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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...
Autores principales: | , , , , , , , , , , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2022
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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. |
format | Online Article Text |
id | pubmed-8978177 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
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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