阎子峰
长期从事卟啉化学研究。研究兴趣集中在基于卟啉化合物的“碳氢化合物仿生催化氧化”、“红色荧光有机分子设计、合成及发光器件制备”以及“靶向药物分子设计与合成”。
个性化签名
- 姓名:阎子峰
- 目前身份:
- 担任导师情况:
- 学位:
-
学术头衔:
博士生导师
- 职称:-
-
学科领域:
生物化学工程
- 研究兴趣:长期从事卟啉化学研究。研究兴趣集中在基于卟啉化合物的“碳氢化合物仿生催化氧化”、“红色荧光有机分子设计、合成及发光器件制备”以及“靶向药物分子设计与合成”。
阎子峰,现任湖南大学教授,湖南大学化学化工学院院长,国家985工程湖南大学化学生物科技创新平台负责人,首席科学家。湖南大学有机化学和应用化学双学科博士生导师。享受国务院政府特殊津贴,入选湖南省121人才工程第一层次人选。学术兼职有:湖南省化学化工学会常务理事,湖南省科技进步奖评委,湖南省学位委员会理学学科评审组成员,国家教育部基础化学课程分教学指导委员会委员。J. Org. Chem. 和Org. Lett. 稿件评阅人,《化工学报》编委。1990年开始从事金属卟啉的合成及化学仿生催化性能研究,先后主持包括1项国家863、1项国家自然科学基金重点和5项国家自然科学基金面上在内的研究项目近20项。在J. Org. Chem., Anal. Chem., J. Catal., Bioorg.& Med.Chem., Appl.Catal., J.Mol.Catal.《科学通报》,《化学学报》,《高等学校化学学报》等国内外学术刊物发表论文70多篇,SCI和EI收录40多篇。申请发明专利11项,已获批准3项。获湖南省2001年度科技进步二等奖。长期从事卟啉化学研究。研究兴趣集中在基于卟啉化合物的“碳氢化合物仿生催化氧化”、“红色荧光有机分子设计、合成及发光器件制备”以及“靶向药物分子设计与合成”。在金属卟啉仿生催化碳氢化合物氧化领域的研究攻克了目前国际化学工业中碳氢化合物空气氧化反应中转化率低和选择性差的难题,形成了能同时提高碳氢化合物氧化反应转化率和选择性的具有自主知识产权的仿生催化新技术,在国际上第一次将仿生催化基础研究用于改造现有环境不友好的碳氢化合物氧化工艺的实践并获得工业上的成功,被中国石化总公司称为“开辟了碳氢化合物催化氧化新领域”。
-
主页访问
2488
-
关注数
0
-
成果阅读
338
-
成果数
10
阎子峰, Can-Cheng Guo*, Xiao-Qin Liu, Yang Liu, Qiang Liu, Ming-Fu Chu, Xiao-Bing Zhang
Journal of Molecular Catalysis A: Chemical 192(2003)289-294,-0001,():
-1年11月30日
We report the use of simple μ-oxo-bis [tetraphenylporphinatoiron (Ⅲ)] ([TPPFeⅢ]2O) as a catalyst for the selective oxidation of cyclohexane into cyclohexanone and cylcohexanol with air. This is the first time that [TPPFeIII] 2O has been used as a catalyst for the aerobic liquid phase oxidation of cyclohexane in absence of any cocatalyst or coreductants. The oxidation of cyclohexane catalyzed by a very small amount of [TPPFeⅢ] 2O gave 90% selectivity to cyclohexanol and cyclohexanone at 12.55% yield and catalyst turnover numbers of 90,000 (based on the metal) under the conditions of 398K and 0.6MPa. We showed that the reaction yields and the turnover numbers of the catalyst changed with reaction temperature, pressure and the amount of catalyst. In contrast with the corresponding monoironporphyrin, chloro [tetraphenylporphinatoiron (Ⅲ)] (TPPFeIIICl), the oxidation of cyclohexane catalyzed by (TPPFeⅢ) 2O with air had higher yields and greater turnovers.
Metalloporphyrin, Biomimetic catalysis, Cyclohexane oxidation, Molecular oxygen
-
35浏览
-
0点赞
-
0收藏
-
0分享
-
159下载
-
0评论
-
引用
阎子峰, Can-Cheng Guo, * He-Ping Li and Xiao-Bing Zhang
Bioorganic & Medicinal Chemistry 11(2003)1745-1751,-0001,():
-1年11月30日
Seven new nitrogen heterocycle porphyrins, 5, 10, 15, 20-tetra [4-(N-pyrrolidinyl) phenyl] porphine (TBPPH2), 5, 10, 15, 20-tetra [4-(4'-ethylpiperazinyl) phenyl] porphine (TEPPH2), 5, 10, 15, 20-tetra [4-(4'-butylpiperazinyl) phenyl] porphine (TUPPH2), 5, 10, 15, 20-tetra [4-(4'-heptylpiperazinyl) phenyl] porphine (THPPH2), 5-[4-(4'-ethylpiperazinyl) phenyl]-10, 15, 20-triphenylporphine (MEPPH2), 5-[4-(4'-buthylpiperazinyl) phenyl] -10, 15, 20-triphenylporphine (MUPPH2) and piperazine bridge porphine dimer N, N0-di (5, 10, 15, 20-tetraphenylporphinato) piperazine (DiPPH2) have been synthesized by the direct condensation of nitrogen heterocycle substituted benzaldehydes with pyrrole. Each porphine bears one or four substituted pyrrolidine or piperazine moieties that have been used as drugs. Their structures were characterized by elementary analysis, MS, 1H NMR, IR and UV-vis. These nitrogen heterocycle porphyrins aggregates in water and THF solution were studied by the spectrophotofluorimetry. The anticancer activity of these porphines for the liver cancer cells, the stomach tumor cells and the nasopharyngeal carcinoma cancer cells were tested by the MTT assay. Compared with cis-platinum (cis-Pt) and 5-Fluorouracil (5-Fu), the nitrogen heterocycle porphyrins have the better biological activity and might have potential application in medicine.
-
47浏览
-
0点赞
-
0收藏
-
0分享
-
256下载
-
0评论
-
引用
阎子峰, Can-Cheng Guo*, Gang Huang, Xiao-Bing Zhang, Dong-Cai Guo
Applied Catalysis A: General 247(2003)261-267,-0001,():
-1年11月30日
The chitosan-supported iron (Ⅲ) tetraphenylporphyrin was prepared and characterized structurally, and its ability to catalyse oxidation of cyclohexane into cyclohexanone and cyclohexanol with air in absence of any reductants and solvents was studied. The research results showed that the amino groups of the chitosan coordinated axially with the iron atoms of chloro [tetraphenylporphinatoiron (Ⅲ)] to form chitosan-supported ironporphyrin, which has better catalytic power for cyclohexane oxidation with air than the corresponding unsupported ironporphyrin. Under reaction conditions of 418K and 0.8MPa, the cyclohexane oxidation catalyzed by chitosan-supported iron (Ⅲ) tetraphenylporphyrin had 1.40×105 catalyst mole turnover (based on the iron atom), 10.48% cyclohexane conversion and the 79.20% cyclohexanone and cyclohexanol selectivity, respectively. The turnover in cyclohexane oxidation catalyzed by the supported ironporphyrin is about 22 times bigger than that by unsupported ironporphyrin and the conversion is about double. The values are also higher than 3.9% conversion and 78% selectivity catalyzed by soluble cobalt catalyst used in industry at present. This paper has also investigated the influences of reaction time, temperature and pressure on the catalyst turnover, cyclohexane conversion and ratio of cyclohexanol to cyclohexanone in the cyclohexane oxidation catalyzed by the chitosan-supported iron (Ⅲ) tetraphenylporphyrin.
Chitosan, Supported metalloporphyrins, Cyclohexane oxidation, Oxygen
-
28浏览
-
0点赞
-
0收藏
-
0分享
-
214下载
-
0评论
-
引用
阎子峰, Can-Cheng Guo*, Ming-Fu Chu, Qiang Liu, Yang Liu, Dong-Cai Guo, Xiao-Qin Liu
Applied Catalysis A: General 246(2003)303-309,-0001,():
-1年11月30日
Simple iron, manganese and cobalt tetraphenylporphyrins were synthesized and used to catalyze cyclohexane oxidation with air in the absence of additives and solvents. These simple metalloporphyrins were first found to be the very effective catalysts for cyclohexane oxidation with air when the reaction temperature was higher than 100℃ and pressure was greater than 0.4MPa. The research results showed that the metalloporphyrins type, temperature, pressure and catalyst concentration influenced the yields and conversion of cyclohexane oxidation with air. The catalytic activity of cobalt porphyrinswas superior to that of iron and manganese porphyrins. For cyclohexane oxidation catalyzed by simple cobalt tetrapherylporphyrin, the conversion of cyclohexanewas up to 16.2%, general yields of cyclohexanol and cyclohexanonewas 82%, and the mole turnover numbers of the catalyst reached 400,000 under the optimum conditions of 0.6MPa and 140℃ and 4ppm cobalt porphyrin.
Metalloporphyrins, Cyclohexane, Oxidation, Air, Catalysis
-
38浏览
-
0点赞
-
0收藏
-
0分享
-
233下载
-
0评论
-
引用
阎子峰, Can-Cheng Guo*, Xiao-Qin Liu, Zhi-Peng Li, Dong-Cai Guo
Applied Catalysis A: General 230(2002)53-60,-0001,():
-1年11月30日
Fourteen μ-oxo-bisironporphyrins and nine μ-oxo-bismanganeseporphyrins were synthesized, and their selective catalysis for the oxidation of the secondary and tertiary carbon-hydrogen bonds of 2-methylbutane with PhIO were also studied. The ratio of the relative reaction selectivity of tertiary carbon-hydrogen bonds to secondary carbon-hydrogen bonds was 3:1 when ironporphyrins were used as catalysts, and 4:1 when manganeseporphyrins were used as catalysts. The research showed that the substituents on the porphyrin rings influenced the catalytic selectivity of metalloporphyrins for the oxidation of the secondary and tertiary carbon-hydrogen bonds as well as the reaction rate. Whether ironporphyrins or manganeseporphyrins, the electron-attracting groups on porphyrin rings increased the catalytic selectivity of metalloporphyrins for the tertiary carbon-hydrogen bonds and the reaction rates, however, the electron-releasing groups increased the catalytic selectivity of metalloporphyrins for secondary carbon-hydrogen bonds, but reduced the reaction rates.
Porphyrins, Oxidation, Catalysis, 2-Methylbutane, Selectivity
-
30浏览
-
0点赞
-
0收藏
-
0分享
-
117下载
-
0评论
-
引用
阎子峰, Can-Cheng Guo*, Guan Huang, Zhi-Peng Li, Jian-Xin Song
Journal of Molecular Catalysis A: Chemical 170(2001)43-49,-0001,():
-1年11月30日
Nine ironporphyrins and eight manganeseporphyrins were synthesized, and their selective catalysis for the oxidation of the secondary and tertiary carbon-hydrogen bonds of 2-methyl-butane with PhIO was studied. The proportion of the oxidation product of tertiary carbon-hydrogen bond to the one of secondary carbon-hydrogen bond was 3:1 when ironporphyrins were used as catalysts, and 2.3:1 when manganeseporphyrins were used as catalysts. The research showed that the substituting groups on the porphyrin rings influenced the catalytic selectivity of metalloporphyrins for the oxidation of the secondary and tertiary carbon-hydrogen bonds as well as the reaction yields. The electron-attracting groups on benzene rings of ironporphyrins increased the catalytic selectivity of ironporphyrins for the tertiary carbon-hydrogen bond oxidation and the reaction speeds, and the electron-releasing groups increased the catalytic selectivity for secondary carbon-hydrogen bond oxidation and reduced the reaction speeds. Both electron-attracting and-releasing groups on benzene rings of manganeseporphyrins enhanced the catalytic selectivity of manganeseporphyrins for the secondary carbon-hydrogen bond oxidation.
Porphyrins, Oxidation, 2-Methyl-butane, Catalysis, Selectivity
-
34浏览
-
0点赞
-
0收藏
-
0分享
-
90下载
-
0评论
-
引用
阎子峰, Can-Cheng Guo)*, Jian-Xin Song, Xin-Bin Chen, Guo-Fang Jiang
Journal of Molecular Catalysis A: Chemical 157(2000)31-40,-0001,():
-1年11月30日
Forty metalloporphyrins with different peripheral substituents (R) on the porphyrin ring, RTPPMⅢCl and [RTPPMⅢ] 2O (M=Fe, Mn), were synthesized, and were used to catalyze cyclohexane hydroxylation with iodosobenzene under mild conditions. A Hammett relationship, log k=ρơ +c, was shown to exist between the rate constants k of the cyclohexane hydroxylation and Hammett constants ơ of substituents on the porphyrin rings. The value of the reaction constant ρ changed from 0.3 to 0.5 for the cyclohexane oxidation catalyzed by metalloporphyrins, and electron-withdrawing groups increased the reaction speeds. This means that the reaction mediator was a radical cation, and that the rate-determining step of the reaction was a radical reaction. These research results provided a new evidence for the high-valent oxo-metal radical cation intermediate and hydrogen radical abstraction mechanism in hydrocarbon hydroxylation catalyzed by metalloporphyrins.
Metalloporphyrins, Catalysis, Hammett relationship
-
23浏览
-
0点赞
-
0收藏
-
0分享
-
69下载
-
0评论
-
引用
阎子峰, Xiao-Bing Zhang, Can-Cheng Guo*, Jian-Bing Xu, Ru-Qin Yu
Journal of Molecular Catalysis A: Chemical 154(2000)31-38,-0001,():
-1年11月30日
Tetrakis [2-(2,3,4,6-tetraacetyl-β-D-glucopyranosyl)-1-O-phenyl] porphyrin (T (o-glu) PPH2) and tetra [3-(2,3,4,6-tetra-acetyl-β-D-glucopyranosyl)-1-O-phenyl] porphyrin (T (m-glu) PPH2) were synthesized from the reaction of pyrrole with ortho-acetylglycosylated benzaldehyde and meta-acetylglycosylated benzaldehyde, respectively, by Lindsay's method. These free acetylglycosylated porphyrins were metallized into acetylglycosylated metalloporphyrins, chloro [tetra (o-2,3,4,6-tetraacetyl-β-D-glucopyranosyl-1-O-phenyl) porphinato]iron (T (o-glu) PPFeCl) chloro [tetra (o-2,3,4,6-tetraacetyl-β-D-gluco-pyranosyl-1-O-phenyl) porphinato] manganese (T9o-glu) PPMnCl), chloro [tetra (m-2,3,4,6-tetraacetyl-β-D-glucopyranosyl-1-O-phenyl) porphinato] iron (T (m-glu) PPFeCl) [tetra (m-2,3,4,6-tetraacetyl-β-D-glucopyranosyl-1-O-phenyl) porphinato] manganese T (m-glu) PPMnCl. The newly synthesized compounds were characterized by UV-VIS spectroscopy, HNMR and elemental analysis. The catalysis of these acetylglycosylated metalloporphyrins for cyclohexane oxidation with PhIO as an oxidant at room temperature and under atmospheric pressure was studied. The changes of the catalytic power of metalloporphyrins were observed when acetylglycosyl groups were introduced into porphyrin rings. In contrast with metalloporphyrins without sugar groups, cyclohexane oxidation catalyzed by acetylglycosylated metalloporphyrins have higher ratio of cyclohexanol to cyclohexanone as well as reaction rates and yields. The catalytic turnover numbers of acetylglycosylated metalloporphyrins were doubled compared to metalloporphyrins without sugar groups. The results indicated that acetylglycosylated metalloporphyrins had better antioxidative stability than metalloporphyrins without sugar groups.
Acetylglycosylated metalloporphyrins, Cyclohexane, PhIO
-
31浏览
-
0点赞
-
0收藏
-
0分享
-
77下载
-
0评论
-
引用
阎子峰, Can-Cheng Guo, He-Ping Li, and Jian-Bing Xu
Journal of Catalysis 185, 345-351 (1999),-0001,():
-1年11月30日
Ten substituted μ-oxo-bis [tetraphenylporphinatomanganese (Ⅲ)] compounds ([TRPPMnⅢ]2O) were synthesized by the reaction of chloro [tetraphenylporphinatomanganese (Ⅲ)] (TRPPMnⅢCl) with NaOH. Their catalysis of cyclohexane monooxygenation by PhIO under moderate conditions was studied. In contrast with other metalloporphyrins reported so far, μ-oxo-bis [tetraphenylporphinatomanganese (Ⅲ)] compounds are shown to have better catalytic power for cyclohexane hydroxylation by PhIO. The kinetic research showed that the rate constants k of the cyclohexane reactions had a Hammett relationship to the characteristic constants ơ of substituents R on porphyrin rings.
[TPPMnIII]2O, hydrocarbon oxidation, catalyze.,
-
38浏览
-
0点赞
-
0收藏
-
0分享
-
78下载
-
0评论
-
引用
阎子峰, Can-Cheng Guo
JOURNAL OF CATALYSIS 178, 182-187 (1998),-0001,():
-1年11月30日
Fourteen substitutedμ-oxo-bis [tetraphenylporphinatoiron (III)] derivants ([TXPPFeIII]2O) were synthesized by passing chlorotetraphenylporphinatoiron (III) (TPPFeIIICl) through a neutral alumina chromatographic column, and nine of which were used in cyclohexane hydroxylation with PhIO as a new type of catalyst under moderate conditions. The experiments have shown that the yields, rate constants k of the cyclohexane hydroxylation have a linear relationship to characteristic constants σ of substituents on porphyrin rings, a physical constant characterizing the electronic effects and steric effects of a substituent group, and that the product distributions and kinetic properties of the reactions are dependent on the reaction temperature, solvent as well as air. In contrast with monoironporphyrin TPPFeIIICl, μ-oxo-bisironporphyrin [TPPFeIII] 2O is shown to have the better catalytic power for cyclohexane hydroxylation with PhIO under moderate conditions and stability to PhIO. The research results show that μ-oxobisironporphyrin can be used as the model compound of cytochrome P-450 monooxygenase.
porphyrin, catalyze, oxidation.,
-
34浏览
-
0点赞
-
0收藏
-
0分享
-
109下载
-
0评论
-
引用