文章摘要
张森,张铁欣,何成,段春迎.P450酶启发的染料后修饰铁卟啉MOF光催化氧化[J].精细化工,2020,37(12):
P450酶启发的染料后修饰铁卟啉MOF光催化氧化
Cytochrome P450 enzyme-inspired photocatalytic C—H oxidation by organic dye post-synthetically modified Fe-porphyrin-based MOF
投稿时间:2020-04-25  修订日期:2020-05-15
DOI:
中文关键词: 酶模拟  细胞色素P450酶  金属有机框架  染料  后修饰  光氧化  碳氢键活化
英文关键词: enzyme mimicking  cytochrome P450  metal-organic framework  organic dye  post-synthetic modification  photocatalytic oxidation  C-H activation
基金项目:国家自然科学基金项目(面上项目,重点项目,重大项目)
作者单位E-mail
张森 大连理工大学 731124466@qq.com 
张铁欣 大连理工大学 zhangtiexin@dlut.edu.cn 
何成 大连理工大学  
段春迎 大连理工大学  
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中文摘要:
      受细胞色素P450酶氧化代谢的启发,将染料酸性红87(Acid Red 87)后修饰到金属有机框架PCN-222(Fe)中,构筑非均相拟酶光催化剂Acid Red 87@PCN-222(Fe),拉近染料与铁卟啉中心的距离,利用光致电子转移模拟P450的电子传递链。以1-(4-甲氧基苯基)乙醇为模板底物,对光催化氧化的条件如溶剂、电子牺牲剂、氧源等进行筛选,得到优化反应条件为高碘酸钠(53.5 mg, 0.25 mmol),2,6-二甲基吡啶三氟甲磺酸盐(64.3 mg, 0.25 mmol),Acid Red 87@PCN-222(Fe)(12.0 mg, 0.00625 mmol),乙腈(2 mL),530 nm波长LED光照反应24 h。催化剂重复使用3次后仍保持活性和晶态结构。该催化体系对苄基碳氢键氧化具有良好的底物适用范围,可应用于非甾体类抗炎药匹美诺芬的区位选择性氧化,产率为48%,该体系还可将芳基硫醚类化合物氧化至相应的亚砜,体现其在精细化工制药、工业脱硫领域的应用潜质。
英文摘要:
      Enzyme-inspired by oxidative metabolism of cytochrome P450, the organic dye Acid Red 87 was introduced into metal-organic framework (MOF) PCN-222(Fe) by post-synthetic modification, to construct the heterogeneous enzyme-mimicking photocatalyst Acid Red 87@PCN-222(Fe) in which the proximal spatial distance between the dye and Fe-porphyrin moiety was expected to facilitate the photoinduced electron transfer for mimicking the electron transfer chain in P450. Employing 1-(4-methoxyphenyl)ethan-1-ol as the model substrate, the reaction conditions such as solvent, electronic sacrificial agent, oxygen source, and et al. were screened, and the optimized conditions were obtained, as shown below: sodium periodate as the oxygen source (53.5 mg, 0.25 mmol), 2,6-lutidine trifluoromethanesulfonate as the proton source (64.3 mg, 0.25 mmol), Acid Red 87@PCN-222(Fe) as the photocatalyst (12.0 mg, 0.00625 mmo), acetonitrile as the solvent (2 mL), under the photoirridation from 530-nm LED for 24 hours. The MOF-based photocatalyst could be recycled and reused for at least 3 times without remarkable deteriorations of catalytic reactivity and structural crystalline. This photocatalytic benzylic C—H oxidation was of broad substrate scope under the optimal conditions, and the highly regioselective benzylic oxidation of the nonsteroidal antiinflammatory drug, Pimeprofen?, at the C7-position, could be achieved in a yield of 48%. This protocol could be further expended to the oxidation of aryl thioethers to the corresponding aryl sulfoxides. Those results demonstrated the potential interests of this enzyme-inspired photocatalytic methodology in pharmaceutical field and industrial desulfurization.
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