Sandersbowden8476

X-ray photoelectron spectroscopy (XPS) has been used to study the effect of mixed H2O/H2 gas plasma on the surfaces of UO2, U2O5 and UO3 thin films at 400 °C. The experiments were performed in situ under ultra-high vacuum conditions. Deconvolution of the U4f7/2 peaks into U(iv), U(v) and U(vi) components revealed the surface composition of the films after 10 min plasma exposure as a function of H2 concentration in the feed gas of the plasma. Some selected films (unexposed and exposed) were also analysed using grazing-incidence X-ray diffraction (GIXRD). The XPS results show that U(v) is formed as a major product upon 10 minutes exposure of UO3 by a mixed H2O/H2 plasma in a fairly wide H2 concentration range. When starting with U(v) (U2O5), rather high H2 concentrations are needed to reduce U(v) to U(iv) in 10 minutes. In the plasma induced oxidation of UO2, U(v) is never observed as a major product after 10 minutes and it would seem that once U(v) is formed in the oxidation of UO2 it is rapidly oxidized further to U(vi). The grazing incidence X-ray diffraction analysis shows that there is a considerable impact of the plasma and heating conditions on the crystal structure of the films in line with the change of the oxidation state. This structural difference is proposed to be the main kinetic barrier for plasma induced transfer between U(iv) and U(v) in both directions.Studies into the Cp*Rh(iii)-catalysed hydroarylation of alkenes with aryl acyl silanes led to the discovery of a new synthetic strategy to access unique silicon derived indene frameworks. Rather than protodemetalation of the metal enolate formed following insertion of an alkene into the aryl C-H bond, intramolecular aldol condensation of the acyl silane occurred to generate a series of 2-formyl- and 2-acetyl-3-silyl indenes. This represents only the second example of rhodium-catalysed C-H functionalisation employing acyl silanes as weakly coordinating directing groups and the intramolecular aldol condensation strategy was extended to access analogous silicon derived benzofurans.A cocktail [1 + 2] dual-fluorescent probe system was developed to realize the real-time visualization of dynamic iron state changes between Fe2+ and Fe3+ at the cellular level and in multicellular organisms, providing insights into the effect of DMT1 and ferroportin on iron regulation.A novel evaluation approach for evaluating the electrical properties of electrode materials for batteries (and the other similar electrochemical systems) is proposed, assuming the reacted-unreacted structure interface acts as a semiconductor junction. Density of state (DOS) diagrams, calculated by different methods of density functional theory (DFT), for practically important case studies are used to explain the approach. The approach allocates a value for each assessed electrode material, providing a semi-quantitative criterion of the rate-capability to allow comparisons between materials. Important cathode materials utilized in Li-ion batteries were considered as the case studies, namely LiCoO2, LiFePO4, LiFeSO4F, and Li2FeSiO4. Our approach considers simultaneously the configuration of the intercalated-deintercalated structures with respect to each other and also the electric-field direction. The reacted and unreacted structures were electrically joined; therefore, to complete the electrical conduction process, electric-charge carriers move across these two structures. In the intercalation batteries, electrons always transfer from the deintercalated to the intercalated structure, and so electrons-holes also move from the intercalated to the deintercalated structure. The approach is inclusive while it simultaneously considers the band gaps, DOS bands' configurations, semiconductor junction features, and configuration of the structures regarding the electric-field direction in the cell. It helps to understand the underlying mechanisms as well as aid the justification, prediction, and design of relevant electrochemical systems.Herein, we report, for the first time, a Pd6L8(NO3)5.4(ICG)6.6 (ICG = indocyanine green) cage-based hexagonal nanoplate (3) via a combined nanoprecipitation and solid-state anion-exchange approach. Nanoplate 3 possesses enhanced near-infrared (NIR) light-triggered 1O2 generation, high cellular uptake selective lysosome-targeting ability, and, consequently, excellent antineoplastic activity.Porous ionic liquids combining alkylphosphonium halides with ZIF-8 absorb large amounts of carbon dioxide that can be catalytically coupled with epoxides to form cyclic carbonates. EGFR cancer High activity and selectivity under mild reaction conditions points towards a new promising, high-performing, sustainable family of sorbents for simultaneous carbon capture and transformation.A strategy for one-pot synthesis of isoindoles is described via a catalytic multicomponent dehydrogenative annulation of diarylimines, vinyl ketones and simple amines. In the presence of a rhodium catalyst and Cu oxidant, four C-H and two N-H bonds are activated along with the formation of one new C-C and two new C-N bonds, leading to a series of isoindole derivatives in good to very high isolated yields.Here, a pseudo-solution-phase ligand exchange (p-SPLE) strategy is developed for fabricating a CsPbI3 quantum dot (QD) solar cell. Using short organic aromatic ligands to partly replace the long-chain ligands in a QD solution, the p-SPLE treated CsPbI3 QD solar cell had an enhanced power conversion efficiency of up to 14.65% together with improved stability.A new copper/silver-co-mediated three-component bicyclization of benzene-linked 1,6-enynes with ICF2CO2Et with TMSN3 was reported, and used to produce a wide range of hitherto unreported difluorinated tetrahydroindeno[1,2-c]azepine-3,6-diones with moderate to good yields. The mechanistic pathway consists of radical-induced 1,6-addition-cyclization, oxidative addition, reductive elimination, nitrene insertion and N-O cleavage, resulting in continuous multiple bond-forming events including C-C and C-N bonds to build up a 6/5/7 tricyclic framework.A mono-mercapto-functionalized pillar[5]arene and its dimer, capable of being reversibly interconverted, were successfully synthesized. Fascinatingly, a faster reversible redox conversion involving a dynamic disulfide bond was observed between their host-guest complexes compared with the hosts themselves.A Ni-catalyzed direct C-H alkylation of N-quinolylbenzamides using alkylsilyl peroxides as alkyl-radical precursors is described. The reaction forms a new C(sp3)-C(sp2) bond via the selective cleavage of both C(sp3)-C(sp3) and C(sp2)-H bonds. This transformation shows a high functional-group tolerance and, due to the structural diversity of alkylsilyl peroxides, a wide range of alkyl chains including functional groups and complex structures can be introduced at the ortho-position of readily available N-quinolylbenzamide derivatives. Mechanistic studies suggest that the reaction involves a radical mechanism.By first applying a thorium-organic framework (Th-SINAP-2) as a radiation attenuator and by incorporating a terpyridine derivative (Htpbz) as a photo-responsive guest, selective photochromism in response to X-rays was achieved in the host-guest assembly of Htpbz@Th-SINAP-2. Such a combination endows the afforded material with the lowest detection limit of X-ray dose among all photochromic sensors and a brand-new function of X-ray dosimetry for thorium containing materials.We report a rare-earth triflate catalyst Sc(OTf)3 for the ring-opening polymerization of 1,3-dioxolane and the in situ production of a quasi-solid-state poly(1,3-dioxolane) electrolyte, which not only demonstrates a superior ionic conductivity of 1.07 mS cm-1 at room temperature, but achieves dendrite-free lithium deposition and a high Coulombic efficiency of 92.3% over 200 Li plating/striping cycles.A highly electron-deficient dicyanomethylene-bridged triarylborane, FMesB-TCN, was reported with a low-lying LUMO and crystallization-induced emission enhancement in its block-shape crystal. DFT calculations revealed lower re-organization energy of the block crystal than that of the weakly emissive acicular crystal. This work explored a novel boron-containing skeleton with interesting optical properties.Aromatic stacking exists widely and plays important roles in protein-ligand interactions. Computational tools to automatically analyze the geometry and accurately calculate the energy of stacking interactions are desired for structure-based drug design. Herein, we employed a Behler-Parrinello neural network (BPNN) to build predictive models for aromatic stacking interactions and further integrated it into an open-source Python package named AromTool for benzene-containing aromatic stacking analysis. Based on extensive testing, AromTool presents desirable precision in comparison to DFT calculations and excellent efficiency for high-throughput aromatic stacking analysis of protein-ligand complexes.Herein, we exploited the double-stranded DNA (dsDNA) binding property of transcription factor (TF), combined with the trans cleavage characteristic of CRISPR-Cas12a, for the detection of NF-κB p50.We report rare examples of exclusive benzylic C-H oxidative addition in industrially important methylarenes using simple η4-arene iridium complexes. Mechanistic studies showed that coordinatively unsaturated η2-arene intermediates are responsible for the selective activation of benzylic, not aromatic C-H bonds and formation of stable benzyl complexes after trapping with a phosphine ligand.In this research, the pH differential method was explored for the first time using a mobile phone as a detector, replacing UV-Vis spectrophotometry. A smartphone digital image colorimetric (SDIC) system was developed for the determination of the total monomeric anthocyanin content in black rice grains using colour values. The change in colour of anthocyanin cyanidin-3-glucoside (C3G) at pH 1.0 and pH 4.5 was investigated and described through colour model systems (RGB and CIELAB). Under optimum conditions, the quantitative method based on the chroma difference, was able to quantify the total amount of monomeric anthocyanins with a linear correlation (R2 = 0.989) to that of UV-Vis spectrophotometry and high performance liquid chromatography (HPLC) (reference method). The SDIC system displayed good precision (≤1.88% RSD) and a low detection limit (2.2 ± 0.1 μg g-1). The validated results demonstrated that the developed method was a cost-effective alternative for the quantitation of anthocyanins. In addition, the effect of six mineral elements on black rice cultivation was investigated. The results showed that the addition of the Ca fertiliser resulted in black rice grains with an anthocyanin content 2-fold higher than that of the control with a significant difference (p less then 0.05).Mixing low molecular weight gelators (LMWGs) shows promise as a means of preparing innovative materials with exciting properties. Here, we investigate the effect of increasing hydrophobic chain length on the properties of the resulting multicomponent systems which are capable of showing ambidextrous phase behaviour on pH perturbation.Thermal treatment of Cp*2YMe(thf) (Cp* = C5Me5), obtained from Cp*2Y(AlMe4) via donor-induced AlMe3 cleavage, in THF resulted in the concomitant formation of vinyl oxide Cp*2Y(OC2H3)(thf) and 2-ethylene-tetrahydrofuranyl complex Cp*2Y(2-C2H4-OC4H7) via the release of methane. In stark contrast, dissolving Cp*2La(AlMe4) in THF/n-hexane led to the quantitative formation of AlMe3-stabilized 2-tetrahydrofuranyl complex Cp*2La(2-AlMe3-OC4H7), with methane elimination.