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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.


The scatter diagram of experimental vs. calculated reduction potentials forfour electrons transfer processes of Bis-CoQ0 1 (A) andBis-CoQ0 2 (B) in five aprotic solvents.
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f5: The scatter diagram of experimental vs. calculated reduction potentials forfour electrons transfer processes of Bis-CoQ0 1 (A) andBis-CoQ0 2 (B) in five aprotic solvents.

Mentions: Figure 5 shows the correction and otherness of experimentaland calculated electrode reduction potentials for the four electrons transferprocesses of Bis-CoQ0 1 and Bis-CoQ0 2 in five solvents,respectively. It can be seen from Fig. 5, there are notsignificant relationships between the experimental and calculated reductionpotentials owing to the fact that the conditions for experimental and calculatedprocesses are not exactly same. Some complicated chemical reactions occurred inelectrons transfer processes and we have not method to simulate these reactionsduring the calculations21. However, several trends are veryclear in the Fig. 5. Firstly, the calculated results alsoindicated that the solvents effect on the latter two electrons transfer is moresignificant than the former two electrons transfer. Secondly, the calculatedreduction potentials are almost same in CH3CN, DMF and DMSO but verydifferent in THF and CH2Cl2, which can explained by thesimilar solvent parameters for CH3CN, DMF and DMSO, such asdielectric constant and polarity. Thirdly, the calculated reduction potentialsin CH3CN, DMF and DMSO are similar for the first two electrontransfer of Bis-CoQ0 1 and Bis-CoQ0 2, which also revealsthat the solvents effect on the intramolecular electronic communication isfeeble. These electrochemical results and DFT calculations indicate the solventsaffect on the intramolecular electronic communications of threeBis-CoQ0s is very week and mostly rely on the nature of thesolvents.


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)

The scatter diagram of experimental vs. calculated reduction potentials forfour electrons transfer processes of Bis-CoQ0 1 (A) andBis-CoQ0 2 (B) in five aprotic solvents.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

f5: The scatter diagram of experimental vs. calculated reduction potentials forfour electrons transfer processes of Bis-CoQ0 1 (A) andBis-CoQ0 2 (B) in five aprotic solvents.
Mentions: Figure 5 shows the correction and otherness of experimentaland calculated electrode reduction potentials for the four electrons transferprocesses of Bis-CoQ0 1 and Bis-CoQ0 2 in five solvents,respectively. It can be seen from Fig. 5, there are notsignificant relationships between the experimental and calculated reductionpotentials owing to the fact that the conditions for experimental and calculatedprocesses are not exactly same. Some complicated chemical reactions occurred inelectrons transfer processes and we have not method to simulate these reactionsduring the calculations21. However, several trends are veryclear in the Fig. 5. Firstly, the calculated results alsoindicated that the solvents effect on the latter two electrons transfer is moresignificant than the former two electrons transfer. Secondly, the calculatedreduction potentials are almost same in CH3CN, DMF and DMSO but verydifferent in THF and CH2Cl2, which can explained by thesimilar solvent parameters for CH3CN, DMF and DMSO, such asdielectric constant and polarity. Thirdly, the calculated reduction potentialsin CH3CN, DMF and DMSO are similar for the first two electrontransfer of Bis-CoQ0 1 and Bis-CoQ0 2, which also revealsthat the solvents effect on the intramolecular electronic communication isfeeble. These electrochemical results and DFT calculations indicate the solventsaffect on the intramolecular electronic communications of threeBis-CoQ0s is very week and mostly rely on the nature of thesolvents.

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.