A Three-Step Kinetic Model for Electrochemical Charge Transfer in the Hopping Regime

Yin, Xing; Wierzbiński, Emil; Lu, Hao; Bezer, Silvia; Leon, Arnie R. de; Davis, Kathryn L.; Achim, Catalina

doi:10.1021/jp502826e

Cited by 6 publications

(9 citation statements)

References 65 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Our understanding of the charge transfer mechanism is based on a three-step process. 47 The first step is the charge generation by the illuminated nanoparticles and the charge injection into the DNA chain after crossing an electron injection barrier; the second step is the actual charge transfer through DNA until it reaches the reaction point. The third step is charge usage by an acceptor group, in our case 8BrdA.…”

Section: Results and Discussionmentioning

confidence: 99%

Section: Results and Discussionmentioning

confidence: 99%

“…In this way, we can rationalize that the highest energy loss will be associated with the injection into the DNA, and later the hot-electron energy will remain the same independent of the position of the modified nucleotide. From the three charge transfer steps, usually the charge injection is considered the rate-limiting step for the charge transfer, with an energy barrier which can vary between 0.2 and 0.4 eV. , …”

Section: Results and Discussionmentioning

confidence: 99%

“…From the three charge transfer steps, usually the charge injection is considered the rate-limiting step for the charge transfer, with an energy barrier which can vary between 0.2 and 0.4 eV. 47,52 This energetics considerations helps us to rationalize how much energy the generated hot electron needs to proceed with the reaction. Previously, our group has shown by low-energy electron attachment experiments in the gas phase that the 8bromoadenine is fragmented at three different energies of electron attachment, ∼0, 0.35, and ∼1 eV.…”

Section: Resultsmentioning

confidence: 99%

See 3 more Smart Citations

Spatial Separation of Plasmonic Hot-Electron Generation and a Hydrodehalogenation Reaction Center Using a DNA Wire

2021

View full text Add to dashboard Cite

Using hot charge carriers far from a plasmonic nanoparticle surface is very attractive for many applications in catalysis and nanomedicine and will lead to a better understanding of plasmon-induced processes, such as hot-charge-carrier- or heat-driven chemical reactions. Herein we show that DNA is able to transfer hot electrons generated by a silver nanoparticle over several nanometers to drive a chemical reaction in a molecule nonadsorbed on the surface. For this we use 8-bromo-adenosine introduced in different positions within a double-stranded DNA oligonucleotide. The DNA is also used to assemble the nanoparticles into nanoparticles ensembles enabling the use of surface-enhanced Raman scattering to track the decomposition reaction. To prove the DNA-mediated transfer, the probe molecule was insulated from the source of charge carriers, which hindered the reaction. The results indicate that DNA can be used to study the transfer of hot electrons and the mechanisms of advanced plasmonic catalysts.

show abstract

Section: Results and Discussionmentioning

confidence: 99%

Section: Results and Discussionmentioning

confidence: 99%

Section: Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

See 2 more Smart Citations

Spatial Separation of Plasmonic Hot-Electron Generation and a Hydrodehalogenation Reaction Center Using a DNA Wire

2021

View full text Add to dashboard Cite

show abstract

“…Figure 2 shows molecular structures for the two linker types. 34 In contrast, if the charge transport proceeds coherently, then the decomposition into resistances for each step is no longer possible; rather the transport should be viewed as a product of transmission probabilities for each step. In recent work on DNA conductance, Tao and coworkers showed that the use of an amino thymidine nucleoside linker significantly increased the conductance relative to a thiol linker.…”

mentioning

confidence: 99%

Effects of the Backbone and Chemical Linker on the Molecular Conductance of Nucleic Acid Duplexes

et al. 2017

Self Cite

View full text Add to dashboard Cite

Scanning tunneling microscope break junction measurements are used to examine how the molecular conductance of nucleic acids depends on the composition of their backbone and the linker group to the electrodes. Molecular conductances of 10 base pair long homoduplexes of DNA, aeg-PNA, γ-PNA, and a heteroduplex of DNA/aeg-PNA with identical nucleobase sequence were measured. The molecular conductance was found to vary by 12 to 13 times with the change in backbone. Computational studies show that the molecular conductance differences between nucleic acids of different backbones correlate with differences in backbone structural flexibility. The molecular conductance was also measured for duplexes connected to the electrode through two different linkers, one directly to the backbone and one directly to the nucleobase stack. While the linker causes an order-of-magnitude increase in the overall conductance for a particular duplex, the differences in the electrical conductance with backbone composition are preserved. The highest molecular conductance value, 0.06G, was measured for aeg-PNA duplexes with a base stack linker. These findings reveal an important new strategy for creating longer and more complex electroactive, nucleic acid assemblies.

show abstract

Electronic Transport via Proteins

et al. 2014

View full text Add to dashboard Cite

A central vision in molecular electronics is the creation of devices with functional molecular components that may provide unique properties. Proteins are attractive candidates for this purpose, as they have specific physical (optical, electrical) and chemical (selective binding, self-assembly) functions and offer a myriad of possibilities for (bio-)chemical modification. This Progress Report focuses on proteins as potential building components for future bioelectronic devices as they are quite efficient electronic conductors, compared with saturated organic molecules. The report addresses several questions: how general is this behavior; how does protein conduction compare with that of saturated and conjugated molecules; and what mechanisms enable efficient conduction across these large molecules? To answer these questions results of nanometer-scale and macroscopic electronic transport measurements across a range of organic molecules and proteins are compiled and analyzed, from single/few molecules to large molecular ensembles, and the influence of measurement methods on the results is considered. Generalizing, it is found that proteins conduct better than saturated molecules, and somewhat poorer than conjugated molecules. Significantly, the presence of cofactors (redox-active or conjugated) in the protein enhances their conduction, but without an obvious advantage for natural electron transfer proteins. Most likely, the conduction mechanisms are hopping (at higher temperatures) and tunneling (below ca. 150-200 K).

show abstract

A Three-Step Kinetic Model for Electrochemical Charge Transfer in the Hopping Regime

Cited by 6 publications

References 65 publications

Spatial Separation of Plasmonic Hot-Electron Generation and a Hydrodehalogenation Reaction Center Using a DNA Wire

Spatial Separation of Plasmonic Hot-Electron Generation and a Hydrodehalogenation Reaction Center Using a DNA Wire

Effects of the Backbone and Chemical Linker on the Molecular Conductance of Nucleic Acid Duplexes

Electronic Transport via Proteins

Contact Info

Product

Resources

About