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By virtue of the AIE effect, the thermo-induced aggregation phenomenon has been ingeniously utilized to apply PNVCL as a novel fluorescent thermometer for intracellular temperature determination. This journal is © The Royal Society of Chemistry 2020.Tungsten disulfide (WS2)-based micromotors with enhanced electrochemical and photo-catalytic activities are synthesized using a greatly simplified electrochemical deposition protocol at room temperature involving exclusively tungstic acid and sulfate as metal and sulfur sources without further building chemistry. The WS2-based micromotors exhibit dual electrochemical and photo-catalytic behavior in the inner and outer layers, respectively, due to the combination of the unique properties of the sp2 hybridized WS2 outer layer with highly reactive WS2-induced inner catalytic layers, accounting for this material's exclusive enhanced performances. A rough inner Pt-Ni layer allows tailoring the micromotor propulsion, with a speed increase of up to 1.6 times after external control of the micromotor with a magnetic field due to enhanced fuel accessibility. Such a coupling of the attractive capabilities of WS2 with enhanced micromotor movement holds considerable promise to address the growing energy crisis and environmental pollution concerns. This journal is © The Royal Society of Chemistry 2020.Monomeric boroles have been gaining attention as reagents for the synthesis of heterocycles due to their ability to insert atoms into the BC4 ring in a single step. Although unique boron frameworks can be accessed via this methodology, the products feature aryl substitution on the carbon centers as steric bulk is required to preclude borole dimerization. This work demonstrates that insertion chemistry is possible with Diels-Alder dimeric boroles and that such reactivity is not exclusive to monomeric boroles with bulky groups. With 1-phenyl-2,3,4,5-tetramethylborole dimer, the formal 1,1-insertion of a nitrene and sulfur generate the six-membered aromatic 1,2-azaborine and 1,2-thiaborine, respectively. The isolation of the 1,2-thiaborine enabled the synthesis of an η6-chromium complex. Benzophenone and diphenylketene readily insert a CO unit to generate BOC5 seven-membered rings confirming dimeric boroles can serve as monomeric synthons in 1,2-insertion reactions. An epoxide did not furnish the anticipated eight-membered BOC6 ring, instead provided a bicyclic system with a BOC3 ring. The insertion chemistry was demonstrated with two other borole dimers featuring different substitution with diphenylketene as a substrate. This work elevates borole insertion chemistry to a new level to access products that do not require bulky substitution. This journal is © The Royal Society of Chemistry 2020.Although host-guest pairing interactions between bisradical dicationic cyclobis(paraquat-p-phenylene) (BB2(˙+) ) and the bipyridinium radical cation (BIPY˙+ ) have been studied extensively, host molecules other than BB2(˙+) are few and far between. Herein, four bisradical dicationic cyclophanes with tunable cavity sizes are investigated as new bisradical dicationic hosts for accommodating the methyl viologen radical cation (MV˙+ ) to form trisradical tricationic complexes. The structure-property relationships between cavity sizes and binding affinities have been established by comprehensive solution and solid-state characterizations as well as DFT calculations. The association constants of the four new trisradical tricationic complexes are found to range between 7400 and 170 000 M-1, with the strongest one being 4.3 times higher than that for [MV⊂BB]3(˙+) . The facile accessibility and tunable stability of these new trisradical tricationic complexes make them attractive redox-controlled recognition motifs for further use in supramolecular chemistry and mechanostereochemistry. This journal is © The Royal Society of Chemistry 2020.We report the highly enantioselective synthesis of P-chiral tertiary phosphine oxides featuring an ethynyl group via Cu(i)-catalyzed azide-alkyne cycloaddition. Newly developed chiral pyridinebisoxazolines (PYBOX) bearing a bulky C4 shielding group play an important role in achieving excellent enantioselectivity while suppressing side bis-triazoles formation in desymmetrizing prochiral diethynylphosphine oxides. Notably, by tuning the size of the C4 shielding group, it is possible to achieve excellent remote enantiofacial control in desymmetrizing phosphole oxide-diynes with the prochiral P-center farther from the ethynyl group by four covalent bonds. Time-dependent enantioselectivity is observed for these desymmetric CuAAC reactions, suggesting a synergic combination of a desymmetrization and a kinetic resolution, and our ligands prove to be better than unmodified PYBOX in both steps. https://www.selleckchem.com/products/Decitabine.html This finding contributes to a highly enantioselective kinetic resolution of racemic ethynylphosphine oxides. The resulting chiral ethynylphosphine oxides are versatile P-chiral synthons, which can undergo a number of diversifying reactions to enrich structural diversity. This journal is © The Royal Society of Chemistry 2020.Pacman dinuclear CoII triphenylporphyrin-tri(pentafluorophenyl)porphyrin 1 and dinuclear CoII bis-tri(pentafluorophenyl)porphyrin 2, anchored at the two meso-positions of a benzene linker, are synthesized and examined as electrocatalysts for the oxygen reduction reaction (ORR). Both dinuclear Co bisporphyrins are more efficient and selective than corresponding mononuclear CoII tetra(pentafluorophenyl)porphyrin 3 and CoII tetraphenylporphyrin 4 for the four-electron electrocatalytic reduction of O2 to water. Significantly, although the ORR selectivities of the two dinuclear Co bisporphyrins are similar to each other, 1 outperforms 2, in terms of larger catalytic ORR currents and lower overpotentials. Electrochemical studies showed different redox behaviors of the two Co sites of 1 the CoIII/CoII reduction of the Co-TPP (TPP = triphenylporphyrin) site is well-behind that of the Co-TPFP (TPFP = tri(pentafluorophenyl)porphyrin) site by 440 mV. This difference indicated their different roles in the ORR CoII-TPFP is likely the O2 binding and reduction site, while CoIII-TPP, which is generated by the oxidation of CoII-TPP on electrodes, may function as a Lewis acid to assist the O2 binding and activation.
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