NMR and UV-Vis study on phenyl-capped oligoaniline salts

Phenyl-capped oligoanilines in the oxidized state and their salts (by camphor sulfonic acid, CSA) were comparatively studied by UV-Vis and NMR spectroscopy. The UV-Vis spectra revealed a similar electron transfer behaviour and similar structure in the tetraaniline to those in polyaniline. Upon formation of the salt, H-1 NMR CH peaks of the oligomers showed large shifts to lower fields. The longer the molecule of a oligomer is, the more the shift, indicating that the charge brought into the N atoms by the proton was redistributed over the whole molecule. The CH and quaternary carbon peak-shifts support the electron cloud motion route H -->C -->C -->N -->H. This is in agreement with the four ring BQ derivatives model.

Production of active oxygen species from Taxus cuspidata induced by far-UV radiation

In order to understand the role of active oxygen species in mediating plant injuries induced by far-UV radiation, seedlings of Taxus cuspidata Sieb. et Zucc. were irradiated by far-UV rays in laboratory for 4 weeks. The production of organic free-radicals in detached needles, and the production of O-2(radical anion) and O-1(2) in isolated chloroplasts were detected weekly by electron spin resonance (ESR) to evaluate their relative importance. The results show that the cumulative effect of far-UV irradiation, is best indicated by the production of organic free radicals in the needles, O-2(radical anion) production in chloroplasts is the next. The enhancement of O-1(2) production in chloroplasts by the cumulative far-UV irradiation seems to be not so important as O-2(radical anion) in mediating injuries induced by, far-UV radiation because of its high background value.

Synthesis of monodisperse pheyl-capped oligoaniline pentamer and hexamer in the leucoemeraldine oxidation state and EB state and its UV studies

Aniline pentamer and hexamer in the leucoemeraldine oxidation state were synthesized through a novel method. The method was accomplished by the reaction of parent aniline tetramer in the pernigraniline oxidation state with diphenylamine and N-phenyl-1,4-phenylenediamine in the leucoemeraldine oxidation state respectively. The oligomers in the leucoemeraldine oxidation state were characterized by IR, NMR, elemental analysis and MALDI-MS. Aniline pentamer and hexamer in the emeraldine oxidation state were synthesized by the oxidation of Ag2O in DMF. It was found that some fragmentation occurred when the pentamer and hexamer were oxidized by (NH4)(2)S2O8 and FeCl3. 6H(2)O. The pentamer and hexamer in the emeraldine oxidation state was studied by UV/Vis spectra. The relative intensity of exciton peak for pentaaniline showed a little increase compared with that of hexaaniline.

Combination of amperometric detector & UV detector for capillary electrophoresis

A new electrochemical cell assembly with the combination of UV and amperometric detector (AD) based on their complementarity was described. A Nafion tubing junction was used to decouple the high voltage from the separation capillary in the rear of on-column UV detector. In this mode, the electroactive and inert compounds could be detected by UV and AD at the same time. Aromatic amines were determined with the UV and the end-column AD detection to evaluate the performances of the cell assembly. Such an improved electrochemical detector could match the capillary with different diameters. By simple adjustment of the screws, the positioning of the working electrode and the detection capillary was easily gained without microscope. It is also very easy to assemble and disassemble the working electrode when needed. (C) 1999 Elsevier Science B.V. All rights reserved.

In situ UV-vis and CD thin-layer spectroelectrochemistry study of the electrochemical behavior of L-noradrenaline in alkaline solution

Electrochemical redox behavior of noradrenaline in alkaline solution on a glassy carbon electrode has been investigated by in situ UV-vis and CD spectroelectrochemistry by using a long optical path thin-layer cell. The experimental data were processed by using a double logarithmic method of analysis together with nonlinear regression which confirmed that the first step in both the oxidation of noradrenaline and reduction of noradrenochrome is a two-electron irreversible process governed by an EE mechanism. The kinetic parameters of the electrode reactions, i.e., charge transfer coefficient and the number of electrons transferred, alpha(1)n(1) = 0.11 and alpha(2)n(2) = 0.23, formal potentials modified with kinetics, E-1(0') = 0.65 (+/- 0.01) V and E-2(0') = 0.72V and standard rate cnstants, k(1)(0) = 7.0(+/-0.5)x10(-5) cm s(-1), for the first and second steps in the oxidation process of noradrenaline, and similarly, alpha(1)n(1) = 0.33, alpha(2)n(2) = 0.58, E-1(0') = 0.37(+/-0.01) V, E-0' = -0.25 (+/-0.01) V and k(1)(0) approximate to k(2)(0) = 1.06 (+/-0.05)x10(-4) cm s(-1) for the first and second steps in the reduction process of noradrenochrome were also determined.

卟啉和卟啉铜分子的成膜特性和UV－Vis光谱表征

合成了５，１０，１５，２０－四（对－异戊酯苯基）卟啉及其铜配合物，研究了它们在气液界面的成膜性质，制备了上述化合物的ＬＢ膜，利用ＵＶ—Ｖｉｓ光谱对化合物在ＬＢ膜结构中的取向进行了表征．研究结果表明．两种化合物在界面上的成膜性质和分子环面在ＬＢ膜结构中的取向均受到铜离子配位的影响.

IN-SITU UV-VISIBLE SPECTROELECTROCHEMICAL AND CIRCULAR DICHROIC ELECTROCHEMICAL STUDY OF BILIRUBIN AND BILIRUBIN PLUS HUMAN SERUM-ALBUMIN COMPLEX

The electro-oxidation of bilirubin (BR) in aqueous solution was investigated by cyclic voltammetry and in-situ thin-layer spectroelectrochemical techniques, It was found that both oxidation processes of BR are two electron transfer reactions. A mechanism

DETERMINATION OF THE MOLECULAR-ORIENTATION OF A PHTHALOCYANINE DERIVATIVE IN A LANGMUIR-BLODGETT-FILM BY POLARIZED UV VIS SPECTRA

Langmuir-Blodgett (LB) films of (p-carboxyphenoxy)-tri(2,4-di-tert-pentyl phenoxy)phthalocyanine copper(II) (asyCuPc) are prepared; the associated forms of the compound in chloroform solution and the particular orientation of asyCuPc molecular macrocycles in LB films is determined by polarized UV-VIS.

Lack of genetic differentiation in the shrimp Penaeus chinensis in the northwestern pacific

Genetic differentiation of the shrimp Penaeus chinensis in the Yellow Sea and Bohai Sea was investigated using the mitochondrial control region (CR). RFLP of a partial CR segment (613 bp) shows that 106 out of 122 (86.9%) individuals from six sampling localities along the coast of northern China and the west coast of the Korean Peninsula share the same haplotype, and the haplotype frequencies among localities are not significantly different. The findings are further confirmed by sequencing the complete CR. Divergence of the complete CR (992 bp) is less than 1.6% in 14 individuals from the six localities. F-statistics based on RFLP data and the TCS network of sequencing data suggest little genetic differentiation of P. chinensis in the Yellow Sea and Bohai Sea. Mismatch analysis suggests a rapid expansion of P. chinensis population to the Yellow Sea and the Bohai Sea, which probably occurred with the rapid rise in sea level after the last glacial maximum. Despite the lack of genetic heterogeneity, we propose that P. chinensis populations in this region should be treated as separate management units, as fishery management programs have to be applied on a local basis by different governments.

高寒草甸植物抗氧化系统对长期增强UV-B辐射的响应

通过研究自然条件下模拟平流层臭氧破坏5%时近地表面增加的太阳UV-B辐射对高寒草甸4种典型植物（矮嵩草Kobresia humilis、垂穗披碱草Elymus nutans、麻花艽Gentiana straminea和鹅绒委陵菜Po-tentilla anserina）的抗氧化系统的影响表明,尽管各植物的抗氧化系统组分变化不同,但4种植物的膜脂过氧化程度没有加剧,长期增强UV-B辐射没有对膜系统造成损伤。在自然长期增强UV-B条件下,4种植物的膜脂过氧化产物——丙二醛（MDA）含量与对照相比无显著差异。垂穗披碱草、鹅绒委陵菜的谷胱甘肽（GSH）含量增加,麻花艽的超氧化物歧化酶（SOD）活性与鹅绒委陵菜的过氧化氢酶（CAT）活性上升,同时麻花艽的类胡萝卜素（Car）含量亦显著增加。可见这些植物已能很好地适应UV-B强辐射,其抗氧化能力除了与抗氧化系统各组分的协同作用有关外,也可能与种的适应性有关。

野生与栽培药材麻花秦艽的HPLC／UV指纹图谱研究

采用反相高效液相色谱一二极管阵列的检测方法，分析了不同产地11批麻花秦艽药材，建立麻花秦艽药材的指纹图谱，进行野生药材与栽培药材的对比研究。结果表明：最佳条件可较全面的反映麻花秦艽药材的主要成分，栽培药材与野生药材相似度较好。

祁连山海北高寒草甸地区UV-B的气候变化特征

分析祁连山海北高寒草甸地区2002年太阳总辐射（Eg）、UV-B及UV-B占Eg比例的气候变化特征。结果表明：海北站地区UV-B较强，日瞬时最高接近10W•m^-2，日总量最高达0．204MJ•m^-2；日、年变化依Eg的日、年变化具有显著的正相关关系。UV-B与Eg的比值（η），不论是日变化还是年变化表现明显，一日间早晚低，中午高，一年间6月最高，冬季的12月低，与太阳高度角的变化具有一定的正相关关系。年平均η约为0．54％，植物生长期的5～9月约为0．65％。在海北高寒草甸地区Eg和UV-B的年总量分别达6387．436MJ•m^-2和35．981MJ•m^-2。

长期增强UV-B辐射对高寒草甸植物光合速率和抗氧化系统的影响

研究了在野外自然条件下，长期增强UV-B辐射对高寒草甸3种典型植物矮嵩草（Kobresia humilis）、垂穗披碱草（Elymus nutans）和钉柱委陵菜（Potentilla saundersiana）光合放氧速率、光合色素和抗氧化系统的影响。结果表明：长期增强UV-B辐射对3种植物的净光合速率没有明显影响。增强UV-B辐射下，3种植物的叶绿素含量变化不同，Chla／b值，类胡萝卜素（Car）含量，Car／Chl值与对照相比都有升高，说明植物叶片的光合能力、吸收紫外线的能力增强以及忍受逆境能力均有增强，从而产生光保护，有利于光合作用正常进行。由于3种植物膜脂过氧化程度的不同及SOD活性的普遍抑制，植物经受了氧化胁迫。垂穗披碱草叶片GSH含量显著七升，矮嵩草的形态矮小及钉柱委陵菜GSH含量与POD活性显著上升，都能减轻它们所经受的氧化胁迫，使光合器官免受损伤。所以，这些保护性色素的积累和抗氧化系统内部的协同作用可能是高寒草甸植物光合作用正常进行的重要原因。

增强UV-B辐射对麻花艽叶片的抗氧化酶的影响

以青藏高原的特有植物麻花艽为材料,研究麻花艽叶片抗氧化酶系统对增强UV-B辐射的响应.结果表明:在UV-B处理初期,麻花艽叶片SOD、POD的酶活性都能增加,但随着处理时间的延长,SOD、POD的活性呈现下降趋势.麻花艽叶片CAT的酶活性在UV-B处理后下降明显,但作为清除叶绿体中H2O2的关键酶AP的酶活性表现为明显地增加趋势,说明在对麻花艽叶片增强UV-B辐射反应中AP起有着重要作用.MDA的含量随UV-B处理时间延长而增加,表明UV-B降低了细胞内活性氧自由基的清除能力,膜脂过氧化作用加剧,导致了对麻花艽叶片的伤害效应.