Photoredox catalysis is a powerful tool to access challenging and diverse syntheses. Absorption of visible light forms the excited state catalyst (*PC) but photons may be wasted if one of several unproductive pathways occur. Facile dissociation of the charge-separated encounter complex [PC:D], also known as (solvent) cage escape, is required for productive chemistry and directly governs availability of the critical PC intermediate.
View Article and Find Full Text PDFRelative biological effectiveness (RBE) differs between radiation qualities. However, an RBE of 1.0 has been established for photons regardless of the wide range of photon energies used clinically, the lack of reproducibility in radiobiological studies, and outdated reference energies used in the experimental literature.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
A sulfonated tris(1-phenylpyrazolato)iridium(III) complex ([Ir(sppz)]) serves as a proof-of-concept non-emissive enhancer of the widely used ECL detection system of tris(2,2'-bipyridine)ruthenium(II) ([Ru(bpy)]) with tri-n-propylamine (TPrA) co-reactant, acting through electrocatalysis of TPrA oxidation and efficient chemi-excitation of the luminophore. Using self-interference ECL spectroscopy, we show that the enhancer extends diffusion of the required electrogenerated precursors from the electrode surface. Previously reported enhancement through these pathways has been confounded by the inherent ECL of the enhancer, but the increase in [Ru(bpy)] ECL intensity using [Ir(sppz)] was obtained without its concomitant emission.
View Article and Find Full Text PDFTriple-negative breast cancer (TNBC), which constitutes 10-20 percent of all breast cancers, is aggressive, has high metastatic potential, and carries a poor prognosis due to limited treatment options. LT-IIc, a member of the type II subfamily of ADP-ribosylating-heat-labile enterotoxins that bind to a distinctive set of cell-surface ganglioside receptors-is cytotoxic toward TNBC cell lines, but has no cytotoxic activity for non-transformed breast epithelial cells. Here, primary TNBC cells, isolated from resected human tumors, showed an enhanced cytotoxic response specifically toward LT-IIc, in contrast to other enterotoxins that were tested.
View Article and Find Full Text PDFCochrane Database Syst Rev
May 2024
Background: Children with medical complexity (CMC) represent a small, but growing, proportion of all children. Regardless of their underlying diagnosis, by definition, all CMC have similar functional limitations and high healthcare needs. It has been suggested that improving aspects of healthcare delivery for CMC improves health- and quality of life-related outcomes for children and their families and reduces healthcare-related expenditure.
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