研究领域

Physical Chemistry

Bacterial reaction center in a micellar detergent and water generated by computer simulation [J. Phys. Chem. 112 (2008) pp. 10322–10342]. We are interested in understanding of how the energy is transferred in biology and molecular assemblies. Energy chains in biology rely on transmembrane transfer of redox energy from electron donating molecules to catalitic sites where the energy is stored in chemical bonds. A similar mechanism is realized in natural and artificial photosynthesis. The photon energy is first stored in a photoabsorbing molecule and is then transferred away from the point of primary photon absorption to an active site where some catalitic chemical process occurs. In all these mechanisms electron moves between centers of localization on organic cofactors or active sites of enzymes. We are working on understanding the kinetics and energetics of these elementary electron transport events with the goal of formulating the general principles of energetic efficiency of molecular charge-transfer chains. Our research strategy combines the use of computer simulations of realistic systems with the development of theoretical models which can be directly applied to interpreting the experimental data. Two areas of current research include electron transport in bacterial and artificial photosynthesis and the modeling of the electrostatics and dynamics of the protein-water interface. Hydration shells around proteins are significantly polarized producing non-Gaussain enectrostatic fluctuations [J. Phys. Chem. 113 (2009) pp. 12424--12437]. It has long been appreciated that the ability of proteins to participate effectively in the energetic chains of biology is linked to the electrostatics of proteins themselves and the hydration shells of water. The standard textbook description of the local protein polarity ascribes it a low dielectric constant comparable to that of chloroform. Large-scale computer simulations show that this is only partially true. Proteins have a broad distribution of relaxation times and, depending on the process of interest, can be either non-polar or very polar. This feature of polarity switch directly applies to the energetics of bacterial photosynthesis where charge separation reactions occur on short, picosecond times revealing non-polar protein environment while recombination reactions occur on the longer, nanosecond times switching to a strongly polar response of the protein. This latter polar response is characterized by a significantly non-Gaussian statistics of the electrostatic fluctuations. This property, directly observed in MD simulations, can potentially explain how nature performs multiple hops of electrons in its energy chains without loosing all the input energy initiated by either the incoming photon or a redox reaction.

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D. V. Matyushov, Solvent reorganization energy of electron transfer in polar solvents. J. Chem. Phys. 120 (2004) pp. 7532-7556 D. V. Matyushov, On the microscopic theory of polar solvation dynamics. J. Chem. Phys. 122 (2005) p. 044502 D. V. Matyushov, A phenomenological model of dynamic arrest of electron transfer in solvents in the glass-transition region. J. Chem. Phys. 122 (2005) 084507 D. V. Matyushov and A. Okhrimovskyy Paraelectric and ferroelectric order in twp-state dipolar fluids. J. Chem. Phys. 122 (2005) p. 191101 (cond-mat/0503623) A. Milischuk and D. V. Matyushov, Equlibrium solvation in quadrupolar solvents. J. Chem. Phys. 123 (2005) 044501 D. V. Matyushov and C. A. Angell, Two-Gaussian excitations model for the glass transition. J. Chem. Phys. 123 (2005) 034506 P. K. Ghorai and D. V. Matyushov, Dynamical arrest of electron transfer reorganization in in super-cooled water,. JACS 127 (2005) pp. 16390-16391 A. Milischuk, D. V. Matyushov, and M. D. Newton, Activation entropy in electron transfer reactions. Chem. Phys. 324 (2006) pp. 172-194 V. Kapko and D. V. Matyushov, Theory of solvation in polar nematics. J. Chem. Phys. 124 (2006) No. 114904 P. K. Ghorai and D. V. Matyushov, Reorganization energy of electron transfer in polar solvents above the glass transition. J. Phys. Chem. B, 110 (2006) pp. 1866-1871 P. K. Ghorai and D. V. Matyushov, Solvent reorganization of electron transitions in viscous solvents. J. Chem. Phys. 124 (2006) No. 144510 A. Milischuk and D. V. Matyushov, Quadrupolar solvatochromism: 4-amino-phthalamide in toluene Reorganization asymmetry of electron transfer in ferroelectric media and principles of artificial photosynthesis. J. Phys. Chem. B, 110 (2006) pp. 10095-10104 V. Kapko and D. V. Matyushov, Dynamicall arrest of electron transfer in liquid crystalline solvents. J. Phys. Chem. B, 110 (2006) pp. 13184-13194 P. K. Ghorai and D. V. Matyushov, Solvent Reorganization Entropy of Electron Transfer in Polar Solvents. J. Phys. Chem. A, 110 (2006) pp. 8857-8863 N. Ito, K. Duvvuri, D. V. Matyushov, and R. Richert, Solvent response and dielectric relaxation in supercooled butyronitrile. J. Chem. Phys. 125 (2006) No. 024504 D. V. Matyushov and C. A. Angell, Gaussian excitations model for the glass-former dynamics and thermodynamics. J. Chem. Phys. 126 (2007) 094501 D. V. Matyushov, Energetics of electron-transfer reactions in soft condensed media. Acc. Chem. Res., 40 (2007) 294 D. V. Matyushov, Dielectric response of one-dimensional polar chains. J. Chem. Phys., 127 (2007) 054702 D. V. Matyushov, Model energy landscapes of low-temperature fluids: Dipolar hard spheres. Phys. Rev. E, 76 (2007) 011511 D. R. Martin and D. V. Matyushov, Cavity field in liquid dielectrics. Europhys. Lett., 82 (2008) 16003 D. N. LeBard and D. V. Matyushov, Glassy protein dynamics and gigantic reorganization energy of plastocyanin. J. Phys. Chem. B, 112 (2008) pp. 5218-5227 D. N. LeBard and D. V. Matyushov, Redox entropy of plastocyanin: Devloping a microscopic view of mesoscopic polar solvation. J. Chem. Phys, 128 (2008) 155106 V. Kapko, D. V. Matyushov, and C. A. Angell, Thermodynamics and dynamics of a monoatomic glass former. Constant pressure and constant volume behavior.. J. Chem. Phys, 128 (2008) 144505 D. N. LeBard, V. Kapko, and D. V. Matyushov, Energetics and kinetics of primary charge separation in bacterial photosynthesis. J. Phys. Chem. B, 112 (2008) 10322 D. V. Matyushov, Non-Gaussian statistics of binding/unbinding events and the energetics of electron transfer reactions. Chem. Phys., 351 (2008) 46 D. R. Martin and D. V. Matyushov, Electrostatic fluctuations in cavities within polar liquids and thermodynamics of polar solvation Phys. Rev. E, 78 (2008) 041206 D. R. Martin and D. V. Matyushov, Microscopic fields in liquid dielectrics J. Chem. Phys., 129 (2008) 174508 D. N. LeBard and D. V. Matyushov, Dynamical transition, hydrophobic interface, and the temperature dependence of electrostatic fluctuations in proteins. Phys. Rev. E, 78 (2008) 061901 D. N. LeBard and D. V. Matyushov, Energetics of Bacterial Photosynthesis. J. Phys. Chem. B, 78 (2009) 12424–12437 D. V. Matyushov, Nonergodic activated kinetics in polar media. J. Chem. Phys., 130 (2009) 164522 D. V. Matyushov, Standard electrode potential, Tafel equation, and the solvation thermodynamics. J. Chem. Phys., 130 (2009) 234704 D. N. LeBard and D. V. Matyushov, Ferroelectric Hydration Shells around Proteins: Electrostatics of the Protein-Water Interface. J. Phys. Chem. B, 114 (2009) 9246–9258 D. N. LeBard and D. V. Matyushov, Protein–water electrostatics and principles of bioenergetics. Phys. Chem. Chem. Phys. (Perspective), 12 (2010) 15321–15556 D. V. Matyushov and A. Y. Morozov, Protein–water electrostatics and dynamical transition in proteins. Phys. Rev E, submitted (2011)