Kramerhaynes2793

4%. In addition, this novel nanomaterial achieved good therapeutic effects with less toxicity in vitro. The BZ nanomaterial loaded with GA caused tumor shrinkage as well as disappearance and effectively downregulated Hsp90 expression in tumors in vivo. Moreover, this novel nanomaterial exhibited good biocompatibility and potential for application in low-temperature PTT with excellent tumor destruction efficacy.The transamidation of tertiary amides was achieved via nickel catalysis in combination with briphos ligands. N-Methyl-N-phenylbenzamide derivatives reacted with primary amines in the presence of NiCl2/briphos L4 to provide the transamidated products in moderate to good yields. Primary aromatic amines delivered higher product yields than aliphatic amines.1,3-Cyclohexandione derived cyclic ketals and thiol ketals were used as O- and S-nucleophiles, respectively, for the ring opening of donor-acceptor cyclopropanes catalyzed by Cu(OTf)2 and a series of functionalized alkylene glycol diethers and dithiol diethers were obtained in good to high yields under mild conditions.The ongoing interest in all-inorganic cesium lead bromide perovskite nanocrystals (CsPbBr3 NCs) is mainly due to their optical properties, in particular their high photoluminescence quantum yields (PLQYs). Three-precursor synthetic methods, in which the sources of the three elements (cesium, lead and bromine) constituting the perovskite scaffold are chemically independent, often succeed in the achievement of near-unity PLQY perovskite NCs. However, this class of synthetic approaches precludes the accessibility to crystal morphologies different from the traditional cuboidal ones. In order to upgrade three-precursor synthetic schemes to obtain more sophisticated morphologies - such as rods - we propose a conceptually original synthetic methodology, in which a potentially controllable stage of the reaction anticipates the fast crystallization promoted by cesium injection. To this purpose, lead oxide, 1-bromohexane (at different molar ratios with respect to lead) and the ligands (oleic acid and a suitable amine) norods prepared with decylamine also exhibit a remarkable resistance to the presence of water, due to the compact and hydrophobic organic shell passivating the NC surface. These findings can contribute to the development of innovative synthetic methodologies for controlling the shape and stability of near-unity PLQY perovskite NCs.The 2-vinylbenzoic acids have wide applications in the field of polymer chemistry and are key precursors for the synthesis of important bioactive molecules. Herein, an ortho-halogen-induced deoxygenative approach for the generation of 2-vinylbenzoic acids from alkyl aryl ketones by palladium catalysis is discovered and explored. This approach requires no base or stoichiometric additives and can be carried out through a simple one-step process. Furthermore, the present reaction is scalable up to one-gram scale. The commercially available palladium on carbon (5 wt%) was used as a heterogeneous catalyst and showed excellent recyclability ( less then 5 times) without significant loss in catalytic activity. Pleasingly, under our optimized conditions, the alpha alkyl substituted 2-iodoacetophenones exhibit good diastereoselectivity and predominantly (E)-2-vinylbenzoic acids were obtained with good to excellent yields.Novel crystalline covalent organic polymers (COPs) were constructed by reacting 1,4-diaminoanthraquinone with 1,3,5-triformylphloroglucinol or tris(4-formylphenyl)amine (TPDA or TADA). After they were covalently bonded to amine-functionalized graphene oxides, the resulting mesoporous COPs@graphene composites demonstrated efficient capacitance storage performance in both alkaline and acidic media. In particular, the as-synthesized TPDA@graphene displayed a reversible specific capacitance of 522 F g-1 in a 6.0 mol L-1 aqueous KOH electrolyte, superior to the previously reported COPs with inconspicuous capacitance storage properties in alkaline media. Its specific capacitance also reached 390 F g-1 in 2.0 mol L-1 H2SO4. The impressive capacitance storage properties of this composite can be ascribed to its unique structure with abundant pendulous anthraquinone redox groups and better electrical conductivity enhanced by the coupled graphenes.Transition metal phosphides (TMPs) have received considerable attention owing to their great potential in energy conversion and storage technologies. Elaborate design and synthesis of various TMPs with abundant structures in order to meet the requirements of various applications is one of the major goals and challenges of sustainable chemistry. In this work, an electrostatic spray deposition (ESD) approach has been developed and has been demonstrated to be a general strategy to fabricate TMPs for the first time. Various bicontinuous TMPs/carbon nanocomposites can be constructed by this approach. This novel architecture, when applied in energy storage systems, can provide an efficient electron/ion mixed-conducting network, thereby inducing fast electron/ion transfer kinetics and enhancing the structural stability upon long term cycling. As proof of concept application, 3D porous Cu3P/rGO nanocomposites as modeling anodes for Na-ion storage show excellent cycling performance and remarkable rate capacities. The sodium storage mechanism is proposed to be a reversible conversion reaction. The microstructural evolution of the electrodes upon cycling correlates well with the capacity variation. The facile and versatile ESD technique is quite universal and can be further extended to various TMPs. #link# This opens exciting opportunities for the incorporation of TMPs in a variety of new applications.Oligoisocyanides are attractive synthetic targets, however, only a few are known. Here, we describe the smallest stable tetraisocyanide possible, the 1,3-diisocyano-2,2-bis(isocyano-methyl)propane (1) with S4 symmetry. Its four-step synthesis, structure, and reactivity in unprecedented symmetric fourfold Ugi 4CR and fourfold Passerini 3CR are described. Exhibiting high functional group tolerance and moderate to high yields, we foresee multiple applications of 1,3-diisocyano-2,2-bis(isocyanomethyl)propane, for example in MOFs, COFs, dendrimers, or artificial organs.Understanding the biological fate of graphene-based materials such as graphene oxide (GO) is crucial to assess adverse effects following intentional or inadvertent exposure. Here we provide first evidence of biodegradation of GO in the gastrointestinal tract using zebrafish as a model. Raman mapping was deployed to assess biodegradation. The degradation was blocked upon knockdown of nos2a encoding the inducible nitric oxide synthase (iNOS) or by pharmacological inhibition of NOS using l-NAME, demonstrating that the process was nitric oxide (NO)-dependent. NO-dependent degradation of GO was further confirmed in vitro by combining a superoxide-generating system, xanthine/xanthine oxidase (X/XO), with an NO donor (PAPA NONOate), or by simultaneously producing superoxide and NO by decomposition of SIN-1. Finally, by using the transgenic strain Tg(mpxeGFP) to visualize the movement of neutrophils, we could show that inhibition of the degradation of GO resulted in increased neutrophil infiltration into the gastrointestinal tract, indicative of inflammation.A multicomponent catalytic reaction between ketones, Morita-Baylis-Hillman (MBH) carbonates and trifluoromethylthiolating agents is devised for straightforwardly accessing two products, α-trifluoromethylthiolated ketones and α-methylene β-amino esters in a one pot fashion. Particularly noteworthy is that the trifluoromethylthiolating reagent is employed as both the nitrogen and SCF3 source initiated by DABCO. This mild one pot strategy enjoys atom- and step-economic attractiveness, for direct introduction of an SCF3 group onto a variety of acyclic ketones, which have been considered as less effective and less developed substrates.The molecular arrangement of racemic [Ni(phen)3]2+ complexes in the interlayer space of montmorillonite was investigated using X-ray diffraction measurements. When the amount of the adsorbed complexes exceeded the cation exchange capacity, they were found to form a double-molecular layer with the 2D hexagonal arrangement in the interlayer space.The paper reports a simple and cost-effective strategy for the development of a stable and reproducible PANI/Fe2O3 composite coating as an efficient electrode for the electrocatalytic alkaline hydrogen evolution reaction (HER). The surface characteristics of the developed PANI/Fe2O3 composite coatings are tuned to achieve high hardness (510 HVN), thickness (26 μm), porosity, and surface roughness (Sa = 3.760 μm). The PANI/Fe2O3 composite coating with tuned surface characteristics (PANI/Fe2O3-2GL) facilitates the effective conduction of electrons from a highly conducting polymer to a metal. This increases the electron density on the coating surface and enhances the active surface area, which effectively enhances the hydrogen adsorption efficiency on the coating surface to improve HER activity. The composite coating exhibits enhanced HER activity with low overpotential (110 mV) and high exchange current density (95.32 mA cm-2). The mechanism of HER on the coating surface follows the Volmer-Heyrovsky reaction with the Heyrovsky step as the rate-determining step. The stability of the composite coating under aggressive reaction conditions even after long-term HER confirms its competency with commercial electrocatalysts.The high temperature gas phase chemistry of the four butyl radical isomers (n-butyl, sec-butyl, iso-butyl, and tert-butyl) was investigated in a combined experimental and theoretical study. Organic nitrites were used as convenient and clean sources of each of the butyl radical isomers. Rate coefficients for dissociation of each nitrite were obtained experimentally and are at, or close to, the high pressure limit. link2 Low pressure experiments were performed in a diaphragmless shock tube with laser schlieren densitometry at post-shock pressures of 65, 130, and 260 Torr and post-shock temperatures of 700-1000 K. Additional experiments were conducted with iso-butyl radicals at 805 K and 8.7 bar to elucidate changes in mechanism at higher pressures. These experiments were performed in a miniature shock tube with synchrotron-based photoionization mass spectrometry. read more confirmed that scission of the O-NO bond is the primary channel by which the precursors dissociate, but they also provided evidence of a mi. Branching fractions and rate coefficients are presented for these reactions. link3 This study also highlights the importance of the radical structure for determining branching ratios for disproportionation and recombination of alkyl radicals, and these were facilitated by theoretical calculations of recombination rate coefficients for the four butyl radical isomers. The results reveal previously unknown features of butyl radical chemistry under conditions that are relevant to a wide range of applications and reaction mechanisms are presented that incorporate pressure dependent rate coefficients for the key steps.Reaction of the 9,9-dimethylxanthene-bis(imine)-bis(catechol) ligand XbicH4 with half an equivalent of Zr(acac)4 affords the neutral tetracatecholate complex (XbicH2)2Zr, containing four iminium ions hydrogen bonded to the catecholates. The heteroleptic bis(catecholate)-tetraphenylporphyrin complex (TPP)Zr(XbicH2) is formed from reaction of (TPP)Zr(OAc)2 with XbicH4 in the presence of base. Both compounds adopt an eight-coordinate square antiprismatic geometry around the zirconium center. NMR spectra of (TPP)Zr(XbicH2) show that it is fluxional at room temperature, with homoleptic (XbicH2)2Zr showing fluxionality at higher temperatures. Calculations and kinetic isotope effect measurements suggest that the motions involve dissociation of a single catecholate oxygen and subsequent twisting of the seven-coordinate species. The compounds show reversible one-electron oxidations of each of the bound catecholates to bound semiquinones.