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

Mara, Michael W.; Hadt, Ryan G.; Reinhard, Marco Eli; Kroll, Thomas; Lim, Hyeongtaek; Hartsock, Robert W.; Alonso-Mori, Roberto; Chollet, Matthieu; Glownia, James M.; Nelson, Silke; Sokaras, Dimosthenis; Kunnus, Kristjan; Hodgson, Keith O.; Hedman, Britt; Bergmann, Uwe; Gaffney, Kelly J.; Solomon, Edward I.

doi:10.1126/science.aam6203

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

Journal Article · Thu Jun 22 00:00:00 EDT 2017 · Science

DOI:https://doi.org/10.1126/science.aam6203· OSTI ID:1437194

;

; Reinhard, Marco Eli; Kroll, Thomas;

; Hartsock, Robert W.; Alonso-Mori, Roberto; Chollet, Matthieu; Glownia, James M.;

;

; Kunnus, Kristjan;

; Hedman, Britt; Bergmann, Uwe;

;

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 ~4 kcal/mol stronger than in the absence of protein constraints. As a result, 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.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: award301025; AC02-76SF00515; award290961; P41GM103393; award306971; R01GM040392

OSTI ID:: 1437194

Alternate ID(s):: OSTI ID: 1369315

Journal Information:: Science, Journal Name: Science Vol. 356 Journal Issue: 6344; ISSN 0036-8075

Publisher:: American Association for the Advancement of Science (AAAS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 89 works

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