[1]方永勤,等.金属卟啉仿生催化剂进展[J].常州大学学报(自然科学版),2010,(01):72-78.
 FANG Yong -qin,XU Liang,et al.Advances of Metalloporphyrins Biomimetic Catalysts in Oxidation Reactions[J].Journal of Changzhou University(Natural Science Edition),2010,(01):72-78.
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金属卟啉仿生催化剂进展()
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常州大学学报(自然科学版)[ISSN:2095-0411/CN:32-1822/N]

卷:
期数:
2010年01期
页码:
72-78
栏目:
出版日期:
2010-03-25

文章信息/Info

Title:
Advances of Metalloporphyrins Biomimetic Catalysts in Oxidation Reactions
作者:
方永勤1 2 许 亮1 张丽琼1 吕春绪2
1.江苏工业学院精细化工研究所, 江苏 常州 213164 ;2.南京理工大学化工学院, 江苏 南京 210094
Author(s):
FANG Yong -qin 1 2 XU Liang 1 ZHANG Li -qiong1 LV Chun -x u2
1 .Institute of Fine Chemicals , Jiang su Poly technic University , Changzhou 213164 , China ;2 .Schoo l of Chemical Engineering , Nanjing Universi ty of Science and Technology , N anjing 210094 , China
关键词:
细胞色素P -450 金属卟啉仿生催化氧化
Keywords:
cy to chrome P -450 metallopo rphy rin biomime tic catalysi s o xidat ion
分类号:
O 643.3  
文献标志码:
A
摘要:
细胞色素P -450 是一种生物体内催化分子氧氧化内源底物的单加氧酶, 其活性片段的核心结构是金属卟啉络合物。人 工合成的金属卟啉络合物可作为细胞色素P -450 的有效模拟物, 应用于烯烃、直链烷烃、环烷烃、芳烃、芳烃侧链、及各种 杂原子等多种底物的催化氧化。人工合成的金属卟啉络合物可分为:对称型金属卟啉、非对称型金属卟啉、μ-氧代双核金属 卟啉、负载型金属卟啉4 大类。现以金属卟啉络合物的结构为线索, 论述了结构与催化活性及稳定性的内在联系, 重点介绍了 近几年国内外金属卟啉仿生催化剂的氧化应用研究进展, 及仿生催化氧化的工业化发展前景。
Abstract:
Cytochrome P -450 is a kind o f monoo xyg enase , w hich is used as cataly st for the o xidat ion of endo geno us substrates by mo lecula r ox ygen in vivo .The co re structure o f it s act ive segment s i s metallopo rphyrin complexes .Sy nthetic metalloporphy rin comple xes could be used as effectiv e mimics of Cy tochrome P -450 fo r the cataly tic oxidatio n o f o rganic subst rates w hich include alkenes , linear alkanes , cycloalkanes , arenes , aromatic side -chains , and so rt s of heteroatoms .Synthet ic metalloporphy rin complexes could be divided into three catego ries :symmet rical metal lopo rphy rin , asymmetric metallopo rphy rins , μ-o xo -bismetallo po rphyrins , and supported metallo po rphy rins .U sing st ructures of metalloporphy rins as the index , the inte rrelat ionship betw een the structure , ca talyt ic activi ty and stability is review ed .The recent pro gress o f application of me talloporphy rins in oxidatio n reactions and the indust rializa tion prospect of biomimetic o xidation w as mainly reviewed

参考文献/References:

[1] 佘远斌, 王兰芝, 宋旭锋, 等.金属卟啉类仿生催化剂的合 成、构效关系及在催化氧化碳氢化合物中的应用[J] .精细 化工, 2005 , 22 (6):401 -408.
[2] Groves J T , Nemo T E , Myers R S .H ydroxylati on and epoxidation cat alyz ed by iron - porphin e complexes .Oxygen t ransf er f rom iodosylbenzene [J] .Journal of T he Ameri can Chemical Society , 1979 , 101 (4):1 032 -1 033 .
[3] 周贤太, 纪红兵, 裴丽霞, 等.金属卟啉催化剂应用于均相氧 化反应的研究进展[J] .有机化学, 2007 , 27 (9):1 039 -1 049 .
[4] 王兰芝, 佘远斌, 钟儒刚, 等.铁卟啉催化剂前线轨道能量与 其催化活性的关系[J] .化工学报, 2006 , 57 (6):1 339 -1 345 .
[5] Liu N , Jiang G F , Guo C C , et al.Quant it ative st ructu re - acti vi ty relation ship studies on i ron porphyrin -cat alyzed cycl ohexane oxidat ion wi th PhIO [J] .Journal of Molecul ar Cat alysis A :Chemical , 2009 , 304 :40 -46 .
[6] 吕庆章, 卢雁, 王健吉.氯化铁卟啉和氯化四苯基铁卟啉的密 度泛函量子化学计算研究[J] . 计算机与应用化学, 2005 , 22 (11):1 009 -1 012 .
[7] Bikiel D E , Bari S E , Docto rovich F , et al.DFT s tu dy on the reactivit y of i ron p orphyrins tuned by ring subst itut ion [J] . Jou rn al of Inorganic Bi ochemist ry , 2008 , 102 :70 -76 .
[8] Guo C C , Liu Q , Wang X T , et al.Selecti ve liquid phase oxidat ion of t oluene wi th ai r [J] .Applied Catalysi s A :General , 2005 , 282 :55 -59 .
[9] 张帅, 刘强, 郭灿城.锰卟啉-醋酸钴复合催化体系对甲苯氧 气氧化的催化作用[J] .化工学报, 2008 , 59 (6):1 396 -1 400 .
[10] Ji H B , Yuan Q L , Zhou X T , et al.H ighly eff icient selecti ve oxidation of alcohol s to carbonyl compou nds catalyzed by ruthenium (Ⅲ) mes o - tet rapheny lporphyrin chl oride in the presen ce of m olecular oxygen [J] .Bioorgani c & Medicinal Chemist ry Lett ers , 2007 , 17 :6 364 -6 368 .
[11] Lyons J E , Elli s P E , Myers H K .H alogenat ed metall op or- 方永勤等.金属卟啉仿生催化剂进展 · 77 · phy rin complexes as catalys ts f or select ive reaction s of acyclic alk anes w ith m olecular oxygen [J] . Journal of Cat aly sis , 1995 , 155 :59 -73 .
[12] Haber J , Mat achow ski L , Pamin K , et al .The ef fect of perip heral sub sti tu ent s in met al loporphyrins on thei r cat alyt ic act ivit y in Lyons sy st em [J] .Jou rnal of Molecular Cat aly sis A : C hemi cal , 2003 , 198 :215 -221 .
[13] Rez aeifard A , Jaf arpou r M , Moghaddam G K, et al.Cyt ochrome P -450 m odel react ions :Ef fci ent and highly selecti ve oxidat ion of alcohols wi th t et rabu tylammonium peroxymonos ulf ate cat alyz ed by Mn -porphy rins [J] .Bioorganic &Medi cinal C hemi st ry , 2007 , 15 :3 097 -3 101 .
[14] S ilva G F , Si lva D C , Guimaraes A S , et al.Cy clohexan e hydroxylati on by i odosy lben zene and iodobenzene diacet at e catalyz ed by a new oct ah al ogenated Mn -porph yrin com plex :Th e ef fect of meso -3 -pyridyl subs tituent s [J] .J ou rnal of Molecul ar Catalysi s A:C hemi cal , 2007 , 266 :274 -283 .
[15] 唐渝, 张渊明, 岑颖洲.β -取代卟啉及卟啉锰对氧化破坏的 稳定性[J] .化学世界, 2004 , 10 :515 -518 .
[16] Woggon W D , Wagenknech t H A , Clau de C .Syntheti c act ive si te anal ogu es of heme -thiolat e prot ein s Charact eriz at ion and ident ifi cati on of int ermediates of the cat alyti c cy cles of cyt ochromeP450cam and chl oroperoxidase [J] .Journal of Inorganic Biochemi st ry , 2001 , 83 :289 -300 .
[17] 佘远斌, 范丽丽, 张燕慧, 等.金属卟啉仿生催化绿色合成 对硝基苯甲醛的新方法[J] . 化工学报, 2004 , 55 (2):2 032 -2 037 .
[18] Mohajer D , S adeghian L.Co -cat alyti c ef fect s of ni t rogen don ors on the epoxidation of cyclooct ene wi th tet ra -n -but ylammonium hy drogen monopersulf ate in the presence of m anganese (Ⅲ) t etraary lporphyrin s :A com parat ive study [J] . Journal of M olecu lar C at alysis A:Chemi cal , 2007 , 272 :191 -197 .
[19] 郭灿城, 李枝蓬, 梁本熹, 等.金属卟啉催化性能与金属原 子电子构型关系[J] .湖南大学学报, 1996 , 23 (5):66 - 70 .
[20] M arques A , Marin M , Ruasse M F .Hydrogen peroxide oxidati on of Mus tard -Model sul fides cat alyzed by iron and m anganese t et raarylporphyrines .Oxygen t ransf er t o sulf ides vers us HO dismu tat ion and cat alyst b reakdow n [J] .Th e Journal of Organic Chemist ry , 2001 , 66 (23):7 588 -7 595 .
[21] T agliat es ta P , Giovann et ti D , Leoni A , et al.Manganes e (Ⅲ)porphy rins as cat al yst s for the Oxidat ion of aromatic s ubs t rat es An in sight int o the reaction mechanism and the role of the Cocatalys t [J] .Journal of Molecul ar Catalysi s A :Chemical , 2006 , 252 :96 -102 .
[22] 何宏山, 刘勇, 林岩心, 等.2 -氨基苯并咪唑基尾式卟啉及 其过渡金属配合物的合成、谱学性质及催化研究[J] .光谱 实验室, 2002 , 19 (3):293 -298 .
[23] Miyazaki Y, Sat ak e A , Kobuke Y.Oxidation of adaman tane cat aly sed by imidazolylp orphyrinat oi ron (Ⅲ) comp lexes and st ructu ral s tudies of 5 -coo rdin at ing iron (Ⅲ)porphy rin [J] . Jou rn al of Molecular Cat aly si s A :Chemical , 2008 , 283:129 -139 .
[24] 刘丹, 赵小菁, 章应辉, 等. 尾式锌卟啉与含氮类客体轴配 反应的光谱及热力学研究[J] . 南开大学学报(自然科学 版), 2006 , 39 (1):1-7 .
[25] Guo C C , Li H P , Xu J B.S tudy of synthesis of μ-oxo - bism anganese (Ⅲ)porph yrin compoun ds and their cat aly sis of cyclohex ane oxidation by PhIO [J] .J ou rnal of Catalysis , 1999 , 185 :345 -351 .
[26] Polt owi cz J , T ab or E , Pamin K , et al.Ef f ect of sub sti tuen ts in the manganese μ-oxo porphyrin s cat alyzed oxidati on of cyclooct ane w ith molecular oxygen [J] .Ino rganic Ch emi st ry Commu ni cation , 2005 , 8 :1 125 -1 127 .
[27] 郭灿城, 王旭涛, 刘强.选择性催化空气氧化甲苯和取代甲 苯成醛和醇的方法:C N , 1521153A [P] .2004 -08 -18 .
[28] 佘远斌, 罗振华, 宋旭锋, 等.金属卟啉仿生催化氧化邻硝 基甲苯绿色合成邻硝基苯甲醛[J] . 化工学报, 2007 , 58 (11):2 782 -2 786 .
[29] 朱申杰, 桂明德, 郭灿城.μ-氧-双四苯基卟吩合铁(Ⅲ) 在CH 2Cl - 2 氧化剂体系中的反转反应研究[J] .高等学校化 学学报, 1989 , 10 (11):1 100 -1 104 .
[30] Rahim an A K , Rajesh K , Bharathi K S , et al.Man ganese (Ⅲ)p orp hyrin -encap sulated Ti , S i -mes oporou s m olecu lar sieves as heterogeneous catalys t s for the epoxidati on of alkenes [J] .Appli ed Cat alysis A :Gen eral , 2006 , 314 :216 -225 .
[31] 王旭涛, 褚明福, 郭灿城.咪唑修饰硅胶配位固载锰(Ⅲ) 卟啉对环己烷空气氧化的催化作用[J] .高等学校化学学报, 2005 , 26 (1):64 -67.
[32] 章艳, 高保娇, 王蕊欣.固载Mn P-PGMA -SiO2 催化剂的 制备及其对乙苯氧化反应的催化性能[J] .催化学报, 2008 , 29 (3):247 -252 .
[33] 黄冠, 姜权, 郭灿城.甲壳素铁卟啉和壳聚糖铁卟啉催化性 能差异研究[J] .化学试剂, 2005 , 27 (5):261 -264 .
[34] Moghadam M , T angs taninejad S , Mirkh ani V .Polys ty rene -bound Mn (T4PyP)A highly ef fici ent and reusable cat aly st f or biomimet ic oxidati ve decarboxylati on of carb oxylic acids wi th sodium peri odat e [J] . Bi oo rganic & Medicinal Ch emi st ry , 2009 , 17 :3 394 -3 398 .
[35] 刘烨, 张红娇, 吴海虹, 等. 离子液体体系中离子型锰卟啉 对苯乙烯的催化氧化[J] . 高等学校化学学报, 2007 , 28 (8):1 523 -1 527 .

备注/Memo

备注/Memo:
作者简介:方永勤(1966 -), 女, 江苏江堰人, 高级工程师。
更新日期/Last Update: 2010-03-25