Donor–acceptor symmetric and antisymmetric tunneling matrix elements: a pathway model investigation of protein electron transfer

The corpus of electron transfer (ET) theory provides considerable power to describe the kinetics and dynamics of electron flow at the nanoscale. How is it, then, that nucleic acid (NA) ET continues to surprise, while protein-mediated ET is relatively free of mechanistic bombshells? I suggest that this difference originates in the distinct electronic energy landscapes for the two classes of reactions. In proteins, the donor/acceptor-to-bridge energy gap is typically several-fold larger than in NAs. NA ET can access tunneling, hopping, and resonant transport among the bases, and fluctuations can enable switching among mechanisms; protein ET is restricted to tunneling among redox active cofactors and, under strongly oxidizing conditions, a few privileged amino acid side chains. This review aims to provide conceptual unity to DNA and protein ET reaction mechanisms. The establishment of a unified mechanistic framework enabled the successful design of NA experiments that switch electronic coherence effects on and off for ET processes on a length scale of multiple nanometers and promises to provide inroads to directing and detecting charge flow in soft-wet matter.

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Probability current in protein electron transfer reactions: A Green function pathway model

The Journal of Chemical Physics ◽

10.1063/1.1875115 ◽

2005 ◽

Vol 122 (12) ◽

pp. 124713 ◽

Cited By ~ 2

Author(s):

Paulo C. P. de Andrade

Keyword(s):

Electron Transfer ◽

Green Function ◽

Transfer Reactions ◽

Pathway Model ◽

Electron Transfer Reactions ◽

Probability Current ◽

Protein Electron Transfer

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Bulk Heterojunction Solar Cells with Large Open-Circuit Voltage: Electron Transfer with Small Donor-Acceptor Energy Offset (Adv. Mater. 20/2011)

Advanced Materials ◽

10.1002/adma.201190074 ◽

2011 ◽

Vol 23 (20) ◽

pp. 2271-2271 ◽

Cited By ~ 2

Author(s):

Xiong Gong ◽

Minghong Tong ◽

Fulvio G. Brunetti ◽

Junghwa Seo ◽

Yanming Sun ◽

...

Keyword(s):

Electron Transfer ◽

Solar Cells ◽

Open Circuit Voltage ◽

Bulk Heterojunction ◽

Open Circuit ◽

Heterojunction Solar Cells ◽

Bulk Heterojunction Solar Cells ◽

Voltage Electron ◽

Donor Acceptor

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Photoelectrochemical properties of supramolecular composites of an anionic zinc chlorin and Li+@C60 on SnO2

Journal of Porphyrins and Phthalocyanines ◽

10.1142/s1088424614500825 ◽

2014 ◽

Vol 18 (10n11) ◽

pp. 982-990 ◽

Cited By ~ 5

Author(s):

Kei Ohkubo ◽

Yuki Kawashima ◽

Kentaro Mase ◽

Hayato Sakai ◽

Taku Hasobe ◽

...

Keyword(s):

Electron Transfer ◽

Photoinduced Electron Transfer ◽

Photovoltaic Cells ◽

Lithium Ion ◽

Transparent Electrode ◽

Supramolecular Complex ◽

Photoelectrochemical Properties ◽

Triplet Excited State ◽

Optically Transparent ◽

Donor Acceptor

An electron donor–acceptor supramolecular complex was formed between an anionic zinc chlorin carboxylate ( ZnCh -) and lithium-ion-encapsulated [60]fullerene ( Li +@ C 60) by an electrostatic interaction in benzonitrile ( PhCN ). Photoinduced electron transfer in the supramolecular complex of ZnCh -/ Li +@ C 60 resulted in the formation of the charge-separated state via electron transfer from the triplet excited state of ZnCh - to Li +@ C 60. We report herein photovoltaic cells using ZnCh -/ Li +@ C 60 nanoclusters, which are assembled on the optically transparent electrode (OTE) of nanostructured SnO 2 (OTE/ SnO 2). The photoelectrochemical behavior of the nanostructured SnO 2 film of supramolecular nanoclusters of ZnCh - and Li +@ C 60 denoted as OTE/ SnO 2/( ZnCh -/ Li +@ C 60)n is significantly higher than the single component films of ZnCh - or Li +@ C 60 clusters, denoted as OTE/ SnO 2/( ZnCh -)n or OTE/ SnO 2/( Li +@ C 60)n.

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