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Photoinduced phase separation, which limits the available band gap energies for photovoltaic applications, was reported for a range of mixed-halide perovskites. A microscopic understanding of the phase separation mechanism is still lacking but may be beneficial to rationalize limitations as well as enable the design of phase-stable perovskite semiconductors. In this letter, electron-beam-induced phase separations and transformations were investigated in a small crystallite of CsPb(Br0.8I0.2)3 by means of in situ high-resolution imaging in a transmission electron microscope. The acquired time series was evaluated using principal and independent component analysis to classify the structural change during the illumination by the electron beam. A more iodine-rich phase with the approximate composition of CsPb(Br0.6I0.4)3 was found to form at the edges of the particle, while a ternary pure bromide phase of CsPbBr3 remained at its center. These results provide an atomistic picture of in-grain phase segregation into iodide-rich phases at grain boundaries and bromide-rich phases in the interior of the grain.A method for the chemo-, regio-, and stereoselective one-pot synthesis of 1,3-enynes is described. The reaction of 2-chloro-N-(quinolin-8-yl)acetamides with terminal alkynes proceeds smoothly in the presence of a copper catalyst at room temperature to produce (E)-1,3-enynes in satisfactory to excellent yields. The mechanism study reveals that the cross-dimerization of internal alkynes generated in situ with terminal alkynes proceeds via allene intermediates. The directing group 8-aminoquinoline plays a key role in the current selective synthesis of (E)-1,3-enynes.We show by electron spin resonance (ESR) and Raman spectroscopies that the crystal phase transition of the lead-free double-perovskite Cs2AgBiBr6 has a profound symmetry-breaking effect on the high spin states of, for example, a transition-metal ion Fe3+ and the vibrational modes. It lifts their degeneracy when the crystal undergoes the cubic-tetragonal phase transition, splitting the six-fold degenerate S = 5/2 state of Fe3+ to three Kramer doublets and the enharmonic breathing mode Tg of the MBr6 octahedra (M = Ag, Bi, Fe) into Eg + Ag. The magnitudes of both spin and Raman line splitting are shown to directly correlate with the strength of the tetragonal strain field. https://www.selleckchem.com/MEK.html This work, in turn, demonstrates the power of the ESR and Raman spectroscopies in probing structural phase transitions and in providing in-depth information on the interplay between the structural, spin, and vibrational properties of lead-free double perovskites, a newly emerging and promising class of materials for low-cost and high-efficiency photovoltaics and optoelectronics.Using the commercially available and economical 6-hydroxycoumarin (6-HC) as the substrate, a dual-emission ratiometric fluorescence sensor was developed to detect tyrosinase (TYR) activity based on 3-aminophenyl boronic acid functionalized quantum dots (APBA-QDs). TYR can catalyze 6-HC, a monohydroxy compound, to form a fluorescence-enhancing o-hydroxy compound, 6,7-dihydroxycoumarin. Owing to the special covalent binding between the o-hydroxyl and boric acid groups, APBA-QDs react with 6,7-dihydroxycoumarin to form a five-membered ring ester dual-emission fluorescence probe for TYR. With an increase in TYR activity, the fluorescence at 675 nm originating from the QDs is gradually quenched, whereas that at 465 nm owing to 6,7-dihydroxycoumarin increases. Referencing the decreasing signal of the dual-emission probe at 675 nm to measure the increasing signal at 465 nm, a ratiometric fluorescence method was established to detect the TYR activity with high sensitivity and selectivity. Under the conditions optimized via response surface methodology, a linear range of 0-0.05 U/mL was obtained for the TYR activity. The detection limit was as low as 0.003 U/mL. This sensing strategy can also be adopted for the rapid screening of the TYR inhibitors.An extensive experimental and theoretical study of the Kα and Kβ high-resolution X-ray emission spectroscopy (XES) of sulfur-bearing systems is presented. This study encompasses a wide range of organic and inorganic compounds, including numerous experimental spectra from both prior published work and new measurements. Employing a linear-response time-dependent density functional theory (LR-TDDFT) approach, strong quantitative agreement is found in the calculation of energy shifts of the core-to-core Kα as well as the full range of spectral features in the valence-to-core Kβ spectrum. The ability to accurately calculate the sulfur Kα energy shift supports the use of sulfur Kα XES as a bulk-sensitive tool for assessing sulfur speciation. The fine structure of the sulfur Kβ spectrum, in conjunction with the theoretical results, is shown to be sensitive to the local electronic structure including effects of symmetry, ligand type and number, and, in the case of organosulfur compounds, to the nature of the bonded organic moiety. This agreement between theory and experiment, augmented by the potential for high-access XES measurements with the latest generation of laboratory-based spectrometers, demonstrates the possibility of broad analytical use of XES for sulfur and nearby third-row elements. The effective solution of the forward problem, i.e., successful prediction of detailed spectra from known molecular structure, also suggests future use of supervised machine learning approaches to experimental inference, as has seen recent interest for interpretation of X-ray absorption near-edge structure (XANES).Mitochondria have a plethora of functions within a eukaryotic cell, ranging from energy production, cell signaling, and protein cofactor synthesis to various aspects of metabolism. Mitochondrial dysfunction is known to cause over 200 named disorders and has been implicated in many human diseases and aging. Mitochondria have their own genetic material, mitochondrial DNA (mtDNA), which encodes 13 protein subunits in the oxidative phosphorylation system and a full set of transfer and rRNAs. Although more than 99% of the proteins in mitochondria are nuclear DNA (nDNA)-encoded, the integrity of mtDNA is critical for mitochondrial functions, as evidenced by mitochondrial diseases sourced from mtDNA mutations and depletions and the vital role of fragmented mtDNA molecules in cell signaling pathways. Previous research has shown that mtDNA is an important target of genotoxic assaults by a variety of chemical and physical factors. This Perspective discusses the prevalence of mtDNA damage by comparing the abundance of lesions in mDNA and nDNA and summarizes current knowledge on the biological pathways to cope with mtDNA damage, including mtDNA repair, mtDNA degradation, and mitochondrial fission and fusion.
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