The photophysical and photochemical properties of sulfoxide and sulfone derivatives of hemithioindigo photoswitches are scrutinized and compared to the unoxidized parent chromophores. Oxidation results in significantly blue-shifted absorptions and mostly reduction of photochromism while thermal stabilities of individual isomers remain largely unaltered. Effective photoswitching takes place at shorter wavelengths compared to parent hemithioindigos and high isomeric yields can be obtained reversibly in the respective photostationary states. Reversible solid-state photoswitching is observed for a twisted sulfone derivative accompanied by visible color changes. These results establish oxidized hemithioindigo photoswitches as promising and versatile tools for robust light-control of molecular behavior for a wide range of applications.
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http://dx.doi.org/10.1002/chem.202002176 | DOI Listing |
Biosensors (Basel)
February 2023
Key Laboratory of Biomedical Engineering of Hainan Province, School of Biomedical Engineering, Hainan University, Haikou 570228, China.
A photosensitizer furnishing with reversible control singlet oxygen generation (O) is highly desirable for precise photodynamic therapy (PDT), lessening non-specific harm to healthy tissues. Here, a novel photoswitchable aggregation-induced emission (AIE) photosensitizer based on a triarylamine (TPA)-modified hemithioindigo (HTI), 6Br-HTI-TPA-OMe, was rationally designed. The triarylamine AIE photosensitizing moiety and HTI switch unit were covalently linked in one molecule, permitting reversible regulation of O production.
View Article and Find Full Text PDFAdv Sci (Weinh)
October 2022
Department of Chemistry, Rice University, Houston, TX, 77005, USA.
Antibiotic resistance is a growing health threat. There is an urgent and critical need to develop new antimicrobial modalities and therapies. Here, a set of hemithioindigo (HTI)-based molecular machines capable of specifically killing Gram-positive bacteria within minutes of activation with visible light (455 nm at 65 mW cm ) that are safe for mammalian cells is described.
View Article and Find Full Text PDFChem Sci
January 2021
Ludwig-Maximilians-Universität München, Department of Chemistry, Center for Integrated Protein Science CIPSM Butenandtstr. 5-13 81377 München Germany
Introducing responsive elements into supramolecular recognition systems offers great advantages for the control of intermolecular interactions and represents an important stepping stone towards multi-purpose and reprogrammable synthetic systems. Of particular interest is implementation of light-responsiveness because of the unique ease and precision of this signal. Here we present visible light responsive hemithioindigo-based molecular tweezers that bear a highly polar sulfoxide function as an additional recognition unit inside their binding site.
View Article and Find Full Text PDFChemistry
August 2020
Department of Chemistry and Center for Integrated Protein Science CIPSM, Ludwig-Maximilians-Universität München, Butenandtstr. 5-13, 81377, München.
The photophysical and photochemical properties of sulfoxide and sulfone derivatives of hemithioindigo photoswitches are scrutinized and compared to the unoxidized parent chromophores. Oxidation results in significantly blue-shifted absorptions and mostly reduction of photochromism while thermal stabilities of individual isomers remain largely unaltered. Effective photoswitching takes place at shorter wavelengths compared to parent hemithioindigos and high isomeric yields can be obtained reversibly in the respective photostationary states.
View Article and Find Full Text PDFChem Asian J
June 2018
Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST), Av. Països Catalans, 16, 43007, Tarragona, Spain.
We report the synthesis of two 2-(4'-pyridyl-N-oxide)-substituted hemithioindigos (HTIs). We probed their photoisomerization by using UV/Vis and H NMR spectroscopy techniques. Light irradiation at λ=450 nm provoked the isomerization of the HTI Z isomer to the E counterpart to a large extent (≈80 % at the photostationary state).
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