The effect of water on the rate of conformational change in protein allostery

Biophysical Journal
R A GoldbeckD S Kliger

Abstract

The influence of solvation on the rate of quaternary structural change is investigated in human hemoglobin, an allosteric protein in which reduced water activity destabilizes the R state relative to T. Nanosecond absorption spectroscopy of the heme Soret band was used to monitor protein relaxation after photodissociation of aqueous HbCO complex under osmotic stress induced by the nonbinding cosolute poly(ethylene glycol) (PEG). Photolysis data were analyzed globally for six exponential time constants and amplitudes as a function of osmotic stress and viscosity. Increases in time constants associated with geminate rebinding, tertiary relaxation, and quaternary relaxation were observed in the presence of PEG, along with a decrease in the fraction of hemes rebinding CO with the slow rate constant characteristic of the T state. An analysis of these results along with those obtained by others for small cosolutes showed that both osmotic stress and solvent viscosity are important determinants of the microscopic R --> T rate constant. The size and direction of the osmotic stress effect suggests that at least nine additional water molecules are required to solvate the allosteric transition state relative to the R-state hydration, imply...Continue Reading

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Citations

Jul 14, 2004·Biochemistry·Valarie L Tlapak-SimmonsPaul H Weigel
Mar 2, 2005·Proceedings of the National Academy of Sciences of the United States of America·Brian M HoffmanJudith M Nocek
Oct 7, 2005·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Willy B TanGeorge L McLendon
Jan 3, 2013·IUBMB Life·Anna RauscherAndrás Málnási-Csizmadia
Jul 5, 2005·Biophysical Journal·Angela S F Ramos, Simone Techert
Jun 30, 2016·Biochemistry·Raymond M EsquerraRobert A Goldbeck
Aug 15, 2015·Physical Chemistry Chemical Physics : PCCP·Cheolhee YangHyotcherl Ihee
Dec 1, 2006·Photochemical & Photobiological Sciences : Official Journal of the European Photochemistry Association and the European Society for Photobiology·Stefania AbbruzzettiCristiano Viappiani
Jun 5, 2013·Physical Chemistry Chemical Physics : PCCP·Stefania AbbruzzettiCristiano Viappiani
Sep 21, 2006·The Journal of Biological Chemistry·Camille J RocheJoel M Friedman

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