Quantum effects in ultrafast electron transfers within cryptochromes
| العنوان: | Quantum effects in ultrafast electron transfers within cryptochromes |
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| المؤلفون: | Adrien Devolder, Etienne Mangaud, David Mendive-Tapia, Aurélien de la Lande, Christoph Meier, Thiago Firmino, Fabien Gatti, Michèle Desouter-Lecomte, Fabien Cailliez |
| المساهمون: | Laboratoire de Chimie Physique D'Orsay (LCPO), Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Théorie (LCAR), Laboratoire Collisions Agrégats Réactivité (LCAR), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), ANR-05-PADD-0013,DST,Dégradation physique des Sols agricoles et forestiers liée au Tassement : conséquences environnementales et économiques, prévision, prévention, suivi, cartographie(2005), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS) |
| المصدر: | Physical Chemistry Chemical Physics Physical Chemistry Chemical Physics, Royal Society of Chemistry, 2016, 18, pp.21442. ⟨10.1039/c6cp02809h⟩ |
| سنة النشر: | 2016 |
| مصطلحات موضوعية: | Physics, 010304 chemical physics, Diabatic, General Physics and Astronomy, Charge (physics), 010402 general chemistry, 01 natural sciences, Potential energy, 0104 chemical sciences, Marcus theory, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Molecular dynamics, Quantum mechanics, 0103 physical sciences, Density functional theory, Physical and Theoretical Chemistry, Quantum, Quantum tunnelling |
| الوصف: | International audience; Cryptochromes and photolyases are flavoproteins that may undergo ultrafast charge separation uponelectronic excitation of their flavin cofactors. Charge separation involves chains of three or four tryptophanresidues depending on the protein of interest. The molecular mechanisms of these processes are notcompletely clear. In the present work we investigate the relevance of quantum effects like the occurrenceof nuclear tunneling and of coherences upon charge transfer in Arabidopsis thaliana cryptochromes. Thepossible breakdown of the Condon approximation is also investigated. We have devised a simulationprotocol based on the realization of molecular dynamics simulations on diabatic potential energy surfacesdefined at the hybrid constrained density functional theory/molecular mechanics level. The outcomes ofthe simulations are analyzed through various dedicated kinetics schemes related to the Marcus theorythat account for the aforementioned quantum effects. MD simulations also provide a basic material todefine realistic model Hamiltonians for subsequent quantum dissipative dynamics. To carry out quantumsimulations, we have implemented an algorithm based on the Hierarchical Equations of Motion. Withthis new tool in hand we have been able to model the electron transfer chain considering either two- orthree-state models. Kinetic models and quantum simulations converge to the conclusion that quantumeffects have a significant impact on the rate of charge separation. Nuclear tunneling involving atoms ofthe tryptophan redox cofactors as well as of the environment (protein atoms and water molecules) issignificant. On the other hand non-Condon effects are negligible in most simulations. Taken together,the results of the present work provide new insights into the molecular mechanisms controlling chargeseparation in this family of flavoproteins. |
| تدمد: | 1463-9084 1463-9076 |
| الوصول الحر: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::bc56ffc20344352722a8c2fd3c426af9Test https://pubmed.ncbi.nlm.nih.gov/27427185Test |
| رقم الانضمام: | edsair.doi.dedup.....bc56ffc20344352722a8c2fd3c426af9 |
| قاعدة البيانات: | OpenAIRE |
| تدمد: | 14639084 14639076 |
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