Search results for "Biophysics and Computational Biology"

showing 2 items of 2 documents

Quantifying the limits of transition state theory in enzymatic catalysis

2017

Significance Transition state theory (TST) is the most popular theory to calculate the rates of enzymatic reactions. However, in some cases TST could fail due to the violation of the nonrecrossing hypothesis at the transition state. In the present work we show that even for one of the most controversial enzymatic reactions—the hydride transfer catalyzed by dihydrofolate reductase—the error associated to TST represents only a minor correction to the reaction rate. Moreover, this error is actually larger for the reaction in solution than in the enzymatic active site. Based on this finding and on previous studies we propose an “enzymatic shielding” hypothesis which encompasses various aspects …

Surface (mathematics)enzymatic catalysisDegrees of freedom (statistics)Molecular Dynamics Simulation010402 general chemistry01 natural sciencesEnzyme catalysisReaction coordinateReaction rateTransition state theoryMolecular dynamicsdihydrofolate reductasetransmission coefficientComputational chemistry0103 physical sciencesHumansdynamic effectsStatistical physicsIonsMultidisciplinary010304 chemical physicsChemistryState (functional analysis)Biological Sciencesbacterial infections and mycoses0104 chemical sciencesChemistryBiophysics and Computational BiologyKineticsTetrahydrofolate Dehydrogenasetransition state theoryPhysical SciencesBiocatalysisProceedings of the National Academy of Sciences
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Short hydrogen bonds enhance nonaromatic protein-related fluorescence

2021

Significance Intrinsic fluorescence of nonaromatic amino acids is a puzzling phenomenon with an enormous potential in biophotonic applications. The physical origins of this effect, however, remain elusive. Herein, we demonstrate how specific hydrogen bond networks can modulate fluorescence. We highlight the key role played by short hydrogen bonds, present in the protein structure, on the ensuing fluorescence. We provide detailed experimental and molecular evidence to explain these unusual nonaromatic optical properties. Our findings should benefit the design of novel optically active biomaterials for applications in biosensing and imaging.

Chemical transformationOptics and PhotonicsGlutamineIntrinsic fluorescenceMolecular Dynamics SimulationPhotochemistryFluorescenceAb initio molecular dynamicsAmmoniaHumansSingle amino acidshort hydrogen bondDensity Functional TheoryMultidisciplinaryHydrogen bondChemistryintrinsic fluorescenceultraviolet fluorescenceHydrogen BondingConical intersectionFluorescenceBiophysics and Computational BiologyExcited statePhysical Sciences408PeptidesProceedings of the National Academy of Sciences of the United States of America
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