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甲基重氮烷阳离子(CH 3 N 2 + )与DNA碱基的甲基化反应 甲基重氮烷阳离子(CH 3 N 2 + )与DNA碱基的甲基化反应
Science in China. Series B, Chemistry Pub Date : 2008-12-10 DOI: 10.1360/ZB2008-38-12-1075
李澜 瞿志豪 王竑 李宗和, Ji Zhi-Hao Wang Hong Li Zong-He Li Lan
{"title":"甲基重氮烷阳离子(CH 3 N 2 + )与DNA碱基的甲基化反应","authors":"李澜 瞿志豪 王竑 李宗和, Ji Zhi-Hao Wang Hong Li Zong-He Li Lan","doi":"10.1360/ZB2008-38-12-1075","DOIUrl":"https://doi.org/10.1360/ZB2008-38-12-1075","url":null,"abstract":"在B3LYP/6-31G**和MP2/6-311G**水平上, 计算了终致癌物甲基重氮烷阳离子(CH 3 N 2 + )在气相和水溶剂中与四种DNA碱基上10个亲核位发生甲基化过程的反应机理. 结果表明：在气相和溶剂中, 终致癌物CH 3 N 2 + 对碱基上相应亲核位的甲基化反应过程, 活化能都比较小(","PeriodicalId":49128,"journal":{"name":"Science in China. Series B, Chemistry","volume":"10 1","pages":"1075-1080"},"PeriodicalIF":0.0,"publicationDate":"2008-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84485159","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
吡啶-三唑Os(II)配合物的光谱性质和取代基效应的理论研究 吡啶-三唑Os(II)配合物的光谱性质和取代基效应的理论研究
Science in China. Series B, Chemistry Pub Date : 2008-12-10 DOI: 10.1360/ZB2008-38-12-1059
吴玉辉 周欣 张红星, Zhou Xin Zhang Gong-Xing Tun Yu-Hui
{"title":"吡啶-三唑Os(II)配合物的光谱性质和取代基效应的理论研究","authors":"吴玉辉 周欣 张红星, Zhou Xin Zhang Gong-Xing Tun Yu-Hui","doi":"10.1360/ZB2008-38-12-1059","DOIUrl":"https://doi.org/10.1360/ZB2008-38-12-1059","url":null,"abstract":"为了探究吡啶-三唑Os(Ⅱ)配合物的光谱性质及取代基效应对其配合物发光性质的影响, 采用密度泛函理论DFT中的B3LYP方法优化了系列吡啶-三唑Os(Ⅱ)配合物[Os(ptz)2L2](L=PH3; ptzH=(2-吡啶)-1, 2, 4-三唑( 1 ); [Os(bptz)2L2] (bptzH=3-叔丁基-5-(2-吡啶)-1, 2, 4-三唑 ( 2 ); [Os(fptz)2L2] (fptzH=3-(三氟甲基)-5-(2-吡啶)-1, 2, 4-三唑 ( 3 ); [Os(fbtz)2L2] fbtzH=3-(三氟甲基)-5-(4-叔丁基-2-吡啶)-1, 2, 4-三唑) ( 4 ) 的基态和激发态几何结构. 通过TD-DFT方法结合PCM溶剂化模型计算了配合物分子 1~4 在二氯甲烷溶液中的吸收和发射光谱, 指认了它们的跃迁性质. 通过分析比较计算结果, 论述了取代基效应对配合物 1~4 的磷光发射及磷光量子产率的影响.","PeriodicalId":49128,"journal":{"name":"Science in China. Series B, Chemistry","volume":"6 1","pages":"1059-1062"},"PeriodicalIF":0.0,"publicationDate":"2008-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78695482","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
PbCNN ：一个包含Pb≡≡C键的分子 PbCNN ：一个包含Pb≡≡C键的分子
Science in China. Series B, Chemistry Pub Date : 2008-12-10 DOI: 10.1360/ZB2008-38-12-1070
张文斌, 石国升, 丁益宏, 孙家钟
{"title":"PbCNN ：一个包含Pb≡≡C键的分子","authors":"张文斌, 石国升, 丁益宏, 孙家钟","doi":"10.1360/ZB2008-38-12-1070","DOIUrl":"https://doi.org/10.1360/ZB2008-38-12-1070","url":null,"abstract":"为了预测一种含有Pb≡≡ C三键的新型分子, 在CCSD(T)//B3LYP方法下研究了四原子分子[PbCN 2 ]的势能面, 发现线型异构体 PbCNN 具有良好的热力学和动力学稳定性. 分子轨道分析, 加氢热, 键能及键解离能分析均表明该异构体包含Pb≡≡ C三键.","PeriodicalId":49128,"journal":{"name":"Science in China. Series B, Chemistry","volume":"11 1","pages":"1070-1074"},"PeriodicalIF":0.0,"publicationDate":"2008-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80972422","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
新颖蝶状Fe/E／μ-CO（E=S，Se，Te）簇盐的化学研究进展 新颖蝶状Fe/E／μ-CO（E=S，Se，Te）簇盐的化学研究进展
Science in China. Series B, Chemistry Pub Date : 2008-10-10 DOI: 10.1360/ZB2008-38-10-851
宋礼成
{"title":"新颖蝶状Fe/E／μ-CO（E=S，Se，Te）簇盐的化学研究进展","authors":"宋礼成","doi":"10.1360/ZB2008-38-10-851","DOIUrl":"https://doi.org/10.1360/ZB2008-38-10-851","url":null,"abstract":"介绍了一系列含μ-CO配体的蝶状Fe/E (E = S, Se, Te) 簇盐的化学研究进展. 这些簇盐包括11种新颖簇阴离子, 它们是单蝶状单μ-CO阴离子 [(μ-RE)(μ- CO)Fe 2 (CO) 6 ]- (A, E = S, Se, Te), 双蝶状双μ-CO阴离子{[(μ-CO)Fe 2 (CO) 6 ] 2 (μ-EZE-μ)} 2- ( B , E = S; C, E = Se), 三蝶状三μ-CO阴离子{[(μ-CO)Fe 2 (CO) 6 ] 3 [(μ-SCH 2 CH 2 ) 3- N]} 3- ( D ), {[(μ-CO)Fe 2 (CO) 6 ] 3 [1,3,5-(μ-SCH 2 ) 3 C 6 H 3 ]} 3- ( E ), {[(μ-CO)Fe 2 (CO) 6 ] 3 [(μ-SCH 2 ) 3 CMe]} 3- ( F ) 及由 F转化的双蝶状单μ-CO阴离子 {[(μ-CO)Fe 2 (CO) 6 ][Fe 2- (CO) 6 ][(μ-SCH 2 ) 3 CMe]} - ( G ), 四蝶状四μ-CO阴离子 {[(μ-CO)Fe 2 (CO) 6 ] 4 [1,2,4,5-(μ-SCH 2 ) 4 C 6 H 2 ]} 4- ( H ) 及由它转化的三蝶状双μ-CO阴离子 {[(μ-CO)Fe 2 (CO) 6 ] 2 [Fe 2 - (CO) 6 ][1,2,4,5-(μ-SCH 2 ) 4 C 6 H 2 ]} 2- ( I ),四蝶状四μ-CO阴离子 {[(μ-CO)Fe 2 (CO) 6 ] 4 [(μ- SCH 2 ) 4 C]} 4- ( J ) 及由它转化的三蝶状双μ-CO阴离子{[(μ-CO)Fe 2 (CO) 6 ] 2 [Fe 2 (CO) 6 ] - [(μ-SCH 2 ) 4 C]} 2- ( K ). 文中不仅描述了这十一种阴离子簇盐的形成方法, 而且阐述了它们所发生的新颖反应以及由这些反应所生成的多种新型蝶状Fe/E簇合物, 具有重要理论和应用价值.","PeriodicalId":49128,"journal":{"name":"Science in China. Series B, Chemistry","volume":"18 1","pages":"851-866"},"PeriodicalIF":0.0,"publicationDate":"2008-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75265668","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
应用纳米金/TiO 2 中空微球复合膜高灵敏检测转基因植物外源基因特定DNA序列 应用纳米金/TiO 2 中空微球复合膜高灵敏检测转基因植物外源基因特定DNA序列
Science in China. Series B, Chemistry Pub Date : 2008-10-10 DOI: 10.1360/ZB2008-38-10-922
焦奎 张永春杨涛周娜张伟, Zhang Kui
{"title":"应用纳米金/TiO 2 中空微球复合膜高灵敏检测转基因植物外源基因特定DNA序列","authors":"焦奎 张永春杨涛周娜张伟, Zhang Kui","doi":"10.1360/ZB2008-38-10-922","DOIUrl":"https://doi.org/10.1360/ZB2008-38-10-922","url":null,"abstract":"在碳糊电极表面制备的纳米金/TiO 2 中空微球复合膜可以极大地提高DNA检测的灵敏度. 应用循环伏安法和电化学交流阻抗谱法研究了纳米金和TiO2中空微球在碳糊电极上的固载, 并用[Fe(CN) 6 ] 3-/4- 作为指示剂以电化学交流阻抗谱法表征了DNA的杂交. 此DNA电化学生物传感器成功检测了来自于花椰菜花叶病毒的35S启动子基因的DNA特定序列, 其动力学检测范围为1.0×10 -12 ~ 1.0×10 -8 mol/L, 检测限为2.3×10 -13 mol/L; 同时对从一种转基因大豆中提取的外源基因胭脂碱合成酶基因终止子的聚合酶链式反应(PCR)扩增产物进行了检测, 得到了满意的结果.","PeriodicalId":49128,"journal":{"name":"Science in China. Series B, Chemistry","volume":"47 1","pages":"922-928"},"PeriodicalIF":0.0,"publicationDate":"2008-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78552926","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
低掺杂吡咯低聚物-聚苯乙烯复合膜／电解质溶液体系的介电谱解析——选择渗透性和膜内离子扩散行为 低掺杂吡咯低聚物-聚苯乙烯复合膜／电解质溶液体系的介电谱解析——选择渗透性和膜内离子扩散行为
Science in China. Series B, Chemistry Pub Date : 2008-10-10 DOI: 10.1360/ZB2008-38-10-897
贾京津, 赵孔双, 刘丽虹, 高洁, 韩明娟, 李玉红
{"title":"低掺杂吡咯低聚物-聚苯乙烯复合膜／电解质溶液体系的介电谱解析——选择渗透性和膜内离子扩散行为","authors":"贾京津, 赵孔双, 刘丽虹, 高洁, 韩明娟, 李玉红","doi":"10.1360/ZB2008-38-10-897","DOIUrl":"https://doi.org/10.1360/ZB2008-38-10-897","url":null,"abstract":"制备了十二烷基苯磺酸掺杂的吡咯低聚物(DBSA-oligopyrrole, DOPY)/聚苯乙烯复合膜, 首次在40 Hz~4 MHz频率范围测量了该膜在5种电解质中和不同酸度条件下的介电谱, 并在等效电路模型和界面极化理论基础上分析了弛豫的特征并确定了弛豫机制, 并利用介电参数对各测量结果进行了膜参数的解析, 获得了关于该DOPY/PS复合膜对不同电解质的渗透能力和离子导电特征的原位信息, 以及介质环境的酸度对电参数的影响：介电参数给出了聚吡咯在聚苯乙烯中的最佳含量; 理论解析给出了DOPY/PS复合膜对不同电解质溶液的透过性及选择性规律. 结果表明：由于聚吡咯的存在明显提高了纯聚苯乙烯膜的渗透能力, 在本研究条件下, 确定质量百分数为1%的DOPY/PS复合膜的渗透性能最优; 定量计算了膜内大约含有0.80 mol/m3的负电量, 预测了复合膜对含有不同阴离子的电解质具有选择透过性; 此外, 分析了由于膜本身的性质受溶液pH的影响从而造成的透过性随溶液pH变化的原因. 此研究首次将介电解析从以往的分离膜体系拓展到了复合型导电聚合物膜体系.","PeriodicalId":49128,"journal":{"name":"Science in China. Series B, Chemistry","volume":"16 1","pages":"897-906"},"PeriodicalIF":0.0,"publicationDate":"2008-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84644865","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 1
蒙脱土-钌(II)螯合物杂化膜修饰电极对单磷酸鸟苷的光电催化氧化行为 蒙脱土-钌(II)螯合物杂化膜修饰电极对单磷酸鸟苷的光电催化氧化行为
Science in China. Series B, Chemistry Pub Date : 2008-10-10 DOI: 10.1360/ZB2008-38-10-907
常雪琴, 王舜, 林大杰, 周环, 关卫鹏, 黄少铭
{"title":"蒙脱土-钌(II)螯合物杂化膜修饰电极对单磷酸鸟苷的光电催化氧化行为","authors":"常雪琴, 王舜, 林大杰, 周环, 关卫鹏, 黄少铭","doi":"10.1360/ZB2008-38-10-907","DOIUrl":"https://doi.org/10.1360/ZB2008-38-10-907","url":null,"abstract":"研究了利用LB膜技术制备的蒙脱土-钌(Ⅱ)螯合物杂化膜(Clay-Ru)修饰电极对单磷酸鸟苷的光电催化氧化行为. 实验结果表明：(1)蒙脱土-钌(II)螯合物的纳米单层杂化膜的平均厚度约为(3.4 ± 0.5) nm; (2)紧密排列于ITO电极表面的非电活性蒙脱土的加入降低了电极的电化学活性, 但有效提高了电极的稳定性; (3)具有供电子能力的单磷酸鸟苷(GMP)的加入, 能大大提高ITO/Ru和ITO/Clay-Ru修饰电极的电子传递效率; (4)纳米单层蒙脱土-钌(II)螯合物杂化膜修饰电极的电子传递直接通过蒙脱土纳米单层进行.","PeriodicalId":49128,"journal":{"name":"Science in China. Series B, Chemistry","volume":"32 1","pages":"907-913"},"PeriodicalIF":0.0,"publicationDate":"2008-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86167317","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
偶氮水杨醛Schiff碱在含水介质中对HSO 4 - 离子的识别 偶氮水杨醛Schiff碱在含水介质中对HSO 4 - 离子的识别
Science in China. Series B, Chemistry Pub Date : 2008-08-10 DOI: 10.1360/ZB2008-38-8-694
魏太保 王军 张有明, Wei Ta-Bao Wang Jun Zhang Wei-Meng
{"title":"偶氮水杨醛Schiff碱在含水介质中对HSO 4 - 离子的识别","authors":"魏太保 王军 张有明, Wei Ta-Bao Wang Jun Zhang Wei-Meng","doi":"10.1360/ZB2008-38-8-694","DOIUrl":"https://doi.org/10.1360/ZB2008-38-8-694","url":null,"abstract":"设计合成了4种偶氮水杨醛Schiff碱, 利用紫外-可见吸收光谱系统考察了其与阴离子的作用. 研究表明, 该类受体分子不但对碱性较强的F - , CH 3 COO - 和H 2 PO 4 - 有较强的亲和力, 而且对酸性较强的HSO 4 - 通过质子化而具有独特的光谱响应. 通过加入氢氧化钠、高氯酸时出现了上述相似的显色及紫外光谱响应, 从而进一步说明了受体分子脱质子和质子化的过程.","PeriodicalId":49128,"journal":{"name":"Science in China. Series B, Chemistry","volume":"36 1","pages":"694-699"},"PeriodicalIF":0.0,"publicationDate":"2008-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81285327","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
2，4，6-三硝基甲苯的光催化降解 2，4，6-三硝基甲苯的光催化降解
Science in China. Series B, Chemistry Pub Date : 2008-07-20 DOI: 10.1360/ZB2008-38-7-631
刘秀华, 傅依备, 王和义, 钟志京, 许云书
{"title":"2，4，6-三硝基甲苯的光催化降解","authors":"刘秀华, 傅依备, 王和义, 钟志京, 许云书","doi":"10.1360/ZB2008-38-7-631","DOIUrl":"https://doi.org/10.1360/ZB2008-38-7-631","url":null,"abstract":"在模拟日光下利用Pt/TiO 2 光催化剂对水中2,4,6-三硝基甲苯(TNT, 梯恩梯)进行了光催化降解, 在有催化剂存在时, TNT的破坏更快更彻底, 其降解遵循一级反应动力学. TNT分子上的硝基部分转化为硝酸根离子和亚硝酸根离子. Pt/TiO 2 光催化剂加速了亚硝酸根离子向硝酸根离子的氧化, 在2.5 h内, 终产物硝酸根离子的含量比没有催化剂时提高了32.3倍.","PeriodicalId":49128,"journal":{"name":"Science in China. Series B, Chemistry","volume":"19 1","pages":"631-635"},"PeriodicalIF":0.0,"publicationDate":"2008-07-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87394365","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
新一类抗肿瘤药物 N -糖苷类化合物的光化学活性 新一类抗肿瘤药物 N -糖苷类化合物的光化学活性
Science in China. Series B, Chemistry Pub Date : 2008-07-20 DOI: 10.1360/ZB2008-38-7-618
王玫 张淑萍 邵思常 孙晓宇 姚思德 汪世龙 赵萍
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