Molecular model of J-aggregated pseudoisocyanine fibers
Aggregated cyanines form ordered supramolecular structures with the potential to transport energy efficiently over long distances, a hallmark of photosynthetic light-harvesting complexes. In concentrated aqueous solution, pseudoisocyanine (PIC) spontaneously forms fibers with a chiral J-band red-shi...
| Main Authors: | , , , |
|---|---|
| Other Authors: | |
| Format: | Article |
| Language: | English |
| Published: |
AIP Publishing
2020
|
| Subjects: | |
| Online Access: | https://hdl.handle.net/1721.1/124842 |
| _version_ | 1810987055386198016 |
|---|---|
| author | Bricker, William P. Banal, James L. Stone, Matthew B. Bathe, Mark |
| author2 | Massachusetts Institute of Technology. Department of Biological Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Biological Engineering Bricker, William P. Banal, James L. Stone, Matthew B. Bathe, Mark |
| author_sort | Bricker, William P. |
| collection | MIT |
| description | Aggregated cyanines form ordered supramolecular structures with the potential to transport energy efficiently over long distances, a hallmark of photosynthetic light-harvesting complexes. In concentrated aqueous solution, pseudoisocyanine (PIC) spontaneously forms fibers with a chiral J-band red-shifted 1600 cm−1 from the monomeric 0-0 transition. A cryogenic transmission electron microscopy analysis of these fibers show an average fiber width of 2.89 nm, although the molecular-level structure of the aggregate is currently unknown. To determine a molecular model for these PIC fibers, the calculated spectra and dynamics using a Frenkel exciton model are compared to experiment. A chiral aggregate model in which the PIC monomers are neither parallel nor orthogonal to the long axis of the fiber is shown to replicate the experimental spectra most closely. This model can be physically realized by the sequential binding of PIC dimers and monomers to the ends of the fiber. These insights into the molecular aggregation model for aqueous PIC can also be applied to other similar cyanine-based supramolecular complexes with the potential for long-range energy transport, a key building block for the rational design of novel excitonic systems. |
| first_indexed | 2024-09-23T11:44:02Z |
| format | Article |
| id | mit-1721.1/124842 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T11:44:02Z |
| publishDate | 2020 |
| publisher | AIP Publishing |
| record_format | dspace |
| spelling | mit-1721.1/1248422022-09-27T21:33:30Z Molecular model of J-aggregated pseudoisocyanine fibers Bricker, William P. Banal, James L. Stone, Matthew B. Bathe, Mark Massachusetts Institute of Technology. Department of Biological Engineering Physical and Theoretical Chemistry General Physics and Astronomy Aggregated cyanines form ordered supramolecular structures with the potential to transport energy efficiently over long distances, a hallmark of photosynthetic light-harvesting complexes. In concentrated aqueous solution, pseudoisocyanine (PIC) spontaneously forms fibers with a chiral J-band red-shifted 1600 cm−1 from the monomeric 0-0 transition. A cryogenic transmission electron microscopy analysis of these fibers show an average fiber width of 2.89 nm, although the molecular-level structure of the aggregate is currently unknown. To determine a molecular model for these PIC fibers, the calculated spectra and dynamics using a Frenkel exciton model are compared to experiment. A chiral aggregate model in which the PIC monomers are neither parallel nor orthogonal to the long axis of the fiber is shown to replicate the experimental spectra most closely. This model can be physically realized by the sequential binding of PIC dimers and monomers to the ends of the fiber. These insights into the molecular aggregation model for aqueous PIC can also be applied to other similar cyanine-based supramolecular complexes with the potential for long-range energy transport, a key building block for the rational design of novel excitonic systems. United States. Department of Energy. Office of Basic Energy Sciences ( Award DE-SC0016353) United States. Army Research Office (Award W911NF1210420) United States. Office of Naval Research ( Award N00014-17-1-2609) Skoltech-MIT Center for Electrochemical Energy (Award 1911/R) United States. Office of Naval Research (Award N00014-13-1-0664) United States. Office of Naval Research (Award N00014-15-1-2830) National Cancer Institute (U.S.) (Grant P30-CA14051) United States. Department of Energy. Office of Basic Energy Sciences (Award DE-SC0001088) National Science Foundation (U.S.) (Grant NSF-0070319) 2020-04-23T20:46:42Z 2020-04-23T20:46:42Z 2018-07-14 2020-03-04T16:12:32Z Article http://purl.org/eprint/type/JournalArticle 0021-9606 1089-7690 https://hdl.handle.net/1721.1/124842 Bricker, William P. et al. “Molecular model of J-aggregated pseudoisocyanine fibers.” Journal of chemical physics 149 (2018): 024905 © 2018 The Author(s) en 10.1063/1.5036656 Journal of chemical physics Creative Commons Attribution-Noncommercial-Share Alike http://creativecommons.org/licenses/by-nc-sa/4.0/ application/pdf AIP Publishing PMC |
| spellingShingle | Physical and Theoretical Chemistry General Physics and Astronomy Bricker, William P. Banal, James L. Stone, Matthew B. Bathe, Mark Molecular model of J-aggregated pseudoisocyanine fibers |
| title | Molecular model of J-aggregated pseudoisocyanine fibers |
| title_full | Molecular model of J-aggregated pseudoisocyanine fibers |
| title_fullStr | Molecular model of J-aggregated pseudoisocyanine fibers |
| title_full_unstemmed | Molecular model of J-aggregated pseudoisocyanine fibers |
| title_short | Molecular model of J-aggregated pseudoisocyanine fibers |
| title_sort | molecular model of j aggregated pseudoisocyanine fibers |
| topic | Physical and Theoretical Chemistry General Physics and Astronomy |
| url | https://hdl.handle.net/1721.1/124842 |
| work_keys_str_mv | AT brickerwilliamp molecularmodelofjaggregatedpseudoisocyaninefibers AT banaljamesl molecularmodelofjaggregatedpseudoisocyaninefibers AT stonematthewb molecularmodelofjaggregatedpseudoisocyaninefibers AT bathemark molecularmodelofjaggregatedpseudoisocyaninefibers |