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This study investigates the correlation between photocytotoxicity and the prolonged excited-state lifetimes exhibited by certain Ru(II) polypyridyl photosensitizers comprised of π-expansive ligands. The eight metal complexes selected for this study differ markedly in their triplet state configurations and lifetimes. Human melanoma SKMEL28 and human leukemia HL60 cells were used as in vitro models to test photocytotoxicity induced by the compounds when activated by either broadband visible or monochromatic red light. The photocytotoxicities of the metal complexes investigated varied over 2 orders of magnitude and were positively correlated with their excited-state lifetimes. The complexes with the longest excited-state lifetimes, contributed by low-lying IL states, were the most phototoxic toward cancer cells under all conditions.
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http://dx.doi.org/10.1021/acs.inorgchem.8b03223 | DOI Listing |
J Phys Chem A
January 2025
Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109, United States.
Given their molecular properties and electronic structure, graphyne and graphdiyne are promising materials with numerous applications in different fields of material science. Dehydrobenzoannules (DBAs) are candidates that can serve as building blocks for synthesizing and designing new 2D carbon allotropes; however, only a few graphynes have been produced on a practical scale. Herein, we present our investigation of three DBAs, which serve as a model to understand the relationship between the structure and property, contributing to 2D carbon allotropes' rational design and synthetic effort.
View Article and Find Full Text PDFInorg Chem
January 2025
School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, P. R. China.
N-heterocyclic carbene (NHC)-based phosphorescent iridium complexes have attracted extensive attention due to their good optical properties and high stability in recent years. However, currently reported NHC-based iridium complexes can easily achieve emission of blue, green, or even ultraviolet light, while emission of red or deep-red light is relatively rare. Here, we report a new family of NHC-based deep-red iridium complexes (Ir1, Ir2, Ir3, and Ir4) featuring three-charge (0, -1, -2) ligands.
View Article and Find Full Text PDFChem Sci
January 2025
Key Laboratory for Advanced Materials, Institute of Fine Chemicals, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Chemistry and Molecular Engineering, Center of Photosensitive Chemicals Engineering, East China University of Science and Technology Shanghai 200237 China
Given that proteins with minor variations in amino acid sequences cause distinct functional outcomes, identifying and quantifying similar proteins is crucial, but remains a long-standing challenge. Herein, we present a two-dimensional orthogonal fluorescence and chemiluminescence design strategy for the probe DCM-SA, which is sequentially activated by albumin-mediated hydrolysis, exhibiting light-up fluorescence and photo-induced cycloaddition generating chemiluminescence, enabling orthogonal signal amplification for discrimination of subtle differences between similar proteins. By orthogonalizing these dual-mode signals, a two-dimensional work curve of fluorescence and chemiluminescence is established to distinguish and quantify similar proteins HSA and BSA.
View Article and Find Full Text PDFOrg Process Res Dev
January 2025
School of Chemistry, The University of Nottingham, University Park, Nottingham NG7 2RD, U.K.
We report the development and optimization of a scalable flow process for metallaphotoredox (Ir/Ni) C-O coupling, a mild and efficient approach for forming alkyl-aryl ethers, a common motif in medicinal and process chemistry settings. Time-resolved infrared spectroscopy (TRIR) highlighted the amine as the major quencher of the photocatalyst triplet excited state, along with the formation of an Ir(II) species that, in the presence of the Ni cocatalyst, has its lifetime shortened, suggesting reductive quenching of Ir(III)*, followed by reoxidation facilitated by the Ni cocatalyst. TRIR and batch reaction screening was used to develop conditions transferrable to flow, and many processing benefits of performing the reaction in flow were then demonstrated using a simple to construct/operate, small-footprint FEP coil flow reactor, including short (<10 min) space times and reduced catalyst loadings (down to 0.
View Article and Find Full Text PDFPhotochem Photobiol
January 2025
Departamento de Bioquímica, Facultad de Ciencias Naturales, Exactas y Tecnología, Universidad de Panamá, Panamá, Republic of Panama.
Toluidine blue O (TBO) is a type I-type II photosensitizer that has shown good efficacy and selectivity in antimicrobial and anticancer photodynamic therapy applications. However, its complex photochemistry with multiple photoproducts hinders its application as a photosensitizer. We have previously described the mechanism for photooxidative demethylation of TBO which in acetonitrile yields two main products: demethylated-TBO (d-TBO) and double-demethylated-TBO (dd-TBO).
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