Smart yolk-shell nanoparticles (hollow nanoparticles with a movable core) with an acidic shell and a basic core were fabricated through an organosilane-assisted selective etching method and acted as efficient nanoreactors for catalyzing a deacetalization-Henry cascade reaction with high activity and high selectivity. This strategy is very promising for the design of multifunctional nanoreactors for cascade reactions.
Cancer linked isocitrate dehydrogenase (IDH) 1 variants, notably R132H IDH1, manifest a ‘gain-of-function’ to reduce 2-oxoglutarate to 2-hydroxyglutarate. High-throughput screens have enabled clinically useful R132H IDH1 inhibitors, mostly allosteric binders at the dimer interface. We report investigations on roles of divalent metal ions in IDH substrate and inhibitor binding that rationalise this observation. Mg2+/Mn2+ ions enhance substrate binding to wt IDH1 and R132H IDH1, but with the former manifesting lower Mg2+/Mn2+KMs. The isocitrate-Mg2+ complex is the preferred wt IDH1 substrate; with R132H IDH1, separate and weaker binding of 2-oxoglutarate and Mg2+ is preferred. Binding of R132H IDH1 inhibitors at the dimer interface weakens binding of active site Mg2+ complexes; their potency is affected by the Mg2+ concentration. Inhibitor selectivity for R132H IDH1 over wt IDH1 substantially arises from different stabilities of wt and R132H IDH1 substrate-Mg2+ complexes. The results reveal the importance of substrate-metal ion complexes in wt and R132H IDH1 catalysis and the basis for selective R132H IDH1 inhibition. Further studies on roles of metal ion complexes in TCA cycle and related metabolism, including from an evolutionary perspective, are of interest.
A type of soluble and thermally stable ladder-type poly(p-phenylene) (LPF) with fluorene units in polymer backbone has been synthesized by Suzuki coupling and Friedel-Crafts ring-closing reaction. The full characterization of structures and properties as well as the performances of electroluminescence devices of the new ladder polymers are presented. LPFs show the well-defined structures, high molecular weights, excellent thermal stability, and good solubility in common organic solvents. The high-efficiency emission and absence of low-energy emission band in photoluminescence spectra are observed from LPFs both in the solution and in the solid film. Furthermore, the single layer light-emitting device using LPFs as the active layer shows very stable blue-green emission with maximum luminescence of 5400 cd/m 2 and maximum luminance efficiency of 0.66 cd/A. The extraordinary low concentration of keto defects in LPFs may be corresponding to the improvement in optical and device properties. The attractive properties exhibited by new ladder-type poly(p-phenylene)s establish them as good candidates for active layers in light-emitting devices.
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