clean heteronuclear S3 excitation, generated by simultaneous co-addition of two independent in-phase and anti-phase components created during the mixing heteronuclear J-cross-polarization (HCP) step, which is finally transferred to other protons by a conventional homonuclear TOCSY mechanism. Selective 1D and non-selective 2D approaches for the easy determination of long-range proton-carbon and proton-nitrogen coupling constants on any protonated and non-protonated heteronuclei are presented and discussed for several organic molecules.     

二氧化碳和氧气的快速电化学方法联合测定

根据Ｏ２和ＣＯ２在二甲亚砜（ＤＭＳＯ）介质中Ｐｔ电极上的伏安特性，采用微电极并结构计算机控制的电位调制技术，建立了快速联合测定ＣＯ２和Ｏ２的调制电位脉冲库仑法和调制电位脉冲电流法，取得了满意的结果。一次测量时间快达４０ｍｓ。ＣＯ２检测范围０￣１０％（体积百分比）；Ｏ２检测范围不受限制。通过编程设计特定的调制电位－时间波形，可保持连续检测的长期稳定性。     

以催化油浆窄馏分为添加剂的Al－MCM－41分子筛的合成

 采用阳离子表面活性剂十六烷基三甲基溴化铵为模板剂，以正硅酸乙酯为硅源，以硫酸铝为铝源，水热合成了以催化油浆窄馏分为添加剂的高比表面积Al－MCM－41介孔分子筛，并利用XRD，HREM，TG－DTA及N2吸附－脱附等测试手段对合成样品进行了表征．合成的Al－MCM－41分子筛的比表面积和孔体积分别达到1295m2／g和1．5cm3／g，其平均孔径为4．3nm．重点研究了Al－MCM－41分子筛结晶度、晶胞参数、比表面积、孔体积及平均孔径等结构性质随催化油浆窄馏分添加量及其组成的变化规律，并从合成机理上进行了解释．