Small-Molecule Fluorophores with Large Stokes Shifts:
9-Iminopyronin Analogues as Clickable Tags

J 2015

Small-Molecule Fluorophores with Large Stokes Shifts: 9-Iminopyronin Analogues as Clickable Tags

HORVÁTH, Peter, Peter ŠEBEJ, Tomáš ŠOLOMEK and Petr KLÁN

Basic information

Original name

Small-Molecule Fluorophores with Large Stokes Shifts: 9-Iminopyronin Analogues as Clickable Tags

Authors

HORVÁTH, Peter (703 Slovakia, belonging to the institution), Peter ŠEBEJ (703 Slovakia, belonging to the institution), Tomáš ŠOLOMEK (703 Slovakia, belonging to the institution) and Petr KLÁN (203 Czech Republic, guarantor, belonging to the institution)

Edition

The journal of organic chemistry, 2015, 0022-3263

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10401 Organic chemistry

Country of publisher

United States of America

Confidentiality degree

není předmětem státního či obchodního tajemství

References:

URL

Impact factor

Impact factor: 4.785

RIV identification code

RIV/00216224:14310/15:00081568

Organization unit

Faculty of Science

DOI

http://dx.doi.org/10.1021/jo502213t

UT WoS

000349934600002

Keywords in English

photochemistry; spectroscopy; pyronins; DFT calculations

Abstract

V originále

The design, synthesis, and both experimental and theoretical studies of several novel 9-(acylimino)- and 9-(sulfonylimino)pyronin derivatives containing either an oxygen or a silicon atom at position 10 are reported. These compounds, especially the Si analogues, exhibit remarkably large Stokes shifts (around 200 nm) while still possessing a high fluorophore brightness, absorption bands in the near-UV and visible part of the spectrum, and high thermal and photochemical stabilities in protic solvents. The reason for the observed large Stokes shifts is an intramolecular charge-transfer excitation of an electron from the HOMO to the LUMO of the chromophore, accompanied by elongation of the C9-N bond and considerable solvent reorganization due to hydrogen bonding to the solvent. Due to the photophysical properties of the studied compounds and their facile and high-yielding synthesis, as well as a simple protocol for their bioorthogonal ligation to a model saccharide using a Huisgen alkyne-azide cycloaddition, they represent excellent candidates for biochemical and biological applications as fluorescent tags and indicators for multichannel imaging. 9-(Acylimino)pyronins alter their optical properties upon protonation and may also be used as pH sensors.

Links

GA13-25775S, research and development project

Name: Vývoj viditelným světlem aktivovatelných skupin a fluorescenčních značek pro chemii a biologii

Investor: Czech Science Foundation

LM2011028, research and development project

Name: RECETOX ? Národní infrastruktura pro výzkum toxických látek v prostředí

Investor: Ministry of Education, Youth and Sports of the CR

LO1214, research and development project

Name: Centrum pro výzkum toxických látek v prostředí (Acronym: RECETOX)

Investor: Ministry of Education, Youth and Sports of the CR

Citovat

HORVÁTH, Peter, Peter ŠEBEJ, Tomáš ŠOLOMEK and Petr KLÁN. Small-Molecule Fluorophores with Large Stokes Shifts: 9-Iminopyronin Analogues as Clickable Tags. The journal of organic chemistry. 2015, vol. 80, No 3, p. 1299-1311. ISSN 0022-3263. Available from: https://dx.doi.org/10.1021/jo502213t.

@article{1335110,
   author = {Horváth, Peter and Šebej, Peter and Šolomek, Tomáš and Klán, Petr},
   article_number = {3},
   doi = {http://dx.doi.org/10.1021/jo502213t},
   keywords = {photochemistry; spectroscopy; pyronins; DFT calculations},
   language = {eng},
   issn = {0022-3263},
   journal = {The journal of organic chemistry},
   title = {Small-Molecule Fluorophores with Large Stokes Shifts: 9-Iminopyronin Analogues as Clickable Tags},
   url = {http://pubs.acs.org/doi/abs/10.1021/jo502213t},
   volume = {80},
   year = {2015}
}

TY  - JOUR
ID  - 1335110
AU  - Horváth, Peter - Šebej, Peter - Šolomek, Tomáš - Klán, Petr
PY  - 2015
TI  - Small-Molecule Fluorophores with Large Stokes Shifts: 9-Iminopyronin Analogues as Clickable Tags
JF  - The journal of organic chemistry
VL  - 80
IS  - 3
SP  - 1299-1311
EP  - 1299-1311
SN  - 00223263
KW  - photochemistry
KW  - spectroscopy
KW  - pyronins
KW  - DFT calculations
UR  - http://pubs.acs.org/doi/abs/10.1021/jo502213t
N2  - The design, synthesis, and both experimental and theoretical studies of several novel 9-(acylimino)- and 9-(sulfonylimino)pyronin derivatives containing either an oxygen or a silicon atom at position 10 are reported. These compounds, especially the Si analogues, exhibit remarkably large Stokes shifts (around 200 nm) while still possessing a high fluorophore brightness, absorption bands in the near-UV and visible part of the spectrum, and high thermal and photochemical stabilities in protic solvents. The reason for the observed large Stokes shifts is an intramolecular charge-transfer excitation of an electron from the HOMO to the LUMO of the chromophore, accompanied by elongation of the C9-N bond and considerable solvent reorganization due to hydrogen bonding to the solvent. Due to the photophysical properties of the studied compounds and their facile and high-yielding synthesis, as well as a simple protocol for their bioorthogonal ligation to a model saccharide using a Huisgen alkyne-azide cycloaddition, they represent excellent candidates for biochemical and biological applications as fluorescent tags and indicators for multichannel imaging. 9-(Acylimino)pyronins alter their optical properties upon protonation and may also be used as pH sensors.
ER  -

HORVÁTH, Peter, Peter ŠEBEJ, Tomáš ŠOLOMEK and Petr KLÁN. Small-Molecule Fluorophores with Large Stokes Shifts: 9-Iminopyronin Analogues as Clickable Tags. \textit{The journal of organic chemistry}. 2015, vol.~80, No~3, p.~1299-1311. ISSN~0022-3263. Available from: https://dx.doi.org/10.1021/jo502213t.

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