Copper-sulfenate complex from oxidation of a cavity mutant of Pseudomonas aeruginosa azurin
文献类型：期刊论文
| 作者 | Sieracki, Nathan A.1; Tian, Shiliang1; Hadt, Ryan G.2; Zhang, Jun-Long3; Woertink, Julia S.2; Nilges, Mark J.1; Sun, Furong1; Solomon, Edward I.2; Lu, Yi1 |
| 刊名 | PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
 |
| 出版日期 | 2014-01-21 |
| 卷号 | 111期号:3页码:924-929 |
| 关键词 | Bioinorganic Chemistry Metalloprotein Design Protein Engineering Blue Copper Proteins Posttranslational Modification |
| ISSN号 | 0027-8424 |
| DOI | 10.1073/pnas.1316483111 |
| 英文摘要 | Metal-sulfenate centers are known to play important roles in biology and yet only limited examples are known due to their instability and high reactivity. Herein we report a copper-sulfenate complex characterized in a protein environment, formed at the active site of a cavity mutant of an electron transfer protein, type 1 blue copper azurin. Reaction of hydrogen peroxide with Cu(I)-M121G azurin resulted in a species with strong visible absorptions at 350 and 452 nm and a relatively low electron paramagnetic resonance g(z) value of 2.169 in comparison with other normal type 2 copper centers. The presence of a side-on copper-sulfenate species is supported by resonance Raman spectroscopy, electrospray mass spectrometry using isotopically enriched hydrogen peroxide, and density functional theory calculations correlated to the experimental data. In contrast, the reaction with Cu(II)-M121G or Zn(II)-M121G azurin under the same conditions did not result in Cys oxidation or copper-sulfenate formation. Structural and computational studies strongly suggest that the secondary coordination sphere noncovalent interactions are critical in stabilizing this highly reactive species, which can further react with oxygen to form a sulfinate and then a sulfonate species, as demonstrated by mass spectrometry. Engineering the electron transfer protein azurin into an active copper enzyme that forms a copper-sulfenate center and demonstrating the importance of noncovalent secondary sphere interactions in stabilizing it constitute important contributions toward the understanding of metal-sulfenate species in biological systems. |
| 语种 | 英语 |
| WOS记录号 | WOS:000329928400027 |
| 出版者 | NATL ACAD SCIENCES |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/50685]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Solomon, Edward I. |
| 作者单位 | 1.Univ Illinois, Dept Chem, Urbana, IL 61801 USA 2.Stanford Univ, Dept Chem, Stanford, CA 94305 USA 3.Peking Univ, Coll Chem & Mol Engn, Beijing Natl Lab Mol Sci, State Key Lab Rare Earth Mat Chem & Applicat, Beijing 100871, Peoples R China |
| 推荐引用方式 GB/T 7714 | Sieracki, Nathan A.,Tian, Shiliang,Hadt, Ryan G.,et al. Copper-sulfenate complex from oxidation of a cavity mutant of Pseudomonas aeruginosa azurin[J]. PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA,2014,111(3):924-929. |
| APA | Sieracki, Nathan A..,Tian, Shiliang.,Hadt, Ryan G..,Zhang, Jun-Long.,Woertink, Julia S..,...&Lu, Yi.(2014).Copper-sulfenate complex from oxidation of a cavity mutant of Pseudomonas aeruginosa azurin.PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA,111(3),924-929. |
| MLA | Sieracki, Nathan A.,et al."Copper-sulfenate complex from oxidation of a cavity mutant of Pseudomonas aeruginosa azurin".PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA 111.3(2014):924-929. |
入库方式： OAI收割
来源：化学研究所
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