Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
Photocaging of Carboxylic Function Bearing Biomolecules by New Thiazole Derived Fluorophore. / Gagarin, Aleksey A; Minin, Artem S; Shevyrin, Vadim A и др.
в: Chemistry - A European Journal, Том 29, № 59, e202302079, 23.10.2023.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Photocaging of Carboxylic Function Bearing Biomolecules by New Thiazole Derived Fluorophore
AU - Gagarin, Aleksey A
AU - Minin, Artem S
AU - Shevyrin, Vadim A
AU - Kostova, Irena P
AU - Benassi, Enrico
AU - Belskaya, Nataliya P
N1 - Acknowledgements: We thank Russian Science Foundation (project 20-13-00089) for financially supporting. The administrative support received by the Europian Union-Next Generation EU, through the National Recovery and Resilience Plan of the republic of Bulgaria, project No. BG-PRP-2.004-0004-C01-is acknowledged. This work was performed using the equipment of the Shared Research Centre of Scientific Equipment SRC IIP UrB RAS. We also gratefully acknowledge the Siberian Branch of the Russian Academy of Sciences (SB RAS) Siberian Supercomputer Centre for providing supercomputer facilities. All authors have read and agreed to the published version of the manuscript. © 2023 Wiley-VCH GmbH.
PY - 2023/10/23
Y1 - 2023/10/23
N2 - The design and synthesis of a new fluorophore containing an arylidene thiazole scaffold resulted in a compound with good photophysical characteristics. Furthermore, the thiazole C5-methyl group was easily modified into specific functional groups (CH2 Br and CH2 OH) for the formation of a series of photocourier molecules containing model compounds (benzoic acids), as well as prodrugs, including salicylic acid, caffeic acid, and chlorambucil via a "benzyl" linker. Spectral characteristics (1 H, 13 C NMR, and high-resolution mass spectra) corresponded to the proposed structures. The photocourier molecules demonstrated absorption with high values of coefficient of molar extinction, exhibited contrasting green emission, and showed good dark stability. The mechanism of the photorelease was investigated through spectral analysis, HPLC-HRMS, and supported by TD-DFT calculations. The photoheterolysis and elimination of carboxylic acids were proved to occur in the excited state, yielding a carbocation as an intermediate moiety. The fluorophore structure provided stability to the carbocation through the delocalization of the positive charge via resonance structures. Viability assessment of Vero cells using the MTT-test confirmed the weak cytotoxicity of prodrugs without irradiation and it increase upon UV-light.
AB - The design and synthesis of a new fluorophore containing an arylidene thiazole scaffold resulted in a compound with good photophysical characteristics. Furthermore, the thiazole C5-methyl group was easily modified into specific functional groups (CH2 Br and CH2 OH) for the formation of a series of photocourier molecules containing model compounds (benzoic acids), as well as prodrugs, including salicylic acid, caffeic acid, and chlorambucil via a "benzyl" linker. Spectral characteristics (1 H, 13 C NMR, and high-resolution mass spectra) corresponded to the proposed structures. The photocourier molecules demonstrated absorption with high values of coefficient of molar extinction, exhibited contrasting green emission, and showed good dark stability. The mechanism of the photorelease was investigated through spectral analysis, HPLC-HRMS, and supported by TD-DFT calculations. The photoheterolysis and elimination of carboxylic acids were proved to occur in the excited state, yielding a carbocation as an intermediate moiety. The fluorophore structure provided stability to the carbocation through the delocalization of the positive charge via resonance structures. Viability assessment of Vero cells using the MTT-test confirmed the weak cytotoxicity of prodrugs without irradiation and it increase upon UV-light.
KW - TD-DFT calculations
KW - fluorescence
KW - photodissociation
KW - photoreleasing protecting groups
KW - thiazole
UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85171308342&origin=inward&txGid=67993c268d508c19d7b9c24f525bf2a7
UR - https://www.mendeley.com/catalogue/2c1e5aca-fcf6-38b5-8e86-64032746efe7/
U2 - 10.1002/chem.202302079
DO - 10.1002/chem.202302079
M3 - Article
C2 - 37530503
VL - 29
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 59
M1 - e202302079
ER -
ID: 55486386