Metalloprotein entatic control of ligand-metal bonds quantified by ultrafast x-ray spectroscopy

被引：112

作者：

Mara, Michael W. ^{[1
,2
,5
]}

Hadt, Ryan G. ^{[1
,6
]}

Reinhard, Marco Eli ^{[3
]}

Kroll, Thomas ^{[2
]}

Lim, Hyeongtaek ^{[1
,2
]}

Hartsock, Robert W. ^{[3
]}

Alonso-Mori, Roberto ^{[4
]}

Chollet, Matthieu ^{[4
]}

Glownia, James M. ^{[4
]}

Nelson, Silke ^{[4
]}

Sokaras, Dimosthenis ^{[2
]}

Kunnus, Kristjan ^{[3
]}

Hodgson, Keith O. ^{[1
,2
]}

Hedman, Britt ^{[2
]}

Bergmann, Uwe ^{[3
,4
]}

Gaffney, Kelly J. ^{[2
,3
]}

Solomon, Edward I. ^{[1
,2
]}

机构：

[1] Stanford Univ, Dept Chem, Stanford, CA 94305 USA

[2] Stanford Univ, Stanford Synchrotron Radiat Lightsource, SLAC Natl Accelerator Lab, 2575 Sand Hill Rd, Menlo Pk, CA 94025 USA

[3] Stanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Stanford, CA 94305 USA

[4] Stanford Univ, SLAC Natl Accelerator Lab, Linac Coherent Light Source, Menlo Pk, CA 94025 USA

[5] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA

[6] Argonne Natl Lab, Chem Sci & Engn Div, 9700 S Cass Ave, Argonne, IL 60439 USA

来源：

SCIENCE | 2017年 / 356卷 / 6344期

基金：

美国国家卫生研究院; 瑞士国家科学基金会;

关键词：

HEART CYTOCHROME-C; BLUE COPPER PROTEINS; HEME-PROTEINS; ACTIVE-SITE; TEMPERATURE-DEPENDENCE; AXIAL METHIONINE; RESONANCE RAMAN; DYNAMICS; CARDIOLIPIN; SCATTERING;

D O I：

10.1126/science.aam6203

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

The multifunctional protein cytochrome c (cyt c) plays key roles in electron transport and apoptosis, switching function by modulating bonding between a heme iron and the sulfur in a methionine residue. This Fe-S(Met) bond is too weak to persist in the absence of protein constraints. We ruptured the bond in ferrous cyt c using an optical laser pulse and monitored the bond reformation within the protein active site using ultrafast x-ray pulses from an x-ray free-electron laser, determining that the Fe-S(Met) bond enthalpy is similar to 4 kcal/mol stronger than in the absence of protein constraints. The 4 kcal/mol is comparable with calculations of stabilization effects in other systems, demonstrating how biological systems use an entatic state for modest yet accessible energetics to modulate chemical function.

引用

页码：1276 / +

页数：5

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