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The combination of Al nanoparticles (ANPs) and hydrogen peroxide (H2O2) can serve as environmentally friendly bipropellants and maximize the energetic benefits through harnessing heat release and chemical energy stored in H2. This work presents an atomic insight into the combustion mechanism of ANPs/H2O2. Two main paths, including the ANPs oxidation by H2O2 to produce H2 and Al oxides, and the catalytic decomposition of H2O2 on ANP surface to generate O2 and H2O, are confirmed to maintain the combustion. OH and HOO radicals as well as H2O, O2, H2, and Al oxides are detected as dominant intermediates and products therein. It is evidenced that higher temperature, smaller ANP size, and higher H2O2 concentration enhance the combustion. Moreover, atomic details show that the H desorption from ANPs/Al clusters is a critical step for both H2 production and ANP oxidation. In addition, microexplosion that has been confirmed in hot and dense O2 is not observed in H2O2, even with a high concentration, possibly due to a slower heat release. https://www.selleckchem.com/products/r-hts-3.html Besides, the observed excellent specific impulse of the ANP/H2O2 bipropellants could be attributed to the considerable H2 production, instead of heat release. This work is expected to present an overall atomic perspective about the combustion mechanism of ANP/H2O2 bipropellants.We found that 1-phosphanyl-1,2,3,4-tetrahydroquinazolines undergo ring enlargement. Their treatment with trifluoroacetic or hydrochloric acid afforded diazaphosphepinium salts. Deprotonation of these salts gave the corresponding neutral diazaphosphepines. The reaction of 1-phosphanyl-1,2,3,4-tetrahydroquinazolines with diazomethane or phenylazide afforded triazaphosphocine derivatives via insertion of P-N moiety. At the same time, an analogous hexahydropyrimidine derivative reacted with phenylazide in a normal manner at the phosphorus atom to afford the P(V) derivative.Despite rapid progress in recent years, it has remained challenging to prepare well-defined metal-organic complex-based suprastructures. As a result, the physicochemical mechanisms leading to their geometrical complexity remain perplexing. Here, a porphyrin-based metallacage was used as a building block to construct octahedra via self-assembly, and the mechanism for the evolution of the metallacages into octahedra was disclosed by both experiments and theoretical simulations.Disulfide bond formation is a critical post-translational modification of newly synthesized polypeptides in the oxidizing environment of the endoplasmic reticulum and is mediated by protein disulfide isomerase (PDIA1). In this study, we report a series of α-aminobenzylphenol analogues as potent PDI inhibitors. The lead compound, AS15, is a covalent nanomolar inhibitor of PDI, and the combination of AS15 analogues with glutathione synthesis inhibitor buthionine sulfoximine (BSO) leads to synergistic cell growth inhibition. Using nascent RNA sequencing, we show that an AS15 analogue triggers the unfolded protein response in glioblastoma cells. A BODIPY-labeled analogue binds proteins including PDIA1, suggesting that the compounds are cell-permeable and reach the intended target. Taken together, these findings demonstrate an extensive biochemical characterization of a novel series of highly potent reactive small molecules that covalently bind to PDI.Owing to their potential applications in the extraction, purification, and preservation of biomolecules and biocatalysis, ionic liquids (ILs) have gained great attention in biotechnology. Although it is known that the structure and dynamics of proteins in ILs depend on the nature of both proteins and ILs, the biophysical mechanism governing the protein-IL interaction, which determines the stability of proteins or the activity of an enzyme in these nonconventional media, is yet to be understood clearly. Herein, we study the effect of two ammonium ILs, triethylammonium dihydrogen phosphate (TEAP) and tributylammonium dihydrogen phosphate (TBAP), on the stability and conformational dynamics of cytochrome c (Cyt c) in its native and unfolded states, employing primarily the single molecule-based fluorescence correlation spectroscopy (FCS) technique. The results show that the native structure of Cyt c is not significantly altered by TEAP, but the tertiary structure is perturbed to a great extent by TBAP, which comprises a longer alkyl chain. Fluctuations of the fluorescence intensity of Alexa488 dye-labeled Cyt c in FCS measurements reveal conformational dynamics (67 ± 10 μs) in the native state of Cyt c that is accelerated in the presence of both ILs but not affected when Cyt c is in its unfolded state. The present findings demonstrate how the stability of this protein can be modulated by using ammonium ILs of different alkyl chain lengths.An efficient catalytic method to convert an α-C-H bond of N-alkylamines into an α-C-alkynyl bond was developed. In the past, such transformations were carried out under oxidative conditions, and the enantioselective variants were confined to tetrahydroisoquinoline derivatives. Here, we disclose a method for the union of N-alkylamines and trimethylsilyl alkynes, without the presence of an external oxidant and promoted through cooperative actions of two Lewis acids, B(C6F5)3 and a Cu-based complex. A variety of propargylamines can be synthesized in high diastereo- and enantioselectivity. The utility of the approach is demonstrated by the late-stage site-selective modification of bioactive amines. Kinetic investigations that shed light on various mechanistic nuances of the catalytic process are presented.The substitution of 2,7-dibromo-9-fluorenyl phosphaalkenes with heteroaromatic substituents (bithiophene, benzothiophene, pyridine) offers access to interesting push-pull dye molecules. Steric shielding due to the bulky P-substituent gives marked different reactivities at the 2- and 7-positions, allowing the synthesis of mixed/asymmetric derivatives. Further functionalization via gold(I) coordination was demonstrated and increased the acceptor character, concomitant with a red-shifted absorption.R2O3-B2O3 binary glasses (R denotes rare-earth elements or Y) were fabricated in a very wide composition region using a levitation technique. The maximum R2O3 content of light rare-earth compounds reached 63 mol % and decreased with a decrease in the ionic radius of R3+. The thermal, optical, vibrational, and structural properties were investigated, particularly for 50R2O3-50B2O3 glasses. The glass transition temperature increased with a decrease in the ionic radius of R3+, while the thermal stability was not affected by the glass composition. The packing density increased with a decrease in the ionic radius of R3+ due to lanthanoid contraction. Raman scattering and Fourier transform infrared spectra revealed that, in the rare-earth-rich glasses, no conventional three-dimensional networks consisting of corner-sharing BO n (n = 3 or 4) units existed because all B atoms were formed as isolated BO3 units. The simple environment around B atoms in the glasses led to additional IR transmittance regions, irrespective of the kinds of R.
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