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• W2328350166 endingPage "10616" @default.
• W2328350166 startingPage "10609" @default.
• W2328350166 abstract "LOV domains (Light, Oxygen, Voltage) are the light-sensory modules of phototropins, the blue-light photoreceptor kinases in plants, and of a wide variety of flavoproteins found in all three domains of life. These 12 kDa modules bind a flavin chromophore (FMN or FAD) noncovalently and undergo a photochemical activation in which the sulfur atom of a conserved cysteine forms an adduct to the C(4a) carbon of the flavin. The adduct breaks spontaneously in a base-catalyzed reaction involving a rate-limiting proton-transfer step, regenerating the dark state in seconds. This photocycle involves chromophore and protein structural changes that activate the C-terminal serine/threonine kinase. Previous studies (Biochemistry2007, 46, 7016–7021) showed that decreased hydration obtained at high glycerol concentrations stabilizes the adduct state in a manner similar to that attained at low temperatures, resulting in much longer adduct decay times. This kinetic effect was attributed to an increased protein rigidity that hindered structural fluctuations necessary for the decay reaction. In this work, we studied the adduct decay kinetics of oat phototropin 1 (phot1) LOV2 at varying hydration using a specially designed chamber that allowed for measurement of UV–visible and FTIR spectra of the same samples. Therefore, we obtained LOV protein concentrations, adduct decay kinetics, and the different populations of bound water by deconvolution of the broad water absorption peak around 3500 cm–1. A linear dependence of the adduct decay rate constant on the concentration of double and triple hydrogen-bonded waters strongly suggests that the adduct decay is a pseudo-first-order reaction in which both the adduct and the strongly bound waters are reactants. We suggest that a cluster of strongly bound water functions as the proton acceptor in the rate-limiting step of adduct decay." @default.
• W2328350166 created "2016-06-24" @default.
• W2328350166 creator A5031996619 @default.
• W2328350166 creator A5063944606 @default.
• W2328350166 date "2012-07-30" @default.
• W2328350166 modified "2023-10-15" @default.
• W2328350166 title "Structural Water Cluster As a Possible Proton Acceptor in the Adduct Decay Reaction of Oat Phototropin 1 LOV2 Domain" @default.
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• W2328350166 doi "https://doi.org/10.1021/jp304934t" @default.
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• W2328350166 hasPublicationYear "2012" @default.
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