Theoretical determination of absolute free energy of reduction of plastoquinone-9 in photosystem II and of plastoquinone-n in DMF
DSpace at IIT Bombay
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Title |
Theoretical determination of absolute free energy of reduction of plastoquinone-9 in photosystem II and of plastoquinone-n in DMF
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Creator |
MEHTA, N
DATTA, SN |
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Subject |
poisson-boltzmann equation
photosynthetic reaction centers quantum-chemical calculation isoprenoid side-chain binding free-energies solvation free-energy blue copper proteins electron-transfer redox potentials conformational flexibility static continuum electrostatics multi-conformation continuum electrostatics poisson-boltzmann absolute free energy of reduction |
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Description |
We employed static continuum electrostatics and multi-conformation continuum electrostatics (MCCE) methods to determine the reduction potential (E(red)(0)) Of PQ-9 in a section of Photosystem 11 (PSII). Both methods relied on the finite difference Poisson-Boltzmann (FDPB) solution. The static method brings out a E(red)(0) value (0.01 V) that is close to the experimental one (0.05 V), thereby demonstrating that the surrounding environment critically decides the net free energy change. The E(red)(0) value obtained from MCCE (0.04 V) is even closer to the observed value, thereby indicating the importance of protein side-chain and proton motions in the electron transfer process. Furthermore, density functional theory-dielectric polarisable continuum model (DFT-DPCM) was employed to calculate the absolute free energy of reduction of plastoquinone-n (PQ-n, where n is the number of isoprenoid units) in N,N dimethyl formamide (DMF) solvent. The DFT-DPCM method produced reduction potential values of -0.59 and -0.65 V for PQ-1 and PQ-9, respectively. These are more or less in agreement with the experimentally reported values of -0.64 and -0.62 V, respectively. (C) 2008
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Publisher |
ELSEVIER SCIENCE BV
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Date |
2011-07-27T02:48:56Z
2011-12-26T12:53:12Z 2011-12-27T05:40:25Z 2011-07-27T02:48:56Z 2011-12-26T12:53:12Z 2011-12-27T05:40:25Z 2008 |
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Type |
Article
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Identifier |
JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM, 870(40603), 15-22
0166-1280 http://dx.doi.org/10.1016/j.theochem.2008.08.031 http://dspace.library.iitb.ac.in/xmlui/handle/10054/7089 http://hdl.handle.net/10054/7089 |
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Language |
en
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