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
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/255196
Acceder
id CONICETDig_f2e4370138f8e33b1bfd5f47b747de18
oai_identifier_str oai:ri.conicet.gov.ar:11336/255196
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling 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 Técnicas2025-10-22T11:05:12Zoai: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:34982025-10-22 11:05:12.544CONICET 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
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
_version_ 1846781325883736064
score 12.982451

Publicaciones similares