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Hancock Greer posted an update 11 days ago
The probe shows aggregation-induced emissive (AIE) response in ≥70% aqueous media as well as in the solid state. The experimental results are well corroborated by time-resolved photoluminescence (TRPL) and density functional theory (DFT) calculations. An advanced-level OR-AND-NOT logic gate has been constructed from a different chemical combinational input and emission output. The reversible recognition of both Al3+ in MeOH-water (91, v/v) and Zn2+ in DMSO-water (91, v/v) is also ascertained in the presence of Na2EDTA, enabling the construction of a molecular memory device. The probe H 2 L also detects intracellular Al3+/Zn2+ ions in Hela cells. Altogether, our fundamental findings will pave the way for designing and synthesis of unique chemosensors that could be used for cell imaging studies as well as constructing molecular logic gates.Parabens for which the molecules contain hydrolytic and ionizable groups, are emerging pollutants due to their ubiquity in the environment. However, lack of pKa and second-order base-catalyzed hydrolysis kinetics (kB) values limits their environmental persistence assessment. Herein, six parabens were selected as reference compounds for which the pKa and kB values were measured experimentally. A semiempirical quantum chemical (QC) method was selected to calculate pKa of the parabens, and density functional theory (DFT) methods were selected to calculate kB for neutral and anionic forms of the parabens, by comparing the QC-calculated and determined values. Combining the QC-calculated and experimental pKa and kB values, quantitative structure-activity relationships with determination coefficients (R2) being 0.947 and 0.842 for the pKa and kB models, respectively, were developed, which were validated and could be employed to efficiently fill the kB and pKa data gaps of parabens within applicability domains. The base-catalyzed hydrolysis half-lives were estimated to range from 6 h to 1.52 × 106 years (pH 7-9, 25 °C), further necessitating the in silico models due to the tedious and onerous experimental determination, and the huge number of hydrolyzable and ionizable chemicals that may be released into the environment.The coordination of an element-element σ bond to a transition metal (TM) is both a fundamentally intriguing binding mode and of critical importance to metal-mediated bond activation mechanisms and catalysis, particularly the hotly contested field of C-H activation. TM σ complexes of dihydrogen (i.e., H-H) and silanes (H-SiR3) have been extensively studied, the latter being of interest as models for the (generally unstable and unisolable) σ complexes of alkanes (i.e., H-CR3). TM σ complexes of hydroboranes and hydroborates (i.e., H-BR2, H-BR3, (H-)2BR2) are somewhat less well studied but similarly have relevance to catalytic borylation reactions that are of high current interest to organic synthesis. Our two research groups have made significant contributions to elaborating the family of σ-borane/-borate complexes using two distinct approaches while the Ghosh group generally starts from hydrogen-rich tetracoordinate boron species such as borates, the Braunschweig group starts from hypovalent and/or hypocoordinscinating rearrangements with unpredictable outcomes. This Account aims to highlight this recent acceleration of research progress in this area, particularly the distinct but related approaches of-and complexes produced by-our two research groups, in addition to relevant works from other groups where appropriate.A novel equilibrium strategy for measuring the hydrogen atom affinity of colloidal metal oxide nanoparticles is presented. Reactions between oleate-capped cerium oxide nanoparticle colloids (nanoceria) and organic proton-coupled electron transfer (PCET) reagents are used as a model system. Nanoceria redox changes, or hydrogen loadings, and overall reaction stoichiometries were followed by both 1H NMR and X-ray absorption near-edge spectroscopies. These investigations revealed that, in many cases, reactions between nanoceria and PCET reagents reach equilibrium states with good mass balance. Each equilibrium state is a direct measure of the bond strength, or bond dissociation free energy (BDFE), between nanoceria and hydrogen. Further studies, including those with larger nanoceria, indicated that the relevant bond is a surface O-H. Thus, we have measured surface O-H BDFEs for nanoceria-the first experimental BDFEs for any nanoscale metal oxide. Remarkably, the measured CeO-H BDFEs span 13 kcal mol-1 (0.56 eV) with changes in the average redox state of the nanoceria colloid. Possible chemical models for this strong dependence are discussed. We propose that the tunability of ceria BDFEs may be important in explaining its effectiveness in catalysis. More generally, metal oxide BDFEs have been used as predictors of catalyst efficacy that, traditionally, have only been accessible by computational methods. These results provide important experimental benchmarks for metal oxide BDFEs and demonstrate that the concepts of molecular bond strength thermochemistry can be applied to nanoscale materials.Simple n-alcohols, such as 1-dodecanol, show anomalous film-forming and friction behaviors under elastohydrodynamic lubrication (EHL) conditions, as found inside bearings and gears. Using tribometer, diamond anvil cell (DAC), and differential scanning calorimetry (DSC) experiments, we show that liquid 1-dodecanol undergoes a pressure-induced solidification when entrained into EHL contacts. Different solid polymorphs are formed inside the contact depending on the temperature and pressure conditions. Surprisingly, at a moderate temperature and pressure, 1-dodecanol forms a polymorph that exhibits robust macroscale superlubricity. ML349 The DAC and DSC experiments show that superlubricity is facilitated by the formation of lamellar, hydrogen-bonded structures of hexagonally close-packed molecules, which promote interlayer sliding. This novel superlubricity mechanism is similar to that proposed for the two-dimensional materials commonly employed as solid lubricants, but it also enables the practical advantages of liquid lubricants to be maintained.
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Start with a huge, uncovered box, or even a kiddie pool, and fill with a thick layer (about 6 inches) of unscented clay or fine sand-like particulate clumping/scoopable litter. For Ollie, you may need to play around with the substrate types to make it more natural. Try using soil or peat.