Notes

Deep precious stone single-photon solutions cooked by the femtosecond lazer.
Although most of the currently developed supramolecular catalysts that emulate enzymatic reactivity with unique selectivity and activity through specific host-guest interactions work under homogeneous conditions, enzymes in nature can operate under heterogeneous conditions as membrane-bound enzymes. In order to develop such a heterogeneous system, an immobilized chiral supramolecular cluster Ga416 (2) was introduced into cross-linked polymers with cationic functionalities. These heterogeneous supramolecular catalysts were used in aza-Prins and aza-Cope reactions and successfully applied to continuous-flow reactions. They showed high durability and maintained high turnovers for long periods of time. In sharp contrast to the majority of examples of heterogenized homogeneous catalysts, the newly developed catalysts showed enhanced activity and robustness compared to those exhibited by the corresponding soluble cluster catalyst. An enantioenriched cluster was also immobilized to enable asymmetric catalysis, and activity and enantioselectivity of the supported chiral catalyst were maintained during recovery and reuse experiments and under a continuous-flow process. Significantly, the structure of the ammonium cations in the polymers affected stability, reactivity, and enantioselectivity, which is consistent with the hypothesis that the cationic moieties in the polymer support interact with cluster as an exohedral protecting shell, thereby influencing their catalytic performance.Phospholipids, as essential components in joint synovial fluid, play a dominant role in joint lubrication. In this study, atomic force microscopy was used to evaluate the normal and shear forces between two surfaces bearing three types of phospholipids with different acyl chain lengths, which were pre-adsorbed onto silica surfaces at different temperatures (25, 45, and 60 °C). When the pre-adsorption temperature was below the phospholipid phase transition temperature (Tm), a super-low friction coefficient [1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC) 0.002; 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) 0.007] between two opposing silica surfaces in water was achieved because of the super-low shear strength of the hydration shell and robustness of the vesicle when the load was less than the critical value (DSPC 500 nN; DPPC 85 nN). However, when the pre-adsorption temperature exceeded Tm, the silica surface was covered by a bilayer structure with many defects, which exhibited poor adsorption density and low bearing capacity, resulting in a relatively high friction coefficient. This study gains insights into the influence of structure and temperature on the lubrication mechanism of phospholipids as biolubricants, providing guidance for the application of artificial joint synovial fluid.Recently, the bulk electrooxidation of CO on gold or platinum has been used to detect CO produced during CO2 reduction in neutral media. The CO bulk oxidation voltammetry may show two distinct peaks depending on the reaction conditions, which up to now have not been understood. We have used scanning electrochemical microscopy (SECM) to probe CO oxidation and pH in the diffusion layer during CO2 reduction. Our results show that the two different peaks are due to diffusion limitation by two different species, namely, CO and OH-. We find that between pH 7 and 11, CO oxidation by water and OH- gives rise to the first and second peak observed in the voltammetry, respectively. Additional rotating disc experiments showed that specifically in this pH range the current of the second peak is diffusion limited by the OH- concentration, since it is lower than the CO concentration.In situ 1H pulsed field gradient (PFG) NMR was used to investigate the molecular diffusion of n-butane in the pores of the flexible metal-organic framework DUT-49(Cu) at 298 K at different pore loadings, including pressure ranges below and above the negative gas adsorption (NGA) transition caused by structural contraction of the material. Supported by molecular dynamics simulations, the investigation provided crucial insight into confined diffusion within a highly flexible pore environment. The self-diffusion coefficients were derived from the experiment and compared with simulations, capturing the diffusion during n-butane adsorption and desorption. This complementary approach has yielded experimental characterization of molecular diffusion mechanisms during the unique process of NGA. This includes the observation of a 4-fold decrease of diffusivity within a less than 2 kPa gas pressure variation, corresponding to the NGA transition point.The all-inorganic CsPb(I x Br1-x)3 (0 ≤ x ≤ 1) perovskite solar cells (PSCs) are attractive by virtue of their high environmental and thermal stability. Nevertheless, multiple-step deposition and high annealing temperature (>250 °C) and the structural and optoelectronic properties changes upon temperature-dependent phase-transition are potential impediments for highly efficient and stable PSCs. Herein, a space-confined method to fabricate stable lower-order symmetric pure monoclinic CsPbBr3 phase at low temperature ( less then 50 °C) is for the first time reported. It is found that the carbon-based mesoporous fully printable area can inhibit the phase transition to get a pure phase. Therefore, the device exhibits a power conversion efficiency of 7.52% with a low hysteresis index of 0.024. Moreover, the device passed the 1000 h 85 °C thermal test and the 200 cycles thermal cycling test according to IEC-61625 stability tests. These are critical progresses for achieving long-term stability and the stable pure inorganic perovskite phase of high-performance photovoltaics.Myosin regulates muscle function through a complex cycle of conformational rearrangements coupled with the hydrolysis of adenosine triphosphate (ATP). The recovery stroke reorganizes the myosin active site to hydrolyze ATP and cross bridge with the thin filament to produce muscle contraction. Engineered mutations K84M and R704E in Dictyostelium myosin have been designed to specifically inhibit the recovery stroke and have been shown to indirectly affect the ATPase activity of myosin. We investigated these mutagenic perturbations to the recovery stroke and generated thermodynamically correct and unbiased trajectories for native ATP hydrolysis with computationally enhanced sampling methods. Our methodology was able to resolve experimentally observed changes to kinetic and equilibrium dynamics for the recovery stroke with the correct prediction in the severity of these changes. For ATP hydrolysis, the sequential nature along with the stabilization of a metaphosphate intermediate was observed in agreement with previous studies. However, we observed glutamate 459 being utilized as a proton abstractor to prime the attacking water instead of a lytic water, a phenomenon not well categorized in myosin but has in other ATPases. Both rare event methodologies can be extended to human myosin to investigate isoformic differences from Dictyostelium and scan cardiomyopathic mutations to see differential perturbations to kinetics of other conformational changes in myosin such as the power stroke.The α-alkylation of nitriles with primary alcohols to selectively synthesize nitriles by a well-defined molecular homogeneous cobalt catalyst is presented. Thirty-two examples with up to 95% yield are reported. Remarkably, this transformation is environmentally friendly and atom economical with water as the only byproduct.As part of a study on triterpenoid conjugates, the dietary pentacyclic triterpenoids oleanolic (2a) and ursolic acids (3a) were coupled with vanillamine, and the resulting amides (2b and 3b, respectively) were assayed for activity on the vanilloid receptor TRPV1. Despite a structural difference limited to the location of a methyl group in their conformationally rigid pentacyclic core, oleanoloyl vanillamide dramatically outperformed ursoloyl vanillamide in terms of potency (EC50 = 35 ± 2 nM for 2b and 5.4 ± 2.3 μM for 3b). Using molecular docking and dynamics, this difference was translated into distinct accommodation modes at the TRPV1 vanillyl ligand pocket, suggesting a critical role of a C-H πphenyl interaction between the triterpenoid C-29 methyl and Phe591 of TRPV1. Because the molecular mechanisms underlying the activation process of transient receptor channels (TRPs) remain to be fully elucidated, the observation of spatially restricted structure-activity information is of significant relevance to identify the molecular detail of TRPV1 ligand gating.NMR studies have indicated that the anti-tumor therapeutic agent actinomycin D (ACTD) can induce seemingly single-stranded DNA (ssDNA) oligomer 5'-CCGTT3GTGG-3' to form a hairpin structure with tandem GT mismatches at the stem region next to a loop of three stacked thymine bases. In an effort to uncover the preference of binding sequence and to elucidate the thermodynamics properties of the binding, a combination of spectroscopic techniques and computational simulation studies was performed with d(CCGTT n GTGG) and d(CCGAA n GAGG) (denoted as GTT n and GAA n , respectively; n = 3, 5, and 7) sequences. In the presence of 7-amino actinomycin D (7AACTD), all the six oligomers formed stable hairpin structures. The GTT5-7AACTD/GAA5-7AACTD hairpin structure was more stable than the corresponding GTT n -7AACTD and GAA n -7AACTD (n = 3, 7). No significant ΔG difference was observed between GTT n -7AACTD and GAA n -7AACTD complexes with the same loop length. Angiotensin II human concentration In agreement with the 7AACTD-induced hairpin stability results, the binding affinity of GTT n and GAA n with 7AACTD increased from n = 3 to n = 5 and then decreased when n is 7. Moreover, GTT n and GAA n with the same loop length showed comparable binding affinities to 7AACTD. Furthermore, molecular dynamics simulations found that van der Waals interactions between GTT n /GAA n and 7AACTD were the primary attractive forces for 7AACTD binding, and the electrostatic interactions between the carbonyl groups of 7AACTD and bases in the hairpin were the major unfavorable forces. These findings furthered our understanding that 7AACTD is sensitive to the loop size and sequence as well as tandem GT/GA mismatches of their deoxyribonucleic acid (DNA) targets. A deep understanding of the thermodynamics and the molecular recognition mechanism of 7AACTD with ssDNAs would further the development of ACTD-like antitumor agents.The first highly enantioselective construction of chiral cyclopropa[c]coumarins was described. Using commercially available (bis)cinchona alkaloid (DHQ)2PYR as the chiral Lewis base catalyst, together with Cs2CO3 as the achiral base, the reaction of a series of coumarin-3-carboxylate and 3-benzoyl coumarins with tert-butyl 2-bromoacetate could give rise to the corresponding cyclopropa[c]coumarins bearing three continuous chiral stereocenters in 83-93% ee and 90-97% ee, respectively. The reaction is proposed to proceed via an in situ generated ammonium ylide intermediate.A theoretical overview of the core-to-core (3d-4f) resonant inelastic X-ray scattering (RIXS) spectra of actinide dioxides AnO2 (An = Th, U, Np, Pu, Am, Cu, Bk, Cf) is provided. The 3d-4f RIXS maps were calculated using crystal-field multiplet theory and turned out to be significantly different at the An M5 vs M4 edges, because of selection rules and final state effects. The results of the calculations allowed for a general analysis of so-called high-energy-resolution fluorescence-detected X-ray absorption (HERFD-XAS) spectra. The cuts of the calculated RIXS maps along the incident energy axis at the constant emitted energy, corresponding to the maximum of the RIXS intensity, represented the HERFD spectra and provided their comparison with calculated conventional X-ray absorption (XAS) spectra with a reduced core-hole lifetime broadening at the An M5 and M4 edges. Although the An M5 HERFD profiles were found to depart from the X-ray absorption cross-section, in terms of appearing additional transitions, the results of calculations for the An M4 edges demonstrate overall better agreement between the HERFD and XAS spectra for most dioxides, keeping in mind a restricted HERFD resolution, because of the core-hole lifetime broadening in the final state.
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