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Nat Commun ; 11(1): 4248, 2020 08 25.
Artigo em Inglês | MEDLINE | ID: mdl-32843623


Femtosecond time-resolved crystallography (TRC) on proteins enables resolving the spatial structure of short-lived photocycle intermediates. An open question is whether confinement and lower hydration of the proteins in the crystalline state affect the light-induced structural transformations. Here, we measured the full photocycle dynamics of a signal transduction protein often used as model system in TRC, Photoactive Yellow Protein (PYP), in the crystalline state and compared those to the dynamics in solution, utilizing electronic and vibrational transient absorption measurements from 100 fs over 12 decades in time. We find that the photocycle kinetics and structural dynamics of PYP in the crystalline form deviate from those in solution from the very first steps following photon absorption. This illustrates that ultrafast TRC results cannot be uncritically extrapolated to in vivo function, and that comparative spectroscopic experiments on proteins in crystalline and solution states can help identify structural intermediates under native conditions.

Proteínas de Bactérias/química , Proteínas de Bactérias/metabolismo , Cristalografia por Raios X/métodos , Fotorreceptores Microbianos/química , Fotorreceptores Microbianos/metabolismo , Proteínas de Bactérias/efeitos da radiação , Cinética , Luz , Estrutura Molecular , Processos Fotoquímicos , Fotorreceptores Microbianos/efeitos da radiação , Conformação Proteica , Análise Espectral
J Phys Chem A ; 118(17): 3081-9, 2014 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-24701997


Investigation of frequency dependent permittivity of mixture solutions provides information on the role of intermolecular interactions on relaxation processes of solvent and solute molecules. In this study the dielectric properties of ethanol/gasoline mixtures in the terahertz spectral region are investigated. Frequency dependent absorption coefficients, refractive indices, and complex permittivities of pure ethanol and gasoline, and their mixtures at varying ethanol volume percentages (v/v %) are reported. As the mixing ratio changes, meaningful shifts are observed in the frequency dependent refractive index and absorption coefficients associated with the dominant component, ethanol. The relaxation dynamics of the pure gasoline and ethanol are successfully modeled with the Debye model using the ultrafast nature of the terahertz transients, and those of mixture solutions are investigated by an additive model with an assumption of minimum interaction due to the significant differences in their molecular natures; polar and nonpolar. Successful modeling of the mixtures confirms the weak interaction assumption and enables us to accurately determine the ethanol content. Among five ethanol/gasoline blends, except for one mixture, the estimated percent ethanol in gasoline is predicted with an accuracy of ca. 1% with respect to the actual ethanol percentage. In addition, the results show that free OH contribution to the macroscopic polarization is significantly higher at low concentrations (5-20%) and lower at 50% compared to the case of pure ethanol. The measurements and analysis presented here show that time domain terahertz studies can offer invaluable insight into development of new models for polar/nonpolar complex mixture solutions.