Effects of a wall on the self-ignition patterns and flame propagation of high-pressure hydrogen release through a tube

High-pressure hydrogen gas is gaining more attention as the next-generation energy carrier, but its safe handling and storage remains an important issue. The possibility of self-ignition near an obstacle is a realistic concern in practical applications such as a hydrogen car, but only a few studies related to this issue have been conducted. In this paper, experimental investigations were carried out to understand the effects of a wall on ignition patterns by high-speed imaging. This study was conducted using extension tubes of different lengths at burst pressures up to 30 MPa. The wall height, distance of the wall from the tube exit and the burst pressure were considered as the main wall parameters affecting self-ignition. The results showed that the existence of a wall could not change the type of ignition patterns (i.e., the wall does not initiate or extinguish a flame) regardless of the wall height and burst pressure, but only when the tube was too short to generate a strong flame inside the tube. When the tube was long enough to induce a strong flame in the tube, however, the wall promoted flame stabilization, e.g., the flame stabilization time outside the tube was shortened by locating the wall near the tube. But its effect disappeared when the distance of the wall from the tube exceeded 10D.     

Templated syntheses of Pt thin films with feature sizes of 3, 6 and 9 nm and their effects on SERS

We report on the syntheses of nanostructured Pt films with three different feature sizes of 3, 6 and 9 nm and their effects to the surface enhance Raman spectroscopy of rhodamine 6G (Rh6G) analytes. The syntheses of the Pt films have been achieved through templating the pore structures of mesoporous silica thin films (MSTFs). For the purpose of the present study, we synthesized three MSTFs with pore sizes 3, 6 and 9 nm. Other than the pore sizes, the silica thin films have the same pore structures. The Pt films have been synthesized by depositing Pt into the pores of the template MSTFs and removing the templates after the deposition. The Pt films produce strong Raman spectra of Rh6G with the intensity increasing as the feature size of the Pt film increases. Simulations of the induced electromagnetic fields on the Pt films show the same trend as the observed Raman intensity with the feature size. Copyright © 2012 John Wiley & Sons, Ltd.     

Theoretical study of the V(4F)?+?NO(2��r)?��?VO(4��?)?+?N(4S��) reaction compared with the Sc(2D) and Ti(3F) cases

To understand the title reaction, the MRCI, CCSD, CCSD(T), and DFT calculations have been done. A large domain of the ground-state potential energy surface has been explored including the activation energy barrier to form the triatomic complex, two stable intermediate complexes, V[NO] and NVO, the transition state connecting these two conformers, and the detachment of the nitrogen atom. We compared this reaction with the similar ones involving the Sc and Ti atoms. The activation barrier to form the VNO complex made from the ionic-covalent coupling decreases to approach the experimental data when the electron correlation effect is better included as in the Sc and Ti systems. The transition state connecting the two conformers was calculated to be higher than in the Sc and Ti cases probably due to larger number of nonbonding valence electrons and is probably too high with respect to the reactant energy level to allow the interconversion between the two conformers in the VNO. The direct concerted substitution (abstraction) reaction is improbable because this process will have to overcome a too high potential barrier. We have also found the transition state connecting two conformers of ScNO.     

Influence of residual impurities on ring‐opening metathesis polymerization after copper(I)‐catalyzed alkyne‐azide cycloaddition click reaction

Bottlebrush polymers (BBPs) are three‐dimensional polymers with great academic and industrial potential owing to their highly tunable and intricate architecture. The most popular method to synthesize BBPs is ring‐opening metathesis polymerization (ROMP) with Grubbs' catalyst, allowing living grafting‐through polymerization of macromonomers of up to ultrahigh molecular weights with narrow molecular weight distribution. In this case, it has been well recognized that the purity of macromonomers (MMs) is critical for a successful ROMP reaction. For MMs synthesized from reversible‐deactivation radical polymerization, Grubbs and Xia demonstrated that the better control of ROMP reaction can be achieved when they are prepared via “growth‐then‐coupling” method that is coupling a norbornenyl group to end‐functionalized prepolymers. However, these MMs can also contain various residual impurities from previous synthetic steps, which can potentially poison the catalyst and hamper the ROMP reaction. Herein, we intentionally doped possible impurities into purified MMs to identify the most poisoning species. As a result, it was found that alkyne‐functionalized norbornene most significantly retarded the ROMP reaction due to a formation of Ru‐vinyl‐carbene intermediates having low catalytic reactivity, whereas the other reagents such as solvent, Cu‐catalyst, ligands, and azido‐terminated prepolymers were relatively inert. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 726–737     

Influence of absorbed pump profile on the temperature distribution within a diode side-pumped laser rod

In this paper, an analytical model for temperature distribution of the side-pumped laser rod is extracted. This model can be used for side-pumped laser rods whose absorbed pump profile is a Gaussian profile. Then, it is validated by numerical results which exhibit a good agreement with the analytical results. Afterwards, by considering a general expression for super-Gaussian and top-hat profiles, and solving the heat equation, the influence of profile width and super-Gaussian exponent of the profile on temperature distribution are investigated. Consequently, the profile width turns out to have a greater influence on the temperature compared to the type of the profile.     

Multiple Ionic-Covalent Couplings in Molecules and Clusters

由电正和电负组元构成的分子的电子态是共价构型和离子构型相互干涉作用的结果. 研究揭示了在Li2H、Li2F和Li4F等小分子中离子-共价耦合的复杂性. 将这一类分析扩展至金属团簇或者金属表面对亲电分子的吸附将会对于观测到的物理和化学性质提供全新的解释.     

Minimal-basis-adapted pseudopotentials for transition metal atoms

A pseudopotential technique is presented to be used with a single function constructed from the three primitive GTOs for the representation of d orbitals of transition-metal atoms. Applied to Cu, CU₂, and CuF, it has permitted a reduction in the number of 3d-type GTO primitives without reducing the quality of the results.     

Multiple Ionic-Covalent Couplings in Molecules and Clusters

The electronic states of molecules made of electropositive and electronegative components result from the interference between the covalent configurations and the ionic configurations. This work shows complex aspects of these ionic-covalent couplings in small molecules such as Li2H, Li2F, and Li4F. The extension of this type of analysis to the adsorption of the electrophilic molecules on the metal clusters or on the metal surfaces is supposed to lead to a radically new interpretation of the observed physical and chemical properties.     

Heterogeneous photoredox catalysis using fluorescein polymer brush functionalized glass beads

Photocatalysis is a valuable and versatile method to perform a variety of chemical transformations under ambient temperatures and pressures using mild visible light. This work showcases an example of fluorescein-functionalized polymers grafted to micro-scale glass beads as heterogeneous photoredox catalysts. X-ray photoelectron spectroscopy and thermogravimetric analysis were used to analyze the resulting functional glass beads. Model reactions that are demonstrated include a cyclic condensation and a radical dehalogenation that can both be performed to high yields. Successful recyclability of the fluorescein polymer brush beads is demonstrated with detailed characterization confirming that photocatalytic polymer brushes remain tethered to the surface. As such, this allows for purification and reuse of the heterogeneous photocatalyst beads after simple filtration.     

Pancreatic lipase inhibition by C-glycosidic flavones Isolated from Eremochloa ophiuroides

Activity-guided fractionation of a methanolic extract of the leaves of Eremochloa ophiuroides (centipede grass) using a pancreatic lipase inhibitory assay led to the isolation and identification of a new C-glycosidic flavone, luteolin 6-C-?-D-boivinopyranoside (1), as well as eight known compounds. The structures of these compounds were established on the basis of interpretation of their spectroscopic data. Among these isolates, the C-glycosidic flavones 1-5 showed potent inhibitory effects on pancreatic lipase, with IC?? values ranging from 18.5 ± 2.6 to 50.5 ± 3.9 μM.