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Tuning between Quenching and Energy Transfer in DNA-Templated Heterodimer Aggregates

[Image: see text] Molecular excitons, which propagate spatially via electronic energy transfer, are central to numerous applications including light harvesting, organic optoelectronics, and nanoscale computing; they may also benefit applications such as photothermal therapy and photoacoustic imaging...

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Autores principales: Chowdhury, Azhad U., Díaz, Sebastián A., Huff, Jonathan S., Barclay, Matthew S., Chiriboga, Matthew, Ellis, Gregory A., Mathur, Divita, Patten, Lance K., Sup, Aaron, Hallstrom, Natalya, Cunningham, Paul D., Lee, Jeunghoon, Davis, Paul H., Turner, Daniel B., Yurke, Bernard, Knowlton, William B., Medintz, Igor L., Melinger, Joseph S., Pensack, Ryan D.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8978177/
https://www.ncbi.nlm.nih.gov/pubmed/35319215
http://dx.doi.org/10.1021/acs.jpclett.2c00017
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author Chowdhury, Azhad U.
Díaz, Sebastián A.
Huff, Jonathan S.
Barclay, Matthew S.
Chiriboga, Matthew
Ellis, Gregory A.
Mathur, Divita
Patten, Lance K.
Sup, Aaron
Hallstrom, Natalya
Cunningham, Paul D.
Lee, Jeunghoon
Davis, Paul H.
Turner, Daniel B.
Yurke, Bernard
Knowlton, William B.
Medintz, Igor L.
Melinger, Joseph S.
Pensack, Ryan D.
author_facet Chowdhury, Azhad U.
Díaz, Sebastián A.
Huff, Jonathan S.
Barclay, Matthew S.
Chiriboga, Matthew
Ellis, Gregory A.
Mathur, Divita
Patten, Lance K.
Sup, Aaron
Hallstrom, Natalya
Cunningham, Paul D.
Lee, Jeunghoon
Davis, Paul H.
Turner, Daniel B.
Yurke, Bernard
Knowlton, William B.
Medintz, Igor L.
Melinger, Joseph S.
Pensack, Ryan D.
author_sort Chowdhury, Azhad U.
collection PubMed
description [Image: see text] Molecular excitons, which propagate spatially via electronic energy transfer, are central to numerous applications including light harvesting, organic optoelectronics, and nanoscale computing; they may also benefit applications such as photothermal therapy and photoacoustic imaging through the local generation of heat via rapid excited-state quenching. Here we show how to tune between energy transfer and quenching for heterodimers of the same pair of cyanine dyes by altering their spatial configuration on a DNA template. We assemble “transverse” and “adjacent” heterodimers of Cy5 and Cy5.5 using DNA Holliday junctions. We find that the transverse heterodimers exhibit optical properties consistent with excitonically interacting dyes and fluorescence quenching, while the adjacent heterodimers exhibit optical properties consistent with nonexcitonically interacting dyes and disproportionately large Cy5.5 emission, suggestive of energy transfer between dyes. We use transient absorption spectroscopy to show that quenching in the transverse heterodimer occurs via rapid nonradiative decay to the ground state (∼31 ps) and that in the adjacent heterodimer rapid energy transfer from Cy5 to Cy5.5 (∼420 fs) is followed by Cy5.5 excited-state relaxation (∼700 ps). Accessing such drastically different photophysics, which may be tuned on demand for different target applications, highlights the utility of DNA as a template for dye aggregation.
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spelling pubmed-89781772022-04-05 Tuning between Quenching and Energy Transfer in DNA-Templated Heterodimer Aggregates Chowdhury, Azhad U. Díaz, Sebastián A. Huff, Jonathan S. Barclay, Matthew S. Chiriboga, Matthew Ellis, Gregory A. Mathur, Divita Patten, Lance K. Sup, Aaron Hallstrom, Natalya Cunningham, Paul D. Lee, Jeunghoon Davis, Paul H. Turner, Daniel B. Yurke, Bernard Knowlton, William B. Medintz, Igor L. Melinger, Joseph S. Pensack, Ryan D. J Phys Chem Lett [Image: see text] Molecular excitons, which propagate spatially via electronic energy transfer, are central to numerous applications including light harvesting, organic optoelectronics, and nanoscale computing; they may also benefit applications such as photothermal therapy and photoacoustic imaging through the local generation of heat via rapid excited-state quenching. Here we show how to tune between energy transfer and quenching for heterodimers of the same pair of cyanine dyes by altering their spatial configuration on a DNA template. We assemble “transverse” and “adjacent” heterodimers of Cy5 and Cy5.5 using DNA Holliday junctions. We find that the transverse heterodimers exhibit optical properties consistent with excitonically interacting dyes and fluorescence quenching, while the adjacent heterodimers exhibit optical properties consistent with nonexcitonically interacting dyes and disproportionately large Cy5.5 emission, suggestive of energy transfer between dyes. We use transient absorption spectroscopy to show that quenching in the transverse heterodimer occurs via rapid nonradiative decay to the ground state (∼31 ps) and that in the adjacent heterodimer rapid energy transfer from Cy5 to Cy5.5 (∼420 fs) is followed by Cy5.5 excited-state relaxation (∼700 ps). Accessing such drastically different photophysics, which may be tuned on demand for different target applications, highlights the utility of DNA as a template for dye aggregation. American Chemical Society 2022-03-23 2022-03-31 /pmc/articles/PMC8978177/ /pubmed/35319215 http://dx.doi.org/10.1021/acs.jpclett.2c00017 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by-nc-nd/4.0/Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works (https://creativecommons.org/licenses/by-nc-nd/4.0/).
spellingShingle Chowdhury, Azhad U.
Díaz, Sebastián A.
Huff, Jonathan S.
Barclay, Matthew S.
Chiriboga, Matthew
Ellis, Gregory A.
Mathur, Divita
Patten, Lance K.
Sup, Aaron
Hallstrom, Natalya
Cunningham, Paul D.
Lee, Jeunghoon
Davis, Paul H.
Turner, Daniel B.
Yurke, Bernard
Knowlton, William B.
Medintz, Igor L.
Melinger, Joseph S.
Pensack, Ryan D.
Tuning between Quenching and Energy Transfer in DNA-Templated Heterodimer Aggregates
title Tuning between Quenching and Energy Transfer in DNA-Templated Heterodimer Aggregates
title_full Tuning between Quenching and Energy Transfer in DNA-Templated Heterodimer Aggregates
title_fullStr Tuning between Quenching and Energy Transfer in DNA-Templated Heterodimer Aggregates
title_full_unstemmed Tuning between Quenching and Energy Transfer in DNA-Templated Heterodimer Aggregates
title_short Tuning between Quenching and Energy Transfer in DNA-Templated Heterodimer Aggregates
title_sort tuning between quenching and energy transfer in dna-templated heterodimer aggregates
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8978177/
https://www.ncbi.nlm.nih.gov/pubmed/35319215
http://dx.doi.org/10.1021/acs.jpclett.2c00017
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