Arildsencarey0713

The symmetric C-D stretching mode is a spectator mode in the H + CHD3 → H2 + CD3 reaction. Effects of multiple vibrational excitations of the CHD3 reactant are studied with the quantum transition-state (QTS) framework and an eight-dimensional (8D) model Hamiltonian developed by Palma and Clary. By including many thermal flux eigenstates, results have been obtained up to high energies, allowing the study of the symmetric C-D stretching spectator mode. A new concept of a state-specific thermal flux operator is proposed to analyze the C-D stretching spectator mode in detail, providing a new and insightful venue for studying transition-state control of chemical reactions. Furthermore, as a spectator mode, whether the C-D stretching motion can be excluded in a seven-dimensional (7D) model has not been fully interrogated, although the 7D model is a reasonable approximation and has provided accurate theoretical predictions. By comparing with available results of full-dimensional calculations, both the 7D and 8D models predict reasonably accurate results. However, the 7D model underestimates the mixing of two vibrational states that are in Fermi resonance. Despite its spectator nature, the C-D stretch is important in the dynamical modeling of chemical reaction systems affected by state mixing.Neurodegenerative disorder is an illness involving neural dysfunction/death attributed to complex pathological processes, which eventually lead to the mortality of the host. It is generally recognized through features such as mitochondrial dysfunction, protein aggregation, oxidative stress, metal ions dyshomeostasis, membrane potential change, neuroinflammation and neurotransmitter impairment. The aforementioned neuronal dysregulations result in the formation of a complex neurodegenerative microenvironment (NME), and may interact with each other, hindering the performance of therapeutics for neurodegenerative disease (ND). Recently, smart nanoassemblies prepared from functional nanoparticles, which possess the ability to interfere with different NME factors, have shown great promise to enhance the diagnostic and therapeutic efficacy of NDs. Herein, this review highlights the recent advances of stimuli-responsive nanoassemblies that can effectively combat the NME for the management of ND. The first section outlined the NME properties and their interrelations that are exploitable for nanoscale targeting. The discussion is then extended to the controlled assembly of functional nanoparticles for the construction of stimuli-responsive nanoassemblies. Further, the applications of stimuli-responsive nanoassemblies for the enhanced diagnosis and therapy of ND are introduced. Finally, perspectives on the future development of NME-tailored nanomedicines are given.Treatments of N-(pyridin-2-ylmethyl)pyrazine-2-carboxamide (L1), N-(quinolin-8-yl)pyrazine-2-carboxamide (L2), N-(quinolin-8-yl)picolinamide (L3) and N-(quinolin-8-yl)quinoline-2-carboxamide (L4) with [PdCl2(NCMe)]2 afforded the corresponding Pd(ii) complexes, [Pd(L1)Cl] (PdL1); [Pd(L2)Cl] (PdL2); [Pd(L3)Cl] (PdL3); and [Pd(L4)Cl] (PdL4) in moderate yields. Structural characterisation of the compounds was achieved by NMR and FT-IR spectroscopies, elemental analyses and single crystal X-ray crystallography. The solid-state structures of complexes PdL2-PdL4 established the presence of one tridentate carboxamide and Cl ligands around the Pd(ii) coordination sphere, to give distorted square planar complexes. Electrochemical investigations of PdL1-PdL4 showed irreversible one-electron oxidation reactions. Kinetics reactivity of the complexes towards bio-molecules, thiourea (Tu), l-methionine (L-Met) and guanosine 5'-diphosphate disodium salt (5'-GMP) decreased in the order PdL1 > PdL2 > PdL3 > PdL4, in tandem with the density functional theory (DFT) data. The complexes bind favourably to calf thymus (CT-DNA), and bovine serum albumin (BSA), and the order of their interactions agrees with the substitution kinetics trends. The in vitro cytotoxic activities of PdL1-PdL4 were examined in cancer cell lines A549, PC-3, HT-29, Caco-2, and HeLa, and a normal cell line, KMST-6. Overall, PdL1 and PdL3 displayed potent cytotoxic effects on A549, PC-3 HT-29 and Caco-2 comparable to cisplatin. All the investigated complexes exhibited lower toxicity on normal cells than cisplatin.Pressure-induced non-molecular phases of polymeric nitrogen have potential applications in the field of energetic materials. Here, through a structural search method combined with first-principles calculations, we have predicted four novel nitrogen-rich aluminum nitrides C2/m-AlN6, Cm-Al2N7, C2-Al2N7 and P1-AlN7. Nitrogen atoms polymerize into infinite chains in C2/m-AlN6, C2-Al2N7 and P1-AlN7 structures and form N3 chains and N4 rings in Cm-Al2N7. C2/m-AlN6 is stable in the pressure range from 30 to 80 GPa and Cm-Al2N7, C2-Al2N7 and P1-AlN7 are metastable in the pressure ranges of 35-65, 65-80 and 41-80 GPa, respectively. The present study predicts that C2/m-AlN6 has a superconducting transition temperature of 18.9 K at 0 GPa and can be quenched and recovered under ambient conditions. The energy densities of C2/m-AlN6, Cm-Al2N7, C2-Al2N7 and P1-AlN7 compounds are expected to be 4.80, 4.59, 5.46 and 5.59 kJ g-1, respectively, due to their high nitrogen content, indicating that they have potential to be high-energy density materials. L-Histidine monohydrochloride monohydrate The calculated Vickers hardness of C2/m-AlN6, Cm-Al2N7, Cm-Al2N7 and P1-AlN7 is 43.86, 39.32, 63.96 and 33.58 GPa, respectively, showing that the novel nitrogen-rich aluminum nitrides are potential superhard materials as well. This study may encourage further experimental exploration of high N content superhard or high-energy density nitrides.It has over the last few years been reported that the application of a DC electric field and resulting current over a bed of certain catalyst-support systems enhances catalytic activity for several reactions involving hydrogen-containing reactants, and the effect has been attributed to surface protonic conductivity on the porous ceramic support (typically ZrO2, CeO2, SrZrO3). Models for the nature of the interaction between the protonic current, the catalyst particle (typically Ru, Ni, Co, Fe), and adsorbed reactants such as NH3 and CH4 have developed as experimental evidence has emerged. Here, we summarize the electrical enhancement and how it enhances yield and lowers reaction temperatures of industrially important chemical processes. We also review the nature of the relevant catalysts, support materials, as well as essentials and recent progress in surface protonics. It is easily suspected that the effect is merely an increase in local vs. nominal set temperature due to the ohmic heating of the electrical field and current.