Electron-transfer-induced and phononic heat transport in molecular environments

2017 ◽  
Vol 147 (12) ◽  
pp. 124101 ◽  
Author(s):  
Renai Chen ◽  
Galen T. Craven ◽  
Abraham Nitzan
2016 ◽  
Vol 113 (34) ◽  
pp. 9421-9429 ◽  
Author(s):  
Galen T. Craven ◽  
Abraham Nitzan

Charge transfer is a fundamental process that underlies a multitude of phenomena in chemistry and biology. Recent advances in observing and manipulating charge and heat transport at the nanoscale, and recently developed techniques for monitoring temperature at high temporal and spatial resolution, imply the need for considering electron transfer across thermal gradients. Here, a theory is developed for the rate of electron transfer and the associated heat transport between donor–acceptor pairs located at sites of different temperatures. To this end, through application of a generalized multidimensional transition state theory, the traditional Arrhenius picture of activation energy as a single point on a free energy surface is replaced with a bithermal property that is derived from statistical weighting over all configurations where the reactant and product states are equienergetic. The flow of energy associated with the electron transfer process is also examined, leading to relations between the rate of heat exchange among the donor and acceptor sites as functions of the temperature difference and the electronic driving bias. In particular, we find that an open electron transfer channel contributes to enhanced heat transport between sites even when they are in electronic equilibrium. The presented results provide a unified theory for charge transport and the associated heat conduction between sites at different temperatures.


Author(s):  
P. Bonhomme ◽  
A. Beorchia

We have already described (1.2.3) a device using a pockel's effect light valve as a microscopical electron image converter. This converter can be read out with incoherent or coherent light. In the last case we can set in line with the converter an optical diffractometer. Now, electron microscopy developments have pointed out different advantages of diffractometry. Indeed diffractogram of an image of a thin amorphous part of a specimen gives information about electron transfer function and a single look at a diffractogram informs on focus, drift, residual astigmatism, and after standardizing, on periods resolved (4.5.6). These informations are obvious from diffractogram but are usualy obtained from a micrograph, so that a correction of electron microscope parameters cannot be realized before recording the micrograph. Diffractometer allows also processing of images by setting spatial filters in diffractogram plane (7) or by reconstruction of Fraunhofer image (8). Using Electrotitus read out with coherent light and fitted to a diffractometer; all these possibilities may be realized in pseudoreal time, so that working parameters may be optimally adjusted before recording a micrograph or before processing an image.


2004 ◽  
Vol 71 ◽  
pp. 1-14
Author(s):  
David Leys ◽  
Jaswir Basran ◽  
François Talfournier ◽  
Kamaldeep K. Chohan ◽  
Andrew W. Munro ◽  
...  

TMADH (trimethylamine dehydrogenase) is a complex iron-sulphur flavoprotein that forms a soluble electron-transfer complex with ETF (electron-transferring flavoprotein). The mechanism of electron transfer between TMADH and ETF has been studied using stopped-flow kinetic and mutagenesis methods, and more recently by X-ray crystallography. Potentiometric methods have also been used to identify key residues involved in the stabilization of the flavin radical semiquinone species in ETF. These studies have demonstrated a key role for 'conformational sampling' in the electron-transfer complex, facilitated by two-site contact of ETF with TMADH. Exploration of three-dimensional space in the complex allows the FAD of ETF to find conformations compatible with enhanced electronic coupling with the 4Fe-4S centre of TMADH. This mechanism of electron transfer provides for a more robust and accessible design principle for interprotein electron transfer compared with simpler models that invoke the collision of redox partners followed by electron transfer. The structure of the TMADH-ETF complex confirms the role of key residues in electron transfer and molecular assembly, originally suggested from detailed kinetic studies in wild-type and mutant complexes, and from molecular modelling.


2002 ◽  
Vol 12 (3) ◽  
pp. 201-206 ◽  
Author(s):  
Janina Marciak-Kozłowska ◽  
Mirosław Kozłowski
Keyword(s):  

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