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Effect of Hydrophilicity-Imparting Substituents on Exciton Delocalization in Squaraine Dye Aggregates Covalently Templated to DNA Holliday Junctions
Abstract
Molecular aggregates exhibit emergent properties, including the collective sharing of electronic excitation energy known as exciton delocalization, that can be leveraged in applications such as quantum computing, optical information processing, and light harvesting. In a previous study, we found unexpectedly large excitonic interactions (quantified by the excitonic hopping parameter Jm,n) in DNA-templated aggregates of squaraine (SQ) dyes with hydrophilic-imparting sulfo and butylsulfo substituents. Here, we characterize DNA Holliday junction (DNA-HJ) templated aggregates of an expanded set of SQs and evaluate their optical properties in the context of structural heterogeneity. Specifically, we characterized the orientation of and Jm,n between dyes in dimer aggregates of non-chlorinated and chlorinated SQs. Here, three new chlorinated SQs that feature a varying number of butylsulfo substituents were synthesized and attached to a DNA-HJ via a covalent linker to form adjacent and transverse dimers. Various characteristics of the dye, including its hydrophilicity (in terms of log Po/w) and surface area, and of the substituents, including their local bulkiness and electron withdrawing capacity, were quantified computationally.
- Authors:
-
[1];
[1];
[3];
[4];
[1];
[1];
[1];
[1];
[1]
- Boise State University, ID (United States)
- State Scientific Institution “Institute for Single Crystals” of the National Academy of Sciences of Ukraine, Kharkiv (Ukraine)
- SETA BioMedicals, LLC, Urbana, IL (United States)
- Boise State University, ID (United States); Center for Advanced Energy Studies, Idaho Falls, ID (United States)
- Publication Date:
- Research Org.:
- Boise State Univ., ID (United States)
- Sponsoring Org.:
- USDOE Established Program to Stimulate Competitive Research (EPSCoR) program; USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); USDOE
- OSTI Identifier:
- 2234233
- Alternate Identifier(s):
- OSTI ID: 2246680
- Grant/Contract Number:
- SC0020089
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nanoscale
- Additional Journal Information:
- Journal Volume: 16; Journal Issue: 3; Journal ID: ISSN 2040-3364
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 59 BASIC BIOLOGICAL SCIENCES; hydrophilicity; Frenkel exciton; dye aggregate; soft materials; photophysics; spectrophotometry
Citation Formats
Pascual, Gissela, Roy, Simon K., Barcenas, German, Wilson, Christopher K., Cervantes-Salguero, Keitel, Obukhova, Olena M., Krivoshey, Alexander I., Terpetschnig, Ewald, Tatarets, Anatoliy L., Li, Lan, Yurke, Bernard, Knowlton, William, Mass, Olga A., Pensack, Ryan D., and Lee, Jeunghoon. Effect of Hydrophilicity-Imparting Substituents on Exciton Delocalization in Squaraine Dye Aggregates Covalently Templated to DNA Holliday Junctions. United States: N. p., 2023.
Web. doi:10.1039/d3nr04499h.
Pascual, Gissela, Roy, Simon K., Barcenas, German, Wilson, Christopher K., Cervantes-Salguero, Keitel, Obukhova, Olena M., Krivoshey, Alexander I., Terpetschnig, Ewald, Tatarets, Anatoliy L., Li, Lan, Yurke, Bernard, Knowlton, William, Mass, Olga A., Pensack, Ryan D., & Lee, Jeunghoon. Effect of Hydrophilicity-Imparting Substituents on Exciton Delocalization in Squaraine Dye Aggregates Covalently Templated to DNA Holliday Junctions. United States. https://doi.org/10.1039/d3nr04499h
Pascual, Gissela, Roy, Simon K., Barcenas, German, Wilson, Christopher K., Cervantes-Salguero, Keitel, Obukhova, Olena M., Krivoshey, Alexander I., Terpetschnig, Ewald, Tatarets, Anatoliy L., Li, Lan, Yurke, Bernard, Knowlton, William, Mass, Olga A., Pensack, Ryan D., and Lee, Jeunghoon. Wed .
"Effect of Hydrophilicity-Imparting Substituents on Exciton Delocalization in Squaraine Dye Aggregates Covalently Templated to DNA Holliday Junctions". United States. https://doi.org/10.1039/d3nr04499h.
@article{osti_2234233,
title = {Effect of Hydrophilicity-Imparting Substituents on Exciton Delocalization in Squaraine Dye Aggregates Covalently Templated to DNA Holliday Junctions},
author = {Pascual, Gissela and Roy, Simon K. and Barcenas, German and Wilson, Christopher K. and Cervantes-Salguero, Keitel and Obukhova, Olena M. and Krivoshey, Alexander I. and Terpetschnig, Ewald and Tatarets, Anatoliy L. and Li, Lan and Yurke, Bernard and Knowlton, William and Mass, Olga A. and Pensack, Ryan D. and Lee, Jeunghoon},
abstractNote = {Molecular aggregates exhibit emergent properties, including the collective sharing of electronic excitation energy known as exciton delocalization, that can be leveraged in applications such as quantum computing, optical information processing, and light harvesting. In a previous study, we found unexpectedly large excitonic interactions (quantified by the excitonic hopping parameter Jm,n) in DNA-templated aggregates of squaraine (SQ) dyes with hydrophilic-imparting sulfo and butylsulfo substituents. Here, we characterize DNA Holliday junction (DNA-HJ) templated aggregates of an expanded set of SQs and evaluate their optical properties in the context of structural heterogeneity. Specifically, we characterized the orientation of and Jm,n between dyes in dimer aggregates of non-chlorinated and chlorinated SQs. Here, three new chlorinated SQs that feature a varying number of butylsulfo substituents were synthesized and attached to a DNA-HJ via a covalent linker to form adjacent and transverse dimers. Various characteristics of the dye, including its hydrophilicity (in terms of log Po/w) and surface area, and of the substituents, including their local bulkiness and electron withdrawing capacity, were quantified computationally.},
doi = {10.1039/d3nr04499h},
journal = {Nanoscale},
number = 3,
volume = 16,
place = {United States},
year = {Wed Dec 13 00:00:00 EST 2023},
month = {Wed Dec 13 00:00:00 EST 2023}
}
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