Summary & Purpose

Molecular excitons play a foundational role in chromophore aggregates found in light-harvesting systems and offer potential applications in engineered excitonic systems. Controlled aggregation of chromophores to promote exciton delocalization has been achieved by covalently tethering chromophores to deoxyribonucleic acid (DNA) scaffolds. Although many studies have documented changes in the optical properties of chromophores upon aggregation using DNA scaffolds, more limited work has investigated how structural modifications of DNA via bridged nucleotides and chromophore covalent attachment impact scaffold stability as well as the configuration and optical behavior of attached aggregates. Here we investigated the impact of two types of bridged nucleotides, LNA and BNA, as a structural modification of duplex DNA-templated cyanine (Cy5) aggregates. The bridged nucleotides were incorporated in the domain of one to four Cy5 chromophores attached between adjacent bases of a DNA duplex. We found that bridged nucleotides increase the stability of DNA scaffolds carrying Cy5 aggregates in comparison with natural nucleotides in analogous constructs. Exciton coupling strength and delocalization in Cy5 aggregates were evaluated via steady-state absorption, circular dichroism, and theoretical modeling. Replacing natural nucleotides with bridged nucleotides resulted in a noticeable increase in the coupling strength (≥10 meV) between chromophores and increased H-like stacking behavior (i.e., more face-to-face stacking). Our results suggest that bridged nucleotides may be useful for increasing scaffold stability and coupling between DNA templated chromophores.

Author Identifier

Simon K. Roy, ORCID, 0000-0001-8652-1277

William B. Knowlton, ORCID: 0000-0003-3018-2207

Date of Publication or Submission

3-28-2023

DOI

https://doi.org/10.18122/quantum_data.1.boisestate

Funding Citation

This research was supported wholly by the U.S. Department of Energy, Idaho National Laboratory, Laboratory Directed Research and Development project through blanket master contract 154754 between Battelle Energy Alliance and Boise State University, Release 15, except for the following: the circular dichroism spectrometer was made available through the Biomolecular Research Center (BRC) supported by NIH awards P20GM103408 and P20GM109095, the MJ Murdock Charitable Trust, and the Idaho State Board of Education. Molecular graphics images in Figure 6 were produced by using the UCSF Chimera package from the Resource for Biocomputing, Visualization, and Informatics at the University of California, San Francisco (supported by NIH P41 RR-01081) All authors have given approval to the final version of the manuscript.

Single Dataset or Series?

Single Dataset

Data Format

*.csv, *.xlsx, *.docx, *.txt

File Size

2.01 MB

Data Attributes

See "Data_Attribute_README_files" folder containing:

  • Data_Attribute_README_Absorption.txt
  • Data_Attribute_README_Circular_Dichroism.txt
  • Data_Attribute_README_Fluorescence_Emission.txt
  • Data_Attribute_README_KRM_Modeling.txt
  • Data_Attribute_README_Melting_Profiles.txt
  • Data_Attribute_README_PAGE.txt

Time Period

2018-2021

Comments

Dataset Contributors: Christopher K. Wilson1 and Mayzie Houdek1 1Micron School of Materials Science and Engineering, Boise State University

Privacy and Confidentiality Statement

Boise State is explicitly compliant with federal and state laws surrounding data privacy including the protection of personal financial information through the Gramm-Leach-Bliley Act, personal medical information through HIPAA, HITECH and other regulations. All human subject data (e.g., surveys) has been collected and managed only by personnel with adequate human subject protection certification.

Use Restrictions

Users are free to share, copy, distribute and use the dataset; to create or produce works from the dataset; to adapt, modify, transform and build upon the dataset as long as the user attributes any public use of the dataset, or works produced from the dataset, referencing the author(s) and DOI link. For any use or redistribution of the dataset, or works produced from it, the user must make clear to others the license of the dataset and keep intact any notices on the original dataset.

Disclaimer of Warranty

BOISE STATE UNIVERSITY MAKES NO REPRESENTATIONS ABOUT THE SUITABILITY OF THE INFORMATION CONTAINED IN OR PROVIDED AS PART OF THE SYSTEM FOR ANY PURPOSE. ALL SUCH INFORMATION IS PROVIDED "AS IS" WITHOUT WARRANTY OF ANY KIND. BOISE STATE UNIVERSITY HEREBY DISCLAIMS ALL WARRANTIES AND CONDITIONS WITH REGARD TO THIS INFORMATION, INCLUDING ALL WARRANTIES AND CONDITIONS OF MERCHANTABILITY, WHETHER EXPRESS, IMPLIED OR STATUTORY, FITNESS FOR A PARTICULAR PURPOSE, TITLE AND NON-INFRINGEMENT. IN NO EVENT SHALL BOISE STATE UNIVERSITY BE LIABLE FOR ANY SPECIAL, INDIRECT OR CONSEQUENTIAL DAMAGES OR ANY DAMAGES WHATSOEVER RESULTING FROM LOSS OF USE, DATA OR PROFITS, WHETHER IN AN ACTION OF CONTRACT, NEGLIGENCE OR OTHER TORTIOUS ACTION, ARISING OUT OF OR IN CONNECTION WITH THE USE OR PERFORMANCE OF INFORMATION AVAILABLE FROM THE SYSTEM. THE INFORMATION PROVIDED BY THE SYSTEM COULD INCLUDE TECHNICAL INACCURACIES OR TYPOGRAPHICAL ERRORS. CHANGES ARE PERIODICALLY ADDED TO THE INFORMATION HEREIN. COMPANY AND/OR ITS RESPECTIVE SUPPLIERS MAY MAKE IMPROVEMENTS AND/OR CHANGES IN THE PRODUCT(S) AND/OR THE PROGRAM(S) DESCRIBED HEREIN AT ANY TIME, WITH OR WITHOUT NOTICE TO YOU. BOISE STATE UNIVERSITY DOES NOT MAKE ANY ASSURANCES WITH REGARD TO THE ACCURACY OF THE RESULTS OR OUTPUT THAT DERIVES FROM USE OF THE SYSTEM.

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