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联苯基团引起的激发三重态重排活性增长
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作者 吴国生 胡军 +2 位作者 李江平 舒菊坪 徐建华 《有机化学》 SCIE CAS CSCD 北大核心 1991年第6期606-608,共3页
双发色团分子光化学研究兴趣与日俱增。我们在以前报道一个有趣的现象:基态发色团间的分子轨道交叠左右光反应机理。3-甲基-3-联苯基-1-丁烯(1),是有特殊意义的分子。与激发能高达(143 kcal/mol)的孤立双键相比,联苯基的激发能特别低(69... 双发色团分子光化学研究兴趣与日俱增。我们在以前报道一个有趣的现象:基态发色团间的分子轨道交叠左右光反应机理。3-甲基-3-联苯基-1-丁烯(1),是有特殊意义的分子。与激发能高达(143 kcal/mol)的孤立双键相比,联苯基的激发能特别低(69 kcal/mool)。如此大的激发能差使乙烯基与联苯 p电子间的交叠通道更加畅通,基态1的稳定构象是 endo 型,1的光化学行为将不同于无环双π甲烷分子。1000 W 高压汞灯照射1的正已烷溶液, 展开更多
关键词 双发色团分子 光重排 三重态
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对二嗪N,N'-二氧化物光还原的电子自旋共振研究 被引量:1
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作者 汪汉卿 林树坤 《感光科学与光化学》 CSCD 1990年第3期161-170,共10页
报道了利用原位电子自旋共振(ESR)技术研究对二嗪N,N′-二氧化物光解的结果。研究结果表明,化合物5,6,7和8通过光还原过程从溶剂分子夺取氢原子分别生成稳定的自由基,记录出它们分辨良好的ESR谱。文中还讨论了对二嗪N,N′-二氧化物的光... 报道了利用原位电子自旋共振(ESR)技术研究对二嗪N,N′-二氧化物光解的结果。研究结果表明,化合物5,6,7和8通过光还原过程从溶剂分子夺取氢原子分别生成稳定的自由基,记录出它们分辨良好的ESR谱。文中还讨论了对二嗪N,N′-二氧化物的光化学反应的自由基机理。 展开更多
关键词 对二嗪N N`-二氧化物 光重排 ESR
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Complete remission of gastric Burkitt's lymphoma after eradication of Helicobacter pylori 被引量:1
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作者 Isabelle Baumgaertner Christiane Copie-Bergman +5 位作者 Michael Levy Corinne Haioun Antoine Charachon Maryse Baia Iradj Sobhani Jean-Charles Delchier 《World Journal of Gastroenterology》 SCIE CAS CSCD 2009年第45期5746-5750,共5页
Burkitt's lymphoma is a highly aggressive non-Hodgkin lymphoma, often presenting in extra-nodal sites. It generally has a poor spontaneous outcome and needs aggressive treatment with systemic and intrathecal chemothe... Burkitt's lymphoma is a highly aggressive non-Hodgkin lymphoma, often presenting in extra-nodal sites. It generally has a poor spontaneous outcome and needs aggressive treatment with systemic and intrathecal chemotherapy. Occurrence at the gastric site is rare. We report the case of a 39-year old woman who presented with a prominent ulcerated lesion of the antrum corresponding histologically to a Burkitt's lymphoma associated with He/icobacter py/ori (H pylori) infection. Interphase fluorescence in situ hybridization (FISH) demonstrated c-MYC gene rearrangement in tumour cells without BCL2 or BCL6 gene translocations. Ulcer healing and tumour regression with a complete histological response were obtained 8 wk after Hpylori eradication. In spite of this complete remission, taking into account the high risk of recurrence, the patient received systemic and intrathecal chemotherapy. Two years later, the patient remained in complete remission. This is the first report of a gastric Burkitt's lymphoma responding to Hpylori eradication. These findings raise the question of the potential role of H pylori in the pathogenesis of some gastric Burkitt's lymphomas, and show the importance of searching for and eradicating the bacteria in combination with conventional chemotherapy regimens. 展开更多
关键词 Burkitt's lymphoma Gastric lymphoma Helicobacter pylori THERAPY
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Isomerization and rearrangement of boriranes: from chemical rarities to functional materials 被引量:2
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作者 Soren K.Mellerup Suning Wang 《Science China Materials》 SCIE EI CSCD 2018年第10期1249-1256,共8页
Stimuli responsive materials have recently been the subject of tremendous research efforts owing to their numerous potential applications. Although there currently exist many different types of "smart" materials, th... Stimuli responsive materials have recently been the subject of tremendous research efforts owing to their numerous potential applications. Although there currently exist many different types of "smart" materials, those based on photoresponsive transformations are especially attractive. In this review, we focus on a relatively new class of photochromic molecules based on the photochemistry of chelate organoborates, which form intensely colored, base-stabilized boriranes.Recent efforts to exploit the reactivity of these systems are summarized, and future prospects in materials science discussed. 展开更多
关键词 Smart materials PHOTOCHEMISTRY boriranes
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Biocatalytic desymmetrization of 3-substituted glutaronitriles by nitrilases. A convenient chemoenzymatic access to optically active (S)-Pregabalin and (R)-Baclofen 被引量:6
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作者 DUAN YiTao YAO PeiYuan +6 位作者 REN Jie HAN Chao LI Qian YUAN Jing FENG JinHui WU QiaQing ZHU DunMing 《Science China Chemistry》 SCIE EI CAS 2014年第8期1164-1171,共8页
Desymmetrization of prochiral 3-substituted glutaronitriles offers a new approach to access (S)-Pregabalin and (R)-Baclofen. A number of nitrilases from diverse sources were screened with 3-isobutylglutaronitriles... Desymmetrization of prochiral 3-substituted glutaronitriles offers a new approach to access (S)-Pregabalin and (R)-Baclofen. A number of nitrilases from diverse sources were screened with 3-isobutylglutaronitriles (1a) or 3-(4'-chlorophenyl)glutaronitriles (1b) as the substrate. Some nitrilases were found to catalyze the desymmetric hydrolysis of la and lb to form optically active 3-(cyanomethyl)-5-methylhexanoic acid (2a) and 3-(4'-chlorophenyl)-4-cyanobutanoic acid (2b) with high enantiomeric excesse (ee), respectively. This cannot be achieved using traditional chemical hydrolysis. Among them, AtNIT3 generated (R)-2b whereas BjNIT6402 and HsN1T produced the opposite (S)-enantiomer with high conversions and ee values. Not only the nitrilases showed different activities and stereoselectivities toward these 3-substituted glutaronitriles, the 3-substitueut of the substrates also exerted great effect on the enzyme activity and stereoselectivity. (S)-2a and (S)-2b were prepared with high yields and ee values using BjNIT6402 and HsNIT as the biocatalysts, respectively. A straightforward Curtius rearrangement of (S)-2a and (S)-2b, followed by the acidic hydrolysis, afforded (S)-Pregabalin and (R)-Baclofen. This offers a new platform methodology for the synthesis of optically active β-substituted T-amino acids of pharmaceutical importance. 展开更多
关键词 enzymatic desymmetrization nitrilases (S)-Pregabalin (R)-Baclofen
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