DNA分子结构的多态性研究(Ⅰ)——阳离子型表面活性剂诱导λ┐DNA由线圈型向球型的转变

活性细胞众多的遗传信息均通过ＤＮＡ链的碱基序列按一定的自身调节方式表达出各种蛋白质［１］．ＤＮＡ与各种不同性质的组分，如蛋白质、类脂及无机离子等的相互识别作用是确保细胞处于生理活性状态的重要调节机制．阳离子型表面活性剂与带相反电荷的多价离子的相互作用...     

水介质钯卟啉室温磷光探针与小牛胸腺DNA作用的光谱特性

研究水溶性卟啉及其金属配合物与生物大分子 ,特别是核酸的相互作用方式对获得 DNA的碱基序列和识别 DNA的结构进而设计新型药物尤其是抗癌药物具有重要意义 [1] .近年来 ,采用电子吸收光谱、荧光光谱法和电化学技术研究卟啉与 DNA的相互作用多有报道 [2～ 4 ] ,磷光探针 [5]已成为探索有机介质中微环境性质或生物大分子如核酸和蛋白质的构型变化以及它们与药物作用机理的有力工具 .由于磷光具有更高的选择性 ,且与体系氧浓度密切相关 ,而生物分子在接近红外的长波长区几乎没有室温磷光发射 ,因此 ,寻找或合成一种在这一波段具有室温磷…     

外显子周期三行为特征的研究

基因中蛋白质的编码区具有周期三行为这一规律已成为目前基因预测的理论基础, 采用功率谱对外显子的周期三行为特征进行了研究, 结果表明: 大多数外显子独立存在于基因中时并不具有周期三行为, 而当基因被剪切后外显子连在一起编码蛋白质的时候才具有周期三行为. 并且这种行为特征与外显子的长度、碱基在密码子三个位置上的分布以及氨基酸密码子的使用偏好均有密切关系, 同时符合蛋白质翻译次序的外显子也具有对密码子使用的偏好性, 这一研究结果对于提高基因预测的准确率以及内含子功能的研究具有重要意义.     

DNA分子结构的多态性研究 (Ⅱ) 吖啶橙凝聚体变化诱导的质粒DNA大分子构象的研究

利用吸收光谱和荧光光谱方法,研究了吖啶橙（ＡＯ）与质粒ＤＮＡ水溶液、以及含胶束介质的吖啶橙与质粒ＤＮＡ溶液体系的相互结合作用及减色效应。结果表明：吖啶橙对质粒ＤＮＡ的吸收光谱有减色效应;含十二烷基硫酸钠（ＳＤＳ）的ＡＯ水溶液体系中,随着ＳＤＳ浓度的增加,其光谱结果表现为由凝聚态向单体的转化。而在含十二烷基硫酸钠（ＳＤＳ）的ＡＯ与质粒ＤＮＡ溶液体系中,吖啶橙凝聚态随ＳＤＳ浓度的增加,对ＡＯ与质粒ＤＮＡ相互结合产生协同的减色效应,使质粒ＤＮＡ空间结构发生缩拢。进一步采用电泳法研究了ＡＯ凝聚态可能对质粒ＤＮＡ构象的影响,结果表明：在ＡＯ与质粒ＤＮＡ溶液体系中,ＡＯ浓度的增加对质粒ＤＮＡ构象未产生影响;而在含有ＳＤＳ的ＡＯ与质粒ＤＮＡ的溶液体系中,由于ＳＤＳ对ＡＯ凝聚态的解聚作用,以及ＳＤＳ对质粒ＤＮＡ减色效应的协同作用,使得质粒ＤＮＡ的构象发生变化,诱导质粒ＤＮＡ形成超螺旋构象     

硝酸镧与丙氨酸反应的热化学研究

稀土离子具有独特的生理、生化特性．氨基酸是体内蛋白质分子的基本单元,它通过ＤＮＡ,ｍＤ－ＮＡ复制、转录、翻译成不同类型的蛋白质分子．１９２８年Ｆｅｉｆｅｒ首次合成,１９７５年Ａｎｙｈｉｌｅｒｉ报道了稀土氨基酸配合物Ｌａ（Ｇｌｙ）３·Ｃｌ３·Ｈ２Ｏ的抗肿瘤作用．显然,研究稀土氨基酸配合物具有十分重要的意义．近年来,对稀土氨基酸配合物的研究已成为化学和生物学交叉领域的研究热点［１－５］．认识它们的基本热力学性质也变得越来越重要．但是,国内外在这方面的研究尚处于开拓时期． 姜相武等［４］在 ３５℃时对体…     

DNA分子结构的多态性研究(Ⅰ)——阳离子型表面活性剂诱导λ-DNA由线圈型向球型的转变

活性细胞众多的遗传信息均通过DNA链的碱基序列按一定的自身调节方式表达出各种蛋白质[1].DNA与各种不同性质的组分,如蛋白质、类脂及无机离子等的相互识别作用是确保细胞处于生理活性状态的重要调节机制.     

铕苯丙氨酸配合物与DNA相互作用的循环伏安法和紫外光谱法研究

运用循环伏安法和紫外光谱法研究了Ｅｕ（ｐｈｅ）３＾３＋与ＤＮＡ的相互作用。Ｅｕ（ｐｈｅ）３＾３＋与ＤＮＡ作用后，循环伏安曲线的峰电流密度减小，峰电位差稍有增中，扩散系数减小，紫外光谱的特征吸收峰呈明显的减色效应，这可能是Ｅｕ（ｐｈｅ）３＾３＋与ＤＮＡ因静电引力形成加合物以及Ｅｕ（ｐｈｅ）３＾３＋有很强的遮蔽负电荷 作用，促使碱基面与碱基面的进一步堆积所致。     

DNA分子结构的多态性研究：（Ⅱ）吖啶橙凝聚体变化诱导的质粒DNA？…

利用吸收光谱和荧光光谱方法，研究了吖啶橙（ＡＯ）与质粒ＤＮＡ水溶液，以及含胶束介抽的吖啶橙与质粒ＤＮＡ溶液体系的相互结合作用及减色效应。结果表明：吖啶橙时质粒ＤＮＡ的吸收光谱有减色效应；含十二烷基硫酸钠（ＳＤＳ）的ＡＯ水溶液体中，随着ＳＤＳ浓度的增加，其光谱结果表明由凝聚态向单体的转化。而在含十二烷基硫酸钠（ＤＳ）的ＡＯ与质粒ＤＮＡ溶液体系中，吖啶橙凝聚态随ＳＤＳ浓度的增加，对ＡＯ与质粒ＤＮＡ相互     

Fapy-G对碱基氢键复合物影响的理论研究

应用量子化学方法对2,6-二氨基-4-羟基-5-甲酰胺嘧啶(Fapy-G)与正常碱基作用形成的20种氧化碱基对的多种性质进行了理论分析,碱基G的C8位被氧化后N7和N9位分别增加一个H原子,使其由氢键受体变成氢键供体,N7,N9及O6原子所带的电荷变负,同时O6作为氢键受体的能力增强.与碱基单体相比,碱基对中形成氢键的受体原子所带的电荷平均减小0.05 e;供体H原子所带的电荷平均增大0.02 e.Fapy-G分子中六元环上受体N原子参与形成氢键时,环的呼吸振动模式和N与对位C的振动模式的振动频率蓝移;与氢键相关的振动频率红移.所有氧化碱基对中,NH…N比NH…O氢键作用更强,且在NH…N氢键中,在六元环上的供体N原子形成的氢键比在氨基或开环上的供体N原子形成的氢键强.Fapy-G与碱基A作用结合能区域顺序为1>2>4>3,与碱基T(R)作用区域顺序为3=4>1>2;水溶液使Fapy-G与碱基C作用的结合能减弱程度最大,结合能达到41.84~58.58 k J/mol,且使碱基对结合能力次序发生改变.     

铽（Ⅲ）探针法研究一些金属离子与DNA的作用

本文首次选用Ｔｂ（Ⅲ）作为荧光探针，研究了ｃｄ（Ⅱ）、Ｚｎ（Ⅱ）、Ｃａ（Ⅱ）、Ｍｇ（Ⅱ）与ＤＮＡ反应的结合部位。结果表明：Ｃｄ（Ⅱ）、Ｚｎ（Ⅱ）在ＤＮＡ上有两种结合部位，即ＤＮＡ双螺旋外侧的磷酸基和内侧的碱基鸟漂呤上的Ｎ－Ｔ。而ｃａ（Ⅱ）、Ｍｇ（Ⅱ）在ＤＮＡ上只有一个结合部位即磷酸基。说明Ｔｂ（Ⅲ）不仅可以作为ＤＮＡ构象及ＤＮＡ单链成分、不配对碱基残余的探针，而且可以用它探测一些金属离子与ＤＮＡ反应的结合部位。     

自旋标记荧光探针表征生物活性分子的自由基损伤

生命过程中产生的经基自由基(^˙OH)已引起广泛关注.目前,对于^˙OH的研究主要集中在直接对^˙OH进行定量表征^[1~3]和问接检测^˙OH诱导损伤生物大分了的损伤产物.^˙OH诱导损伤生物大分了,能够产生大量的碳中心自由基^[4,5].     

On the electrochemical reduction mechanism of indolinone nitroxide radicals in DMF

A study of the electroreduction of 1,2-dihydro-2-phenyl-2-alkyl (or phenyl)-3 H-indol-3-one-1-oxyls (nitroxide radicals) in dimethylformamide is presented. The techniques of ac and dc voltammetry, controlled potential coulometry, ESR and UV spectrometry were used. In DMF-H₂O nitroxide radicals are reduced in two steps: the first is the reversible monoelectronic formation of the corresponding N-hydroxides, while the second (which involves a chemical reaction) is the irreversible production of 2,3-dihydro-2-phenyl-2-alkyl (or phenyl)-3-hydroxy indoles. A multistep scheme is suggested, based upon the electrochemical and spectrometric data.     

The paramagnetic species produced in the reactions of organometallic compounds XIII—the anion radicals of carboxylates

In the reactions of meta- and para-alkyl substituted benzoic acids with aryl Grignard reagents, in tetrahydrofuran solutions and in the presence of nickel salts, the ESR spectra of the anion radicals of carboxylates derived from the benzoic acids were observed which represent the intermediates in the formation of ketyl radicals.     

Ion-molecule reactions of primary radical cations in the liquid-phase radiolysis of <Emphasis Type="Italic">n</Emphasis>-alkanes: An EPR study

Radiation-chemical yields the liquid-phase radiolysis of C₅–C₁₂ n-alkanes were measured using the spin trap technique. The yields of n-alkyl radicals depended only slightly on the chain length in C₅–C₉ alkanes and amounted up to 30% of the total yield of trapped radicals; they were inhibited by the addition of charge scavengers. An analysis of the experimental results together with data on radicals in irradiated crystalline alkanes and radical cations in freon matrices showed that n-alkyl radicals results from the ion-molecule reactions of primary radical cations, whereas the protonated ions RH₂⁺ as products of these reactions are a source of sec-alkyl radicals. At least 60% of primary radical cations are consumed via these reaction pathways. A part of sec-alkyl radicals is due to gauche-conformers. The relative amount of primary alkyl radicals formed in the degradation of excited states and the subsequent charge neutralization processes should be insignificant.Translated from Khimiya Vysokikh Energii, Vol. 39, No. 1, 2005, pp. 5–14.Original Russian Text Copyright © 2005 by Belevskii, Belopushkin.     

Graphitic Carbon Nitride Microspheres Supportedα-FeO(OH)Hybrids for Visible Light Photodegradation of MO

Graphitic carbon nitride(g-C3N4)microspheres supported a-FeO(OH)hybrids[α-FeO(OH)/g-C3N4]were prepared by means of a self-assembly method in deionized water.By UV-visible diffiise reflectance spectroscopy,it has been confirmed thatα-FeO(OH)/g-C3N4 has a wider absorption range thanThe feature ofα-FeO(OH)/g-C3N4 can be attributed to the efficient separation of the electron-hole pairs with photoluminescence spectra.The degradation rate of methyl orange(MO)is up to 99%under the optimal conditions of 110 min,initial concentration of 30 mg/L,anα-FeO(OH)/g-C3N4 dosage of 15 mg as well as visible light.The mechanism for this photocatalytic reaction was proposed,with hydroxyl radicals being a major active catalytic species.     

Synthesis and Antioxidative Effect of Aromatic Disulfides

Bis(4-hydroxy-3-formylphenyl) and bis[3-alkyl(aryl)iminomethyl-4-hydroxyphenyl] disulfides were prepared. Their reaction with cumylperoxy radicals was studied, and the inhibiting effect on the cumene oxidation was examined.     

Inhibiting activity of isocamphyl substituted phenols and their mixtures with 2,6-di-<Emphasis Type="Italic">tert</Emphasis>-butylphenol in the initiated oxidation of ethylbenzene

The stoichiometric coefficients of inhibition and rate constants for the reaction of several terpenephenols (isocamphyl substituted phenols) with ethylbenzene peroxy radicals were measured. Their reactivity was found to increase as the number of alkyl substituents grew and decreased with an o-alkoxyl compared with o-alkyl substituent because of the formation of an intramolecular H-bond. In spite of similar antiradical activities of terpenephenols with isocamphyl and isobornyl substituents, the reactivities of phenoxyl radicals formed from them in the interaction with sterically hindered phenol molecules are substantially different. They are higher for isocamphylphenols with substituents turned with respect to the aromatic ring plane.     

Photo-oxidation of methionine-containing peptides by the 4-carboxybenzophenone triplet state in aqueous solution. Competition between intramolecular two-centered three-electron bonded (S...S)+ and (S...N)+ formation

Quantum yields for the formation of transients were measured following the quenching of triplet 4-carboxy-benzophenone (3CB*) by methionine-containing peptides in aqueous solutions. Ketyl radicals (CBH.), ketyl radical anions (CB.-) and various sulfur radical cations were identified following the triplet-quenching events. The presence of these intermediates indicated that the triplet-quenching mechanism can be characterized as mainly electron-transfer in nature. The quenching rate constants were of the order of 2 x 10(9) M-1 s-1. There were small, but significant, differences in the triplet-quenching rate constants, and these trends indicate the existence of multiple sulfur targets in the quenchers. The absorption of the transient products was followed in detail by using spectral-resolution analysis. From the absorption data, quantum yields were estimated for the formation of the various transients. There were differences found in the yields of the transient products between the experiments, where the quenchers were the "mixed" stereoisomers of methionylmethionine (L,D and D,L) and experiments where the quenchers were L,L and D,D stereoisomers. Triplet-quenching data from several other methionine-containing small oligopeptides were analyzed in an analogous manner. Systematic variations were observed, and these patterns were discussed in terms of competitive donation of protons to the CB.- within the charge-transfer complex. The competition was between protons on carbons adjacent to the sulfur-radical center and protons on the protonated amino groups of the radical cation. In addition, there was a competition between the two intramolecular two-centered, three-electron bonded species (S therefore S)+ and (S therefore N)+ that play roles in the secondary kinetics.     

烯基取代的甲酸态四氢叶酸辅酶模型的合成及其碳单元转移反应

以邻苯二胺和乙酸为原料,经3步反应合成了8种烃基乙烯基取代的苯并咪唑盐,其结构用元素分析,¹HNMR,IR,MS和UV-Vis进行了表征,并以其作为取代的甲酸态四氢叶酸辅酶模型,同亲核试剂(格氏试剂)反应得到烃基乙烯基取代的一碳单元完全转移的产物α,β-不饱和酮,为α,β-不饱和酮的合成提供了一种简便的仿生合成新方法.     

聚苯乙烯热降解机理的理论研究

采用密度泛函理论B3LYP/6-311G（d）方法,对聚苯乙烯（PS）热降解反应机理进行了研究。PS热降解的主要产物是苯乙烯,其次是甲苯、α-甲基苯乙烯、乙苯和二聚体等芳烃化合物。PS热降解反应主要包括主链C-C键均裂、β-断裂、氢转移和自由基终止等反应。针对以上各类反应进行了路径设计和理论计算分析,对参与反应的分子的几何结构进行了优化和频率计算,获得了各热降解路径的标准动力学和热力学参数。计算结果表明,苯乙烯主要由自由基的链端β-断裂反应形成;二聚体主要由分子内1,3氢转移的反应形成;α-甲基苯乙烯由分子内的1,2氢转移后进行β-断裂形成;甲苯由苯甲基自由基夺取主链上的氢原子形成;乙苯由苯乙基自由基夺取氢原子形成。动力学分析表明,苯乙烯形成所需要的能垒低于其他产物形成所需要的能垒,故苯乙烯为主要的热降解产物;这与相关实验结果基本一致。