Getting a molecular grip on the half-lives of iminothioindoxyl photoswitches

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Dátum

2024

Názov časopisu

ISSN časopisu

Názov zväzku

Vydavateľ

Royal Society of Chemistry : Cambridge

ISBN

ISSN

2041-6520
2041-6539

Abstrakt

Visible-light-operated photoswitches are of growing interest in reversibly controlling molecular processes, enabling for example the precise spatiotemporal focusing of drug activity and manipulating the properties of materials. Therefore, many research efforts have been spent on seeking control over the (photo)physical properties of photoswitches, in particular the absorption maxima and the half-life. For photopharmacological applications, photoswitches should ideally be operated by visible light in at least one direction, and feature a metastable isomer with a half-life of 0.1–10 seconds. Here we present our efforts towards the engineering of the half-life of iminothioindoxyl (ITI) photoswitches, a recently discovered class of visible-light-responsive photochromes, whose applicability was hitherto limited by half-lives in the low millisecond range. Through the synthesis and characterization of a library of ITI photoswitches, we discovered variants with a substantially increased thermal stability, reaching half-lives of up to 0.2 seconds. Based on spectroscopic and computational analyses, we demonstrate how different substituent positions on the ITI molecule can be used to tune its photophysical properties independently to fit the desired application. Additionally, the unique reactivity of the ITI derivative that featured a perfluoro-aromatic ring and had the most long-lived metastable state was shown to be useful for labeling of nucleophilic functional groups. The present research thus paves the way for using ITI photoswitches in photopharmacology and chemical biology.

Popis

In: Chemical Science. Cambridge : Royal Society of Chemistry, 2024. ISSN 2041-6520. Vol. 15, no. 35 (2024), pp. 14379-14389.

Kľúčové slová

svetlo, fyzikálne vlastnosti, fotofarmakológia, photopharmacology

Výstup z projektu

APVV-20-0098 Svetlom riadené molekulové prepínanie Ministerstvo školstva, mládeže a telovýchovy ČR 90254 e-INFRA CZ TAČR CZ.02.01.01/00/22_008/0004587 TECHSCALE: Technologie za hranicí nanosvěta

Citácia

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CC BY Creative Commons Attribution 4.0. International
info:eu-repo/semantics/openAccess