灯盏花素与DNA相互作用的电化学及吸收光谱研究

用电化学方法研究了灯盏花素与DNA的相互作用,考察了扫速对灯盏花素与DNA相互作用的影响,实验表明,DNA存在使灯盏花素氧化峰的电位正移,灯盏花素的氧化峰峰电流减小,灯盏花素335 nm吸收光谱的吸收峰降低,呈减色效应,且出现2个等电吸收点,说明灯盏花素与DNA的相互作用以嵌插作用为主。双链DNA(dsDNA)与灯盏花素的结合能力大于DNA(ssDNA),结合比为3:1,结合常数β为3.63×10¹³。     

咖啡酸与DNA相互作用的电化学研究

用电化学方法研究了咖啡酸与DNA的相互作用,考察了扫速对咖啡酸与DNA相互作用的影响。实验表明,DNA存在使咖啡酸氧化峰的电位正移,咖啡酸的氧化峰峰电流减小,咖啡酸在320 nm吸收光谱的吸收峰降低,呈减色效应,且出现两个等电吸收点,说明咖啡酸与DNA的相互作用以嵌插作用为主。双链DNA(dsDNA)与咖啡酸的结合能力大于单链DNA(ssDNA),结合比为1∶1,结合常数β为2.32×106。     

烟酰胺与DNA相互作用的电化学研究

利用示差脉冲伏安法研究了烟酰胺(NA)与小牛胸腺DNA在pH 8.0条件下相互作用的电化学行为.双链DNA(dsDNA)或单链DNA(ssDNA)的存在导致NA的峰电流明显降低且峰电位负移,表明NA与DNA发生相互作用,生成了复合物,且其作用模式主要是静电模式,但NA与dsDNA的相互作用强于与ssDNA的相互作用,可用于识别dsDNA和ssDNA.通过dsDNA加入前后峰电流的变化,计算得出NA与dsDNA结合常数β=4.946×10(11),结合位点数m=3.此外,NA的峰电流Ip与DNA质量浓度在1～14mg/L的范围内呈线性关系,线性回归方程为Ip(10-5A)=-0.03451cDNA(mg/L)+1.7408,相关系数R为0.9998.该法具有良好的回收率和选择性,可用于样品中DNA的测定.     

更生霉素-DNA反应的电化学研究

研究了更生霉素(Act-D)在活化浸蜡石墨电极上的电化学特性,发现在-0.19和-0.51V分别出现一个灵敏的氧化峰和还原峰,加入DNA使Act-D的峰电流明显降低,生成了非电活性络合物.采用电化学方法研究了Act-D与小牛胸腺DNA的结合平衡,根据不可逆电活性分子与DNA相互作用的电化学公式对实验数据进行非线性拟合,获得了Act-D的扩散系数、Act-D与DNA的结合常数和结合位点数等重要信息,发现Act-D与DNA的8个碱基对紧密结合,其侧链加强了结合程度.     

不可逆电活性药物米托蒽醌与脱氧核糖核酸的相互作用

研究了抗癌新药米托蒽醌(MXT)的电化学行为及与脱氧核糖核酸(DNA)的相互作用，推导了适用于研究不可逆电活性分子与DNA相互作用的电化学公式，运用该公式可以简便、快速地测定靶向分子与DNA的结合常数和结合位点数。实验发现，MXT与小牛胸腺DNA的结合以蒽醌母核的嵌插作用为主，同时，烃氨基侧链与骨架磷酸基团之间的静电吸引对母核起稳定作用，使化合物易于嵌入DNA的平面结构。MXT与DNA相互作用引起的峰电流的变化可以用于分析测定DNA。     

灯盏花素在多壁碳纳米管丝网印刷电极上的电化学行为及测定

采用循环伏安法(CV)和差分脉冲伏安法(DPV)研究了黄酮化合物灯盏花素在多壁碳纳米管丝网印刷电极(MWCNT/SPE)上的电化学行为及其测定方法.实验表明,在pH=5.0的HAc-NaAc缓冲溶液中,浓度为5.0×10-4 g/L的灯盏花素在MWC-NT/SPE电极上出现了一对准可逆氧化还原峰,峰电位Epa=0.21 V,Epc=-0.05 V,△E=0.26 V,峰电流ipa=1.18 μA,ipc＝0.205 μA,ipa/ipc=5.76.灯盏花素的DPV氧化峰电流值与其浓度在1.2×10-4～2.8×10-3 g/L范围内呈线性关系(R=0.9990),检出限为1.2×10-4g/L.结果表明,该法测定灯盏花素便捷、可靠、较灵敏.     

锌(Ⅱ)存在下灯盏花素与BSA相互作用的光谱分析

运用荧光光谱、吸收光谱研究了灯盏花素(Breviscapinun,BR)与牛血清白蛋白(Bovine Serum Albumin,BSA)的相互作用.BR对BSA的荧光光谱具有猝灭作用,其猝灭机制为静态-动态联合猝灭,BSA发射峰蓝移.Zn2+的存在使得BSA发射峰蓝移程度降低,猝灭常数、结合常数、结合位点数减小.在较大浓度Zn2+存在下,BR与BSA作用的相关系数增大,猝灭机制变为静态猝灭.从Zn2+与BR的竞争作用,热力学参数的变化、配位化合物的形成3个方面分析了影响BR与BSA作用的因素.     

席夫碱Cu(Ⅱ)配合物与鲱鱼精DNA的相互作用研究

采用电化学和光谱法,研究了糠醛缩对氨基苯磺酸席夫碱Cu(Ⅱ)配合物与鲱鱼精DNA的相互作用。结果发现:糠醛缩对氨基苯磺酸席夫碱Cu(Ⅱ)中加入DNA后,氧化还原峰电流降低,式量电位正移;席夫碱Cu(Ⅱ)配合物使DNA的最大吸收峰强度增强,DNA使席夫碱Cu(Ⅱ)配合物的荧光强度增强。表明席夫碱Cu(Ⅱ)配合物以嵌插模式与DNA作用。     

土霉素的电化学性质及其与DNA相互作用的研究

研究了土霉素在玻碳电极上的电化学行为。并利用电化学方法研究了土霉素与小牛胸腺DNA(ctDNA)的相互作用,DNA的存在能导致土霉素还原峰电流降低,峰电位正移,推测土霉素与DNA在该条件下以键合模式相互结合。紫外-可见吸收光谱的研究进一步确证了上述结果。     

灯盏花素与牛血清白蛋白相互作用的荧光光谱研究

采用荧光光谱法和紫外吸收光谱法研究了灯盏花素(BR)与牛血清白蛋白(BSA)的相互作用;利用热力学方程计算了295K和308K下的热力学参数ΔH、ΔG和ΔS,根据Stern-Volmer方程求出了猝灭常数和结合常数.结果表明,BR对BSA的荧光具有猝灭作用,其猝灭机制为动态-静态联合猝灭,BSA发射峰略有蓝移.BR与BSA之间的作用力主要为疏水作用.     

Furyl- and thienyl-silatranes and germatranes

We review our research on the synthesis and study of the physical and biological properties of furyl- and thienylgermatranes and -silatranes.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 725–732, June, 1992.     

Review and patents and literature

The use of the insect cell/baculovirus expression system for producing recombinant proteins of bacterial, plant, insect, and mammalian origin has become widespread. The popularity of this eukaryotic expression system is due to many factors, including (1) potentially high protein expression levels, (2) ease and speed of genetic engineering, (3) ability to accommodate large DNA inserts, (4) protein processing similar to higher eukaryotic cells (e.g., mammalian cells), and (5) ease of insect cell growth (e.g., suspension growth). The following review of the literature discusses two engineering aspects of recombinant protein synthesis by insect cell cultures: bioreactor scale-up and insect cell line selection. Following this review patent abstracts and additional literature pertaining to expression of recombinant proteins in insect cell culture are listed.     

Ground- and excited-state aromaticity and antiaromaticity in benzene and cyclobutadiene

The aromaticity and antiaromaticity of the ground state (S 0), lowest triplet state (T 1), and first singlet excited state (S 1) of benzene, and the ground states (S 0), lowest triplet states (T 1), and the first and second singlet excited states (S 1 and S 2) of square and rectangular cyclobutadiene are assessed using various magnetic criteria including nucleus-independent chemical shifts (NICS), proton shieldings, and magnetic susceptibilities calculated using complete-active-space self-consistent field (CASSCF) wave functions constructed from gauge-including atomic orbitals (GIAOs). These magnetic criteria strongly suggest that, in contrast to the well-known aromaticity of the S 0 state of benzene, the T 1 and S 1 states of this molecule are antiaromatic. In square cyclobutadiene, which is shown to be considerably more antiaromatic than rectangular cyclobutadiene, the magnetic properties of the T 1 and S 1 states allow these to be classified as aromatic. According to the computed magnetic criteria, the T 1 state of rectangular cyclobutadiene is still aromatic, but the S 1 state is antiaromatic, just as the S 2 state of square cyclobutadiene; the S 2 state of rectangular cyclobutadiene is nonaromatic. The results demonstrate that the well-known "triplet aromaticity" of cyclic conjugated hydrocarbons represents a particular case of a broader concept of excited-state aromaticity and antiaromaticity. It is shown that while electronic excitation may lead to increased nuclear shieldings in certain low-lying electronic states, in general its main effect can be expected to be nuclear deshielding, which can be substantial for heavier nuclei.     

多环芳二酐型聚酯亚胺膜的透气性能

多环芳二酐型聚酯亚胺膜的透气性能李悦生，丁孟贤，徐纪平（浙江大学高分子科学与工程研究所，杭州，３１００２７）（中国科学院长春应用化学研究所）关键词聚醚酰亚胺，聚酯酰亚胺，膜，透气性通常的聚酰亚胺加工性能较差，在芳环二酐的苯环间引入醚键等柔性基团后，其...     

Determination and study on residue and dissipation of benazolin-ethyl and quizalofop-p-ethyl in rape and soil

A QuEChERS (quick, easy, cheap, effective, rugged, and safe) method for the determination of benazolin-ethyl and quizalofop-p-ethyl in rape and soil by high-performance liquid chromatography-tandem mass spectrometry has been developed in this study. The residue and dissipation of benazolin-ethyl and quizalofop-p-ethyl in rape and soil were determined with the developed method. The half-lives of benazolin-ethyl in rape straw and soil were 3.7–5.1 days and 14.3–26.3 days, respectively. The half-lives of quizalofop-p-ethyl in rape straw and soil were 5.0-6.1 days and 0.3–9.7 days, respectively. The residue of benazolin-ethyl and quizalofop-p-ethyl in rapeseed and soil were below the detection limit (i.e., 0.5?mg?kg^?1, the maximum residue level of European Union for quizalofop-p-ethyl).