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Bridge- and solvent-mediated intramolecular electronic communications in ubiquinone-based biomolecular wires.

Liu XY, Ma W, Zhou H, Cao XM, Long YT - Sci Rep (2015)

Bottom Line: We found that the bridges linkers have a significant effect on the electronic communications between the two peripheral ubiquinone moieties and solvents effects are limited and mostly depend on the nature of solvents.The DFT calculations also demonstrates the effect of solvents on the latter two-electron transfer of Bis-CoQ0s is more significant than the former two electrons transfer as the observed electrochemical behaviors of three Bis-CoQ0s.In addition, the electrochemistry and theoretical calculations reveal the intramolecular electronic communications vary in the four-electron redox processes of three Bis-CoQ0s.

View Article: PubMed Central - PubMed

Affiliation: Key Laboratory for Advanced Materials &Department of Chemistry, East China University of Science and Technology, Shanghai 200237, P. R. China.

ABSTRACT
Intramolecular electronic communications of molecular wires play a crucial role for developing molecular devices. In the present work, we describe different degrees of intramolecular electronic communications in the redox processes of three ubiquinone-based biomolecular wires (Bis-CoQ0s) evaluated by electrochemistry and Density Functional Theory (DFT) methods in different solvents. We found that the bridges linkers have a significant effect on the electronic communications between the two peripheral ubiquinone moieties and solvents effects are limited and mostly depend on the nature of solvents. The DFT calculations for the first time indicate the intensity of the electronic communications during the redox processes rely on the molecular orbital elements VL for electron transfer (half of the energy splitting of the LUMO and LUMO+1), which is could be affected by the bridges linkers. The DFT calculations also demonstrates the effect of solvents on the latter two-electron transfer of Bis-CoQ0s is more significant than the former two electrons transfer as the observed electrochemical behaviors of three Bis-CoQ0s. In addition, the electrochemistry and theoretical calculations reveal the intramolecular electronic communications vary in the four-electron redox processes of three Bis-CoQ0s.

No MeSH data available.


Structures of three Bis-CoQ0s in the research.
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f1: Structures of three Bis-CoQ0s in the research.

Mentions: To this end, in the present study we designed and synthesized three ubiquinone-basedbiomolecular wires (Bis-CoQ0s) (depicted in Fig. 1)coupled by different bridge linkers and studied the electronic communications betweentwo ubiquinone groups during the four electrons redox processes using theelectrochemistry and Density Functional Theory (DFT) methods in aprotic organic solventsand oxygen-free environment mimicking the nonpolar environment in living cells. In thisway, we hope to fine-tune the level of electronic communications between the twoperipheral ubiquinone groups and explore the molecular structures-based reasons causingthe different degree electronic communications and further extend the applications ofubiquinone as biomolecular wires in artificial photosynthetic system and electroniccomponents.


Bridge- and solvent-mediated intramolecular electronic communications in ubiquinone-based biomolecular wires.

Liu XY, Ma W, Zhou H, Cao XM, Long YT - Sci Rep (2015)

Structures of three Bis-CoQ0s in the research.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4440530&req=5

f1: Structures of three Bis-CoQ0s in the research.
Mentions: To this end, in the present study we designed and synthesized three ubiquinone-basedbiomolecular wires (Bis-CoQ0s) (depicted in Fig. 1)coupled by different bridge linkers and studied the electronic communications betweentwo ubiquinone groups during the four electrons redox processes using theelectrochemistry and Density Functional Theory (DFT) methods in aprotic organic solventsand oxygen-free environment mimicking the nonpolar environment in living cells. In thisway, we hope to fine-tune the level of electronic communications between the twoperipheral ubiquinone groups and explore the molecular structures-based reasons causingthe different degree electronic communications and further extend the applications ofubiquinone as biomolecular wires in artificial photosynthetic system and electroniccomponents.

Bottom Line: We found that the bridges linkers have a significant effect on the electronic communications between the two peripheral ubiquinone moieties and solvents effects are limited and mostly depend on the nature of solvents.The DFT calculations also demonstrates the effect of solvents on the latter two-electron transfer of Bis-CoQ0s is more significant than the former two electrons transfer as the observed electrochemical behaviors of three Bis-CoQ0s.In addition, the electrochemistry and theoretical calculations reveal the intramolecular electronic communications vary in the four-electron redox processes of three Bis-CoQ0s.

View Article: PubMed Central - PubMed

Affiliation: Key Laboratory for Advanced Materials &Department of Chemistry, East China University of Science and Technology, Shanghai 200237, P. R. China.

ABSTRACT
Intramolecular electronic communications of molecular wires play a crucial role for developing molecular devices. In the present work, we describe different degrees of intramolecular electronic communications in the redox processes of three ubiquinone-based biomolecular wires (Bis-CoQ0s) evaluated by electrochemistry and Density Functional Theory (DFT) methods in different solvents. We found that the bridges linkers have a significant effect on the electronic communications between the two peripheral ubiquinone moieties and solvents effects are limited and mostly depend on the nature of solvents. The DFT calculations for the first time indicate the intensity of the electronic communications during the redox processes rely on the molecular orbital elements VL for electron transfer (half of the energy splitting of the LUMO and LUMO+1), which is could be affected by the bridges linkers. The DFT calculations also demonstrates the effect of solvents on the latter two-electron transfer of Bis-CoQ0s is more significant than the former two electrons transfer as the observed electrochemical behaviors of three Bis-CoQ0s. In addition, the electrochemistry and theoretical calculations reveal the intramolecular electronic communications vary in the four-electron redox processes of three Bis-CoQ0s.

No MeSH data available.