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111.
112.
The growth of ordered domains in lattice gas models, which occurs after the system is quenched from infinite temperature to a state below the critical temperatureT
c, is studied by Monte Carlo simulation. For a square lattice with repulsion between nearest and next-nearest neighbors, which in equilibrium exhibits fourfold degenerate (2×1) superstructures, the time-dependent energy E(t), domain size L(t), and structure functionS(q, t) are obtained, both for Glauber dynamics (no conservation law) and the case with conserved density (Kawasaki dynamics). At late times the energy excess and halfwidth of the structure factor decrease proportional tot
–x, whileL(t) t
x, where the exponent x=1/2 for Glauber dynamics and x1/3 for Kawasaki dynamics. In addition, the structure factor satisfies a scaling lawS(k,t)=t
2xS(ktx). The smaller exponent for the conserved density case is traced back to the excess density contained in the walls between ordered domains which must be redistributed during growth. Quenches toT>T
c, T=Tc (where we estimate dynamic critical exponents) andT=0 are also considered. In the latter case, the system becomes frozen in a glasslike domain pattern far from equilibrium when using Kawasaki dynamics. The generalization of our results to other lattices and structures also is briefly discussed. 相似文献
113.
相转移催化元素硫的歧化反应 总被引:1,自引:0,他引:1
本工作将相转移催化(PTC)应用于元素硫歧化反应,大大降低了反应温度,提高了反应速度。该反应被证实与熔态硫在水溶液中的歧化相同,即4S+6OH~-=2S~(2-)+S_2O_3~(2-)+3H_2O。比较了四乙基铵、四丁基铵、十六烷基三甲基铵和三辛基甲基铵四种相转移催化剂及四氯乙烯、二甲苯和四氯乙烷三种溶剂的影响。讨论了本体系相转移催化的证据。为改进以元素硫歧化反应为基础的提取冶金过程提供了依据。 相似文献
114.
A relationship between the X-H (X = N, O, C, and so on) equilibrium bond length in a Morse oscillator and the X-H stretching overtone frequency shifts is obtained theoretically. We use the equation to discuss the empirical linear relationships that have been proposed for heterocyclics, alkanes and fluorinated benzenes. On the other hand, a unified relationship between the X-H bond angles and the experimental quantities (ω(?) and the coupling strength λ) is also presented for XH2, XH, and XH4 molecules or molecular fragments. Calculations of X-H bond angles for a number of molecules show that the results from our equations are in excellent agreement with the experimental values. Also we can extract the information of relative magnitude of bond coupling force field. 相似文献
115.
Yu. B. Vysotsky V. S. Bryantsev O. A. Gorban 《Chemistry of Heterocyclic Compounds》2002,38(12):1451-1468
The effects of benzannellation, phenyl substitution at the nitrogen atom, protonation at the carbene carbon, ionization, and the state of the carbene center (2 or 2) on the electronic structure, diamagnetic susceptibility, induced -electron ring currents, the 1H, 13C, and 14N chemical shifts, and the energies of the lowest electronic transitions of imidazol-2-ylidenes and their oxo and thio analogs were examined in the bound version of -electron perturbation theory. The calculated and experimental data are compared. 相似文献
116.
The separation of a selected group of naturally occurring, heterocyclic nitrosoamino acids was achieved by capillary zone electrophoresis and the resolution of the syn and anti conformers improved as the temperature was lowered to 5 °C. The double peaks observed for each nitrosoamino acid are probably caused by the slow kinetics of conformational isomerism. The experimental setup consisted of a P/ACE 5510 electrophoresis system, a 57 cm polyacrylamidecoated capillary, and a 10 mM phosphate buffer, pH 7.2, containing 2 mM of 3-(N-N-dimethylmyristylammonio)propanesulfonate (DMMAPS) and 0.1% Tween 20. Our study shows that (a) the lower the temperature, the greater the resolution and the longer the migration times; and (b) different nitrosoamino acid conformers were resolved at different temperatures because of differences in the rate of isomerization. For example, the conformers of N-nitrosothiazolidine-4-carboxylic acid were partially resolved at 30 °C while those of N-nitrosoproline were well resolved at the same temperature. 相似文献
117.
The addition of secondary and primary amines to ethyl (1-amino-9,10-anthraquinon-2-yl)propynoate affords an easily separable
mixture of the corresponding ethyl 3-dialkylaminoor 3-alkylamino-3-(1-amino-9,10-anthraquinon-2-yl)acrylate and 3-dialkylamino-
or 3-alkylaminonaphthol[2,3-h]quinoline-2(1H), 7,12-trione (in ∼4: 1 ratio). Intramolecular cyclization of the resulting substituted ethyl acrylates results in the formation
of 4-dialkylaminoor 4-alkylamino-2-chlorinated pyridine rings. Subsequent nucleophilic substitution of the chlorine atom gives
2-functionalized 4-dialkylamino- or 4-alkylaminonaphtho[2,3-h]quinoline-7,12-diones.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2327–2332, November, 1998. 相似文献
118.
Modeling and simulation of free radical polymerization of styrene under semibatch reactor conditions
The first part of this approach is concerned with the elaboration of a radical polymerization model of styrenne, based on
a kinetic diagram that includes chemical and thermal initiation, propagation, termination by recombination and chain transfer
to the monomer. Furthermore, volume contraction during polymerization is considered, as well as the gel and glass effects.
The mathematical formalism that describes the model in terms of moments is explored in detail. The model was then used to
predict the changes in monomer conversion and molecular weight after intermediate addition of initiator and monomer. The results
of this operation are dependent on the conditions of the reaction mass, quantity, and moment of substance addition. Therefore,
the simulations were performed at different times with respect to the gel effect; before, during and after this phenomenon,
and also with respect to different temperatures and initiators. Increasing the initiator concentration before the gel effect
leads to an earlier appearance of the phenomenon and to a decrease in molecular weight. The ratio
reveals a polydispersity index smaller for the intermediate addition of initiator. No significant changes take place during
or after the gel effect. If along with the initiator, unreacted monomver (used to dissolve the initiator) enters the reactor,
a small dip in conversion is observed. The general conclusion of this paper reveals the intermediate addition of initiator
as a method to control polymer properties and to prevent the “dead-end” polymerization of styrene. 相似文献
119.
B. Natalini R. Sardella E. Camaioni S. Natalini R. Pellicciari 《Chromatographia》2006,64(5-6):343-349
With the aim of optimizing the chromatographic process by avoiding any preliminary derivatizing step, we examined the chromatographic behaviour of a selected set of unconjugated bile acids looking at the dominant factors that affect the performances of three different stationary phases: RP-8, RP-18 and RP-18 Base Deactivated (RP-18-BD). Accordingly to its structural peculiarity, the RP-18-BD column combined with a specific mobile phase has proved to be the most suitable one, in enhancing both separation factor α and resolution R
S
within the selected set of analytes. Pronounced changes in the chromatographic profiles by only slightly changing the mobile phase composition (pH, buffer concentration, percentage and kind of organic modifier) prompted us to achieve satisfactory results in the separation and resolution of the selected set of bile acids.Presented at: CE in the Biotechnology & Pharmaceutical Industries: 7th symposium on the practical applications for the analysis of proteins, nucleotides and small molecules, Montreal, Canada, August 12–16, 2005.An erratum to this article can be found at 相似文献
120.
Antonella Leggio 《Tetrahedron》2007,63(34):8164-8173
A highly efficient and practical synthesis of peptides in solution phase has been developed. The procedure is based on the use of p-nitrobenzenesulfonyl (nosyl) group for the protection of the amino function of α-amino acids. Every step of the procedure, protection of the amino function by the nosyl group, formation of the peptide bond, and removal of the sulfonamide group, is characterized by high yields and excellent purity of the final products. The described strategy allows the preparation of short peptide sequences keeping the chiral integrity of amino acid precursors. Compatibility of nosyl group with the side-chain protecting groups used in Fmoc-based strategy is demonstrated. The method here presented is an alternative strategy that could provide advantages for future peptide synthesis. 相似文献