Mohrmcclure6111

ich confirms H2O2 as the key oxygen supplier. Overall, the coordination geometry of the complexes strongly influenced the catalytic efficiencies. The geometry of one of the CuII-OOH intermediates has been optimized by the density functional theory method, and its calculated electronic and vibrational spectra are almost similar to the experimentally observed values.Caspase-3 (Casp-3) is an enzyme that efficiently induces apoptosis, a form of programmed cell death. We report a dendritic molecular glue PCGlue that enables intracellular delivery of Casp-3 and its photoactivation. Selleckchem garsorasib PCGlue carrying multiple guanidinium (Gu+) ion pendants via photocleavable linkages can tightly adhere to Casp-3 and deliver it into the cytoplasm mainly by direct penetration through the plasma membrane. Casp-3, whose surface is covered by PCGlue, is unable to interact with its cellular substrates and can therefore not induce apoptosis. However, upon exposure to UV or two-photon near-infrared (NIR) light, PCGlue is cleaved off to liberate Casp-3, triggering the apoptotic signaling cascade. This intracellular photoactivation of Casp-3 allows spatiotemporal induction of apoptosis in irradiated cells.Phosphor-converted white-light-emitting diodes (pc-WLEDs) rely on combining a near-ultraviolet (n-UV) or blue chip with trichromatic and yellow-emitting phosphors. It is challenging to discover cyan-green-emitting (480-520 nm) phosphors for compensating the spectral gap and producing full-spectrum white light. In this work, we successfully discovered two unprecedented bright cyan-green emitting Rb3RV2O8 (R = Y, Lu) phosphors that gives emission bands centered at 500 nm upon 362 nm n-UV light excitation. Interestingly, the both self-activated compounds exhibit high internal quantum efficiencies (IQEs) of 71% for Rb3YV2O8 and 85% for Rb3LuV2O8, respectively. Moreover, controllable emission color can be successfully tuned from cyan-green to orange-red across the warm white light region by design strategy of VO43- → Eu3+ energy transfer. The thermal quenching of as-prepared phosphors could be effectively mitigated by this design strategy. Finally, the as-fabricated n-UV (λex = 370 nm) pumped phosphor-converted (pc) W-LED devices utilizing Rb3RV2O8 (R = Y, Lu) along with commercial phosphors demonstrate well-distributed warm white light with high color-rendering index (CRI) of 91.9 and 93.5, and a low correlated color temperature (CCT) of 5095 and 4946 K. It suggests that the both vanadate phosphors have potential applications in full-spectrum pc-WLEDs.Metallocorroles involving 5d transition metals are currently of interest as near-IR phosphors and as photosensitizers for oxygen sensing and photodynamic therapy. Their syntheses, however, are often bedeviled by capricious and low-yielding protocols. Against this backdrop, we describe rhenium-imido corroles, a new class of 5d metallocorroles, synthesized simply and in respectable (∼30%) yields via the interaction of a free-base corrole, Re2(CO)10, K2CO3, and aniline in 1,2,4-trichlorobenzene at ∼190 °C in a sealed vial under strict anaerobic conditions. The generality of the method was shown by the synthesis of six derivatives, including those derived from meso-tris(pentafluorophenyl)corrole, H3[TPFPC], and five different meso-tris(p-X-phenyl)corroles, H3[TpXPC], where X = CF3, F, H, CH3, OCH3. Single-crystal X-ray structures obtained for two of the complexes, Re[TpFPC](NPh) and Re[TpCF3PC](NPh), revealed relatively unstrained equatorial Re-N distances of ∼2.00 Å, a ∼ 0.7-Å displacement of the Re from the mean plane of the corrole nitrogens, and an Re-Nimido distance of ∼1.72 Å. Details of the corrole skeletal bond distances, diamagnetic 1H NMR spectra, relatively substituent-independent Soret maxima, and electrochemical HOMO-LUMO gaps of ∼2.2 V all indicated an innocent corrole macrocycle. Surprisingly, unlike several other classes of 5d metallocorroles, the Re-imido complexes proved nonemissive in solution at room temperature and also failed to sensitize singlet oxygen formation, indicating rapid radiationless deactivation of the triplet state, presumably via the rapidly rotating axial phenyl group. By analogy with other metal-oxo and -imido corroles, we remain hopeful that the Re-imido group will prove amenable to further elaboration and thereby contribute to the development of a somewhat challenging area of coordination chemistry.Gregatin A (1) is a fungal polyketide featuring an alkylated furanone core, but the biosynthetic mechanism to furnish the intriguing molecular skeleton has yet to be elucidated. Herein, we have identified the biosynthetic gene cluster of gregatin A (1) in Penicillium sp. sh18 and investigated the mechanism that produces the intriguing structure of 1 by in vivo and in vitro reconstitution of its biosynthesis. Our study established the biosynthetic route leading to 1 and illuminated that 1 is generated by the fusion of two different polyketide chains, which are, amazingly, synthesized by a single polyketide synthase GrgA with the aid of a trans-acting enoylreductase GrgB. Chain fusion, as well as chain hydrolysis, is catalyzed by an α/β hydrolase, GrgF, hybridizing the C11 and C4 carbon chains by Claisen condensation. Finally, structural analysis and mutational experiments using GrgF provided insight into how the enzyme facilitates the unusual chain-fusing reaction. In unraveling a new biosynthetic strategy involving a bifunctional PKS and a polyketide fusing enzyme, our study expands our knowledge concerning fungal polyketide biosynthesis.A new family of layered alkali uranyl borates, A2(UO2)B2O5 (A = Cs, Rb, K), was synthesized as high quality single crystals via high temperature flux growth methods. At room temperature, the compounds are structurally closely related although they crystallize in different monoclinic space groups, specifically P21/c (Cs), C2/m (Rb), and C2/c (K). At a low temperature (100 K), Cs2(UO2)B2O5 becomes isostructural with K2(UO2)B2O5 as the result of a reversible structure transition by Cs2(UO2)B2O5. The title phases represent the first examples of uranyl borates resulting from high temperature flux growth utilizing alkali halide fluxes. The synthesis, structures, and thermal, optical, and ion exchange properties are reported, and modeling of the atomic structure and disorder of the ion exchanged phases is discussed.