Microsolvation Effects on the Excited-State Dynamics of Protonated Tryptophan Export

@article{citeulike:1439530, abstract = {Abstract: To better understand the complex photophysics of the amino acid tryptophan, which is widely used as a probe of protein structure and dynamics, we have measured electronic spectra of protonated, gas-phase tryptophan solvated with a controlled number of water molecules and cooled to \~{}10 K. We observe that, even at this temperature, the bare molecule exhibits a broad electronic spectrum, implying ultrafast, nonradiative decay of the excited state. Surprisingly, the addition of two water molecules sufficiently lengthens the excited-state lifetime that we obtain a fully vibrationally resolved electronic spectrum. Quantum chemical calculations at the RI-CC2/aug-cc-pVDZ level, together with TDDFT/pw based first-principles MD simulations of the excited-state dynamics, clearly demonstrate how interactions with water destabilize the photodissociative states and increase the excited-state lifetime.}, address = {Contribution from the Institute of Chemical Sciences and Engineering, \'{E}cole Polytechnique F\'{e}d\'{e}rale de Lausanne, CH-1015 Lausanne, Switzerland}, author = {Mercier, S. R. and Boyarkin, O. V. and Kamariotis, A. and Guglielmi, M. and Tavernelli, I. and Cascella, M. and Rothlisberger, U. and Rizzo, T. R.}, citeulike-article-id = {1439530}, citeulike-linkout-0 = {http://dx.doi.org/10.1021/ja065980n}, citeulike-linkout-1 = {http://pubs.acs.org/doi/abs/10.1021/ja065980n}, day = {27}, doi = {10.1021/ja065980n}, journal = {J. Am. Chem. Soc.}, keywords = {microsolvation, spectrum, tryptophane}, month = {December}, number = {51}, pages = {16938--16943}, posted-at = {2007-07-06 14:23:48}, priority = {2}, title = {Microsolvation Effects on the Excited-State Dynamics of Protonated Tryptophan}, url = {http://dx.doi.org/10.1021/ja065980n}, volume = {128}, year = {2006} }

TY - JOUR ID - citeulike:1439530 L3 - citeulike-article-id:1439530 N2 - Abstract: To better understand the complex photophysics of the amino acid tryptophan, which is widely used as a probe of protein structure and dynamics, we have measured electronic spectra of protonated, gas-phase tryptophan solvated with a controlled number of water molecules and cooled to ~10 K. We observe that, even at this temperature, the bare molecule exhibits a broad electronic spectrum, implying ultrafast, nonradiative decay of the excited state. Surprisingly, the addition of two water molecules sufficiently lengthens the excited-state lifetime that we obtain a fully vibrationally resolved electronic spectrum. Quantum chemical calculations at the RI-CC2/aug-cc-pVDZ level, together with TDDFT/pw based first-principles MD simulations of the excited-state dynamics, clearly demonstrate how interactions with water destabilize the photodissociative states and increase the excited-state lifetime. IS - 51 JF - J. Am. Chem. Soc. AD - Contribution from the Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland EP - 16943 TI - Microsolvation Effects on the Excited-State Dynamics of Protonated Tryptophan VL - 128 SP - 16938 KW - microsolvation KW - spectrum KW - tryptophane AU - Mercier, SR AU - Boyarkin, OV AU - Kamariotis, A AU - Guglielmi, M AU - Tavernelli, I AU - Cascella, M AU - Rothlisberger, U AU - Rizzo, TR PY - 2006/12/27/ UR - http://dx.doi.org/10.1021/ja065980n ER -