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31.
Nonreactive and reactive computational fluid dynamic simulations were applied to optimize the design of a laboratory scale jet stirred reactor for measuring intrinsic kinetics of gas‐phase and gas‐solid reactions, i.e. kinetics determined by chemical steps only and not by heat or mass transfer. In the past these reactors were designed and tested based on empirical design criteria and residence time distribution experiments. This work shows that these do not always capture important local effects that are vital for kinetic studies. First the degree of macro–mixing was evaluated for three different geometries (down case, 45° case and 90° case) by performing in silico residence time distribution experiments at 900 K, showing that with these type of experiments only minor differences are observed. However, the ethane steam cracking simulations revealed major differences, with the 45° case being the most uniform in terms of temperature and the 90° case being by far the worst. The species nonuniformity in all geometries was acceptable and was in some cases even partly masked by important shortcut streams such as those observed in the 90° case. The existing gradients on the substrate surface are sufficiently small to be neglected in modeling efforts. As temperature is the major parameter determining the rate of the surface reactions, the 45° case is suggested as the best geometry for measuring intrinsic kinetics. 相似文献
32.
Matiide Angulo Mercedes Ruiz Montoya Rafael Marin Galvin José Miguel Rodriguez Mellado 《Electroanalysis》1997,9(4):345-349
The electroreductions of the NAD+ model compounds nicotinamide (I), N1-methyl nicotinamide (II), N′-methyl nicotinamide (III) and isonicotinamide (IV) on carbon electrodes have been studied in aqueous media in the pH range 0–12 by linear-sweep cyclic voltammetry (Scheme 1, I-IV). Logarithmic analyses of the reduction peaks were performed by computing the convolution of the current with time as a function of the potential. On the basis of the experimental results it was concluded that the irreversibility of the electron transfers increased when a glassy carbon electrode was used, and this irreversibility being more marked when a plastic formed carbon electrode was employed. The reduction processes occurred with more difficulty on carbon electrodes than on mercury electrodes. Both the reduction and the reoxidation (when occurred) processes changed with respect to those observed on mercury electrodes, being irreversible electron transfers the rate-determining steps in most cases. Thus, for compounds I, II and III at pH < 2 the reductions occurred by the uptake of two electrons and two H+ ions, and the rate determining step was found to be the first one-electron transfer, for I and III, and the irreversible second electron transfer, preceded by the uptake of an H+ ion, for II. At pH>3 the processes consisted of electrodimerization reactions, preceded by the protonation of the heterocyclic nitrogen in cases I and III. The second electron transfer of the electroreduction of IV always appeared irreversible, in contrast with that found for mercury electrodes. 相似文献
33.
E. Marin F. Boschetto M. Zanocco W. Zhu T. Adachi N. Kanamura T. Yamamoto B.J. McEntire E.N. Jones C. Powell J. Hendry R.M. Bock B.S. Bal G. Pezzotti 《Materials Today Chemistry》2021
Most structural bioceramics are comprised of metallic oxides such as alumina and zirconia. They are generally considered to be completely bioinert, but a non-oxide ceramic, silicon nitride, achieves equivalent levels of mechanical reliability while being bioactive. Silicon nitride can not only stimulate cellular proliferation but it is also antipathogenic with demonstrated efficacy against Gram-positive and Gram-negative bacteria, fungi, and viruses. In this work, three physical vapor deposition coatings with different Si:N ratios (silicon-rich, stoichiometric, and nitrogen-rich) were deposited on mirror-polished silica glass substrates. The coatings were characterized by spectroscopic and microscopic techniques and tested in vitro against E. coli and KUSA-A1 mesenchymal cells. Results showed that nitrogen-enriched SixNy has a strong antibacterial effect against E. coli and contributes to cellular proliferation while silicon-enriched SixNy stimulates the production of bone tissue, with higher indexes for mineralization and quality. These results suggest that SixNy's biological properties can be optimized for specific applications by carefully tuning its surface chemistry. 相似文献
34.
Luminita Marin Marcel Popa Alexandru Anisiei Stefan-Andrei Irimiciuc Maricel Agop Tudor-Cristian Petrescu Decebal Vasincu Loredana Himiniuc 《Molecules (Basel, Switzerland)》2021,26(7)
The aim of the study was to create a mathematical model useful for monitoring the release of bioactive aldehydes covalently bonded to the chitosan by reversible imine linkage, considered as a polymer–drug system. For this purpose, two hydrogels were prepared by the acid condensation reaction of chitosan with the antifungal 2-formyl-phenyl-boronic acid and their particularities; influencing the release of the antifungal aldehyde by shifting the imination equilibrium to the reagents was considered, i.e., the supramolecular nature of the hydrogels was highlighted by polarized light microscopy, while scanning electron microscopy showed their microporous morphology. Furthermore, the in vitro fungicidal activity was investigated on two fungal strains and the in vitro release curves of the antifungal aldehyde triggered by the pH stimulus were drawn. The theoretical model was developed starting from the hypothesis that the imine-chitosan system, both structurally and functionally, can be assimilated, from a mathematical point of view, with a multifractal object, and its dynamics were analyzed in the framework of the Scale Relativity Theory. Thus, through Riccati-type gauges, two synchronous dynamics, one in the scale space, associated with the fungicidal activity, and the other in the usual space, associated with the antifungal aldehyde release, become operational. Their synchronicity, reducible to the isomorphism of two SL(2R)-type groups, implies, by means of its joint invariant functions, bioactive aldehyde compound release dynamics in the form of “kink–antikink pairs” dynamics of a multifractal type. Finally, the theoretical model was validated through the experimental data. 相似文献
35.
Ernesto Carmona Jose M. Marin Manuel L. Poveda Robin D. Rogers Jerry L. Atwood 《Journal of organometallic chemistry》1982,238(4):C63-C66
The reduction of [WCl4(PMe3)3] with dispersed sodium, under dinitrogen, gives cis-[W(N2)2(PMe3)4], while under ethylene trans-[W(C2H4)2(PMe3)4] is obtained. The ethylene complex can also be prepared by displacement of the dinitrogen molecules in cis-[W(N2)2(PMe3)4] by ethylene at room temperature and pressure. Interaction of cis-[M(N2)2(PMe3)4] complexes (M = Mo, W), with PMe3, under helium or argon, yields [M(N2)(PMe3)5]. The molybdenum complex crystallizes in the orthorhombic space group Pnma, with a 22.063(6), b 12.106(4), c 9.745(4) Å. The Mo—P distance trans to the dinitrogen ligand (2.483(7) Å) is slightly longer than the average of the other four Mo—P bonds (2.460(5) Å). 相似文献
36.
Marin Marin 《Nonlinear Analysis: Real World Applications》2009,10(3):1572-1578
In the present paper we generalize the results obtained by Iesan and Quintanilla for microstretch elastic bodies in order to cover dipolar elastic materials with stretch. For the boundary value problem considered in this context, we prove a generalized existence result and, also, an extension of the principle of minimum potential energy. 相似文献
37.
V. S. Litvin A. D. Belyaev S. M. Ignatov V. G. Nedorezov R. A. Sadykov A. A. Alekseev E. V. Kuznetsova V. L. Kuznetsov V. N. Marin V. I. Ivanov 《Bulletin of the Russian Academy of Sciences: Physics》2009,73(2):219-221
ZnS(Ag)/6LiF and LiI(Eu) scintillators for thermal neutron detectors have been investigated and neutron detectors based on these scintillators and photomultipliers have been tested. The efficiencies of these detectors are 5 and 66%, respectively. The possibility of developing position-sensitive detectors of thermal neutrons with high space and time resolution is discussed. 相似文献
38.
We study, theoretically and experimentally, the evolution of patterns in a passive nonlinear cavity that is longer than the coherence length of the light circulating in it. The patterns exhibit spatial line narrowing as the feedback is increased, resembling the line narrowing in lasers. 相似文献
39.
Ph. Gavillet C. Dionisi A. Gurtu R.J. Hemingway M.J. Losty J.C. Marin M. Mazzucato L. Montanet E. Pagiola R. Blokzijl B. Jongejans J.C. Kluyver G.G.G. Massaro J.J. Engelen J.S.M. Vergeest M. Zralek B. Foster P. Grossmann J. Wells 《Physics letters. [Part B]》1978,78(1):158-161
The backward production of the B(1235) meson is studied in the reaction K?p→Σ?π+ω. This reaction is observed in the final state Σ?π+π+π?π0. A π+ω mass enhancement is visible in the region of the B meson for events with small |u|K? →Σ?) squared four-momentum transfer. The properties of the enhancement agree with those of the B meson. The cross section for K?p→Σ?B+ at incident K? momentum is (3.2 ± 0.5) μb. The backward production of the B meson is compared with similar baryon exchange productions of the A1 and C(Q1) axial vector mesons observed in the same experiment. 相似文献
40.