The carbonyl-lock mechanism underlying non-aromatic fluorescence in biological matter
- Autores
- Díaz Mirón, Gonzalo; Semelak, Jonathan Alexis; Grisanti, Luca; Rodriguez, Alex; Conti, Irene; Stella, Martina; Velusamy, Jayaramakrishnan; Seriani, Nicola; Došlić, Nadja; Rivalta, Ivan; Garavelli, Marco; Estrin, Dario Ariel; Kaminski Schierle, Gabriele S.; González Lebrero, Mariano Camilo; Hassanali, Ali; Morzan, Uriel N.
- Año de publicación
- 2023
- Idioma
- inglés
- Tipo de recurso
- artículo
- Estado
- versión publicada
- Descripción
- Challenging the basis of our chemical intuition, recent experimental evidencereveals the presence of a new type of intrinsic fluorescence in biomoleculesthat exists even in the absence of aromatic or electronically conjugated che-mical compounds. The origin of this phenomenon has remained elusive so far.In the present study, we identify a mechanism underlying this new type offluorescence in different biological aggregates. By employing non-adiabatic abinitio molecular dynamics simulations combined with a data-driven approach,we characterize the typical ultrafast non-radiative relaxation pathways activein non-fluorescent peptides. We show that the key vibrational mode for thenon-radiative decay towards the ground state is the carbonyl elongation. Non-aromatic fluorescence appears to emerge from blocking this mode with stronglocal interactions such as hydrogen bonds. While we cannot rule out theexistence of alternative non-aromatic fluorescence mechanisms in other sys-tems, we demonstrate that this carbonyl-lock mechanism for trapping theexcited state leads to the fluorescence yield increase observed experimentally,and set the stage for design principles to realize novel non-invasive bio-compatible probes with applications in bioimaging, sensing, andbiophotonics.
Fil: Díaz Mirón, Gonzalo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Semelak, Jonathan Alexis. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Grisanti, Luca. Ruder Bošković Institute; Croacia
Fil: Rodriguez, Alex. The Abdus Salam. International Centre for Theoretical Physics; Italia
Fil: Conti, Irene. Università di Bologna; Italia
Fil: Stella, Martina. The Abdus Salam. International Centre for Theoretical Physics; Italia
Fil: Velusamy, Jayaramakrishnan. University of Cambridge; Estados Unidos
Fil: Seriani, Nicola. The Abdus Salam. International Centre for Theoretical Physics; Italia
Fil: Došlić, Nadja. Ruder Bošković Institute; Croacia
Fil: Rivalta, Ivan. Università di Bologna; Italia
Fil: Garavelli, Marco. Università di Bologna; Italia
Fil: Estrin, Dario Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Kaminski Schierle, Gabriele S.. University of Cambridge; Estados Unidos
Fil: González Lebrero, Mariano Camilo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Hassanali, Ali. The Abdus Salam. International Centre for Theoretical Physics; Italia
Fil: Morzan, Uriel N.. The Abdus Salam. International Centre for Theoretical Physics; Italia - Materia
-
fluorescence
TD-DFT
QM-MM - Nivel de accesibilidad
- acceso abierto
- Condiciones de uso
- https://creativecommons.org/licenses/by/2.5/ar/
- Repositorio
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/255196
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The carbonyl-lock mechanism underlying non-aromatic fluorescence in biological matterDíaz Mirón, GonzaloSemelak, Jonathan AlexisGrisanti, LucaRodriguez, AlexConti, IreneStella, MartinaVelusamy, JayaramakrishnanSeriani, NicolaDošlić, NadjaRivalta, IvanGaravelli, MarcoEstrin, Dario ArielKaminski Schierle, Gabriele S.González Lebrero, Mariano CamiloHassanali, AliMorzan, Uriel N.fluorescenceTD-DFTQM-MMhttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1Challenging the basis of our chemical intuition, recent experimental evidencereveals the presence of a new type of intrinsic fluorescence in biomoleculesthat exists even in the absence of aromatic or electronically conjugated che-mical compounds. The origin of this phenomenon has remained elusive so far.In the present study, we identify a mechanism underlying this new type offluorescence in different biological aggregates. By employing non-adiabatic abinitio molecular dynamics simulations combined with a data-driven approach,we characterize the typical ultrafast non-radiative relaxation pathways activein non-fluorescent peptides. We show that the key vibrational mode for thenon-radiative decay towards the ground state is the carbonyl elongation. Non-aromatic fluorescence appears to emerge from blocking this mode with stronglocal interactions such as hydrogen bonds. While we cannot rule out theexistence of alternative non-aromatic fluorescence mechanisms in other sys-tems, we demonstrate that this carbonyl-lock mechanism for trapping theexcited state leads to the fluorescence yield increase observed experimentally,and set the stage for design principles to realize novel non-invasive bio-compatible probes with applications in bioimaging, sensing, andbiophotonics.Fil: Díaz Mirón, Gonzalo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Semelak, Jonathan Alexis. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Grisanti, Luca. Ruder Bošković Institute; CroaciaFil: Rodriguez, Alex. The Abdus Salam. International Centre for Theoretical Physics; ItaliaFil: Conti, Irene. Università di Bologna; ItaliaFil: Stella, Martina. The Abdus Salam. International Centre for Theoretical Physics; ItaliaFil: Velusamy, Jayaramakrishnan. University of Cambridge; Estados UnidosFil: Seriani, Nicola. The Abdus Salam. International Centre for Theoretical Physics; ItaliaFil: Došlić, Nadja. Ruder Bošković Institute; CroaciaFil: Rivalta, Ivan. Università di Bologna; ItaliaFil: Garavelli, Marco. Università di Bologna; ItaliaFil: Estrin, Dario Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Kaminski Schierle, Gabriele S.. University of Cambridge; Estados UnidosFil: González Lebrero, Mariano Camilo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Hassanali, Ali. The Abdus Salam. International Centre for Theoretical Physics; ItaliaFil: Morzan, Uriel N.. The Abdus Salam. International Centre for Theoretical Physics; ItaliaNature2023-11info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/255196Díaz Mirón, Gonzalo; Semelak, Jonathan Alexis; Grisanti, Luca; Rodriguez, Alex; Conti, Irene; et al.; The carbonyl-lock mechanism underlying non-aromatic fluorescence in biological matter; Nature; Nature Communications; 14; 1; 11-2023; 1-132041-1723CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1038/s41467-023-42874-3info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:37:04Zoai:ri.conicet.gov.ar:11336/255196instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 09:37:04.615CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse |
dc.title.none.fl_str_mv |
The carbonyl-lock mechanism underlying non-aromatic fluorescence in biological matter |
title |
The carbonyl-lock mechanism underlying non-aromatic fluorescence in biological matter |
spellingShingle |
The carbonyl-lock mechanism underlying non-aromatic fluorescence in biological matter Díaz Mirón, Gonzalo fluorescence TD-DFT QM-MM |
title_short |
The carbonyl-lock mechanism underlying non-aromatic fluorescence in biological matter |
title_full |
The carbonyl-lock mechanism underlying non-aromatic fluorescence in biological matter |
title_fullStr |
The carbonyl-lock mechanism underlying non-aromatic fluorescence in biological matter |
title_full_unstemmed |
The carbonyl-lock mechanism underlying non-aromatic fluorescence in biological matter |
title_sort |
The carbonyl-lock mechanism underlying non-aromatic fluorescence in biological matter |
dc.creator.none.fl_str_mv |
Díaz Mirón, Gonzalo Semelak, Jonathan Alexis Grisanti, Luca Rodriguez, Alex Conti, Irene Stella, Martina Velusamy, Jayaramakrishnan Seriani, Nicola Došlić, Nadja Rivalta, Ivan Garavelli, Marco Estrin, Dario Ariel Kaminski Schierle, Gabriele S. González Lebrero, Mariano Camilo Hassanali, Ali Morzan, Uriel N. |
author |
Díaz Mirón, Gonzalo |
author_facet |
Díaz Mirón, Gonzalo Semelak, Jonathan Alexis Grisanti, Luca Rodriguez, Alex Conti, Irene Stella, Martina Velusamy, Jayaramakrishnan Seriani, Nicola Došlić, Nadja Rivalta, Ivan Garavelli, Marco Estrin, Dario Ariel Kaminski Schierle, Gabriele S. González Lebrero, Mariano Camilo Hassanali, Ali Morzan, Uriel N. |
author_role |
author |
author2 |
Semelak, Jonathan Alexis Grisanti, Luca Rodriguez, Alex Conti, Irene Stella, Martina Velusamy, Jayaramakrishnan Seriani, Nicola Došlić, Nadja Rivalta, Ivan Garavelli, Marco Estrin, Dario Ariel Kaminski Schierle, Gabriele S. González Lebrero, Mariano Camilo Hassanali, Ali Morzan, Uriel N. |
author2_role |
author author author author author author author author author author author author author author author |
dc.subject.none.fl_str_mv |
fluorescence TD-DFT QM-MM |
topic |
fluorescence TD-DFT QM-MM |
purl_subject.fl_str_mv |
https://purl.org/becyt/ford/1.3 https://purl.org/becyt/ford/1 |
dc.description.none.fl_txt_mv |
Challenging the basis of our chemical intuition, recent experimental evidencereveals the presence of a new type of intrinsic fluorescence in biomoleculesthat exists even in the absence of aromatic or electronically conjugated che-mical compounds. The origin of this phenomenon has remained elusive so far.In the present study, we identify a mechanism underlying this new type offluorescence in different biological aggregates. By employing non-adiabatic abinitio molecular dynamics simulations combined with a data-driven approach,we characterize the typical ultrafast non-radiative relaxation pathways activein non-fluorescent peptides. We show that the key vibrational mode for thenon-radiative decay towards the ground state is the carbonyl elongation. Non-aromatic fluorescence appears to emerge from blocking this mode with stronglocal interactions such as hydrogen bonds. While we cannot rule out theexistence of alternative non-aromatic fluorescence mechanisms in other sys-tems, we demonstrate that this carbonyl-lock mechanism for trapping theexcited state leads to the fluorescence yield increase observed experimentally,and set the stage for design principles to realize novel non-invasive bio-compatible probes with applications in bioimaging, sensing, andbiophotonics. Fil: Díaz Mirón, Gonzalo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina Fil: Semelak, Jonathan Alexis. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina Fil: Grisanti, Luca. Ruder Bošković Institute; Croacia Fil: Rodriguez, Alex. The Abdus Salam. International Centre for Theoretical Physics; Italia Fil: Conti, Irene. Università di Bologna; Italia Fil: Stella, Martina. The Abdus Salam. International Centre for Theoretical Physics; Italia Fil: Velusamy, Jayaramakrishnan. University of Cambridge; Estados Unidos Fil: Seriani, Nicola. The Abdus Salam. International Centre for Theoretical Physics; Italia Fil: Došlić, Nadja. Ruder Bošković Institute; Croacia Fil: Rivalta, Ivan. Università di Bologna; Italia Fil: Garavelli, Marco. Università di Bologna; Italia Fil: Estrin, Dario Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina Fil: Kaminski Schierle, Gabriele S.. University of Cambridge; Estados Unidos Fil: González Lebrero, Mariano Camilo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina Fil: Hassanali, Ali. The Abdus Salam. International Centre for Theoretical Physics; Italia Fil: Morzan, Uriel N.. The Abdus Salam. International Centre for Theoretical Physics; Italia |
description |
Challenging the basis of our chemical intuition, recent experimental evidencereveals the presence of a new type of intrinsic fluorescence in biomoleculesthat exists even in the absence of aromatic or electronically conjugated che-mical compounds. The origin of this phenomenon has remained elusive so far.In the present study, we identify a mechanism underlying this new type offluorescence in different biological aggregates. By employing non-adiabatic abinitio molecular dynamics simulations combined with a data-driven approach,we characterize the typical ultrafast non-radiative relaxation pathways activein non-fluorescent peptides. We show that the key vibrational mode for thenon-radiative decay towards the ground state is the carbonyl elongation. Non-aromatic fluorescence appears to emerge from blocking this mode with stronglocal interactions such as hydrogen bonds. While we cannot rule out theexistence of alternative non-aromatic fluorescence mechanisms in other sys-tems, we demonstrate that this carbonyl-lock mechanism for trapping theexcited state leads to the fluorescence yield increase observed experimentally,and set the stage for design principles to realize novel non-invasive bio-compatible probes with applications in bioimaging, sensing, andbiophotonics. |
publishDate |
2023 |
dc.date.none.fl_str_mv |
2023-11 |
dc.type.none.fl_str_mv |
info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion http://purl.org/coar/resource_type/c_6501 info:ar-repo/semantics/articulo |
format |
article |
status_str |
publishedVersion |
dc.identifier.none.fl_str_mv |
http://hdl.handle.net/11336/255196 Díaz Mirón, Gonzalo; Semelak, Jonathan Alexis; Grisanti, Luca; Rodriguez, Alex; Conti, Irene; et al.; The carbonyl-lock mechanism underlying non-aromatic fluorescence in biological matter; Nature; Nature Communications; 14; 1; 11-2023; 1-13 2041-1723 CONICET Digital CONICET |
url |
http://hdl.handle.net/11336/255196 |
identifier_str_mv |
Díaz Mirón, Gonzalo; Semelak, Jonathan Alexis; Grisanti, Luca; Rodriguez, Alex; Conti, Irene; et al.; The carbonyl-lock mechanism underlying non-aromatic fluorescence in biological matter; Nature; Nature Communications; 14; 1; 11-2023; 1-13 2041-1723 CONICET Digital CONICET |
dc.language.none.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
info:eu-repo/semantics/altIdentifier/doi/10.1038/s41467-023-42874-3 |
dc.rights.none.fl_str_mv |
info:eu-repo/semantics/openAccess https://creativecommons.org/licenses/by/2.5/ar/ |
eu_rights_str_mv |
openAccess |
rights_invalid_str_mv |
https://creativecommons.org/licenses/by/2.5/ar/ |
dc.format.none.fl_str_mv |
application/pdf application/pdf application/pdf |
dc.publisher.none.fl_str_mv |
Nature |
publisher.none.fl_str_mv |
Nature |
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reponame:CONICET Digital (CONICET) instname:Consejo Nacional de Investigaciones Científicas y Técnicas |
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CONICET Digital (CONICET) |
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Consejo Nacional de Investigaciones Científicas y Técnicas |
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CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas |
repository.mail.fl_str_mv |
dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar |
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13.070432 |