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11.
Rami Suleiman Abdelletif Ibdah Bassam El Ali 《Journal of organometallic chemistry》2011,696(11-12):2355-2363
A DFT study on the palladium-bisphosphine catalyzed alkoxycarbonylation and aminocarbonylation of alkyne (propyne) is reported. The theoretical study explores the feasibility and the regioselectivity control of two independent mechanisms: the first is based on the active intermediate [Pd(II)(P2)(H)]+ (where P2 = PH2CH2CH2CH2CH2PH2) for the alkoxycarbonylation reaction, and the second is based on the active species [Pd(II)(P2)(NR2)]+ for the aminocarbonylation reaction. The study explains the role of solvent in increasing the yield and in controlling the selectivity of reaction to produce selectively the trans isomer in the alkoxycarbonylation reaction (hydride cycle) and the gem isomer in the aminocarbonylation reaction (amine cycle). In hydride cycle, the regioselectivity is mainly determined by the stability of the complex [Pd(II)(P2)(COC3H5)(CH3CN)]+; however, for the amine cycle, the regioselectivity is determined by the stability of the complex [Pd(II)(P2)(C3H5CON(CH3)2)]+. The calculations reveal that ligand simplification is not valid in addressing the regioselectivity behavior of alkoxycarbonylation and aminocarbonylation reactions. The kinetic data for the formation of the two key complexes show no difference between the gem and trans isomers which predict the regioselectivity to be a thermodynamically controlled process. 相似文献
12.
A new method for separation/preconcentration of trace amounts of Cr, Cu and Pb in environmental samples by magnetic solid-phase extraction (SPE) with Bismuthiol-II-immobilized magnetic nanoparticles and their determination by ICP-OES has been developed. The separation of the target analytes from the aqueous solution containing the target analytes and Bismuthiol-II-immobilized magnetic nanoparticles was simply achieved by applying external magnetic field. Optimal experimental conditions including pH, sample volume, eluent concentration and volume and co-existing ions have been studied and established. Under the optimal experimental conditions, the detection limits for Cr, Cu and Pb with enrichment factors of 96, 95 and 87 were found to be 0.043, 0.058 and 0.085 ng mL−1 and their relative standard deviations (R.S.D.s) were 3.5%, 4.6% and 3.7% (n = 5, C = 2 ng mL−1), respectively. The method was validated with certified reference material (GBW50009-88) of environmental water sample and the analytical results coincided well with the certified values. Furthermore, the method was successfully applied to the determination of target analytes in river and lake water samples. Compared with established methods, the proposed method is characterized with high enrichment factor, fast separation and low detection limits. 相似文献
13.
The regioselective alkoxycarbonylation of phenylacetylene into various cinnamate esters was achieved with a catalyst system formed from palladium (II), 1,4‐bis(diphenylphosphino) butane (dppb) and salicylborate complex in acetonitrile as a solvent. The influence of various parameters on the overall conversion of phenylacetylene and the selectivity of the reaction were studied systematically by varying the type of palladium complex, acids promoter, CO pressure, temperature and the reaction time. This investigation allowed us to obtain the predominant formation of cinnamate esters with excellent selectivity (90–96%). Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
14.
The classical theory of radiation is extended to a relativistic linear oscillator, and the radiation properties are determined. Some basic particular cases are analyzed.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 7–11, November, 1975.In conclusion the authors thank Prof. A. A. Sokolov for his interest in the work. 相似文献
15.
Marta L. Suleiman Juliana C. Precioso Andréa C. Prokopczyk 《Mathematical Methods in the Applied Sciences》2020,43(9):6103-6116
In this work, we present conditions to obtain a global-in-time existence of solutions to a class of nonlinear viscous transport equations describing aggregation phenomena in biology with sufficiently small initial data in Besov-Morrey spaces and gradient potential as a Radon measure. We also study the self-similarity and asymptotic stability of solutions at large times. 相似文献
16.
Eduardo Vyhmeister Anthony J. Muscat David Suleiman L. Antonio Estvez 《Fluid Phase Equilibria》2008,270(1-2):121-128
Fluid-phase equilibria, including dew points, bubble points, and critical points were measured for four binary systems composed of a chlorosilane and carbon dioxide. The measurements were carried out in a constant-composition, variable-volume cell equipped with a sapphire window, which allowed visual observation of the phases in the cell. A syringe pump was used to inject the CO2 into the cell and to control its pressure. Methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, and diethyldichlorosilane up to about 0.14 mol fraction were studied in this apparatus and a total of 243 phase-boundary points were obtained. Displacements in the critical point with respect to pure CO2 of up to 11.81 MPa and 348.05 K were observed. Modeling of the fluid-phase equilibria for three of the four binary systems was done using the Peng–Robinson equation of state, standard van der Waals mixing rules with two binary interaction parameters, and a φ–φ formulation of the equilibrium. The binary interaction parameters were obtained by fitting the model to the experimental data. The model produced excellent agreement between computed and experimental data. Graphical representations of the modeling results are presented and compared to experimental results. The results indicate that the largest chlorosilane (diethyldichlorosilane) produced the largest shift in critical pressure and critical temperature with respect to pure CO2. 相似文献
17.
α-Nitro-azides were prepared by two routes involving intermediate radical-anions, and undergo substitution by an SRN1 mechanism with azides, sulphinates, and thiolates to give loss of nitrite, and with nitronates to give loss of azide. 相似文献
18.
S. Mehrkanoon Z.A. Majid M. Suleiman 《Journal of Computational and Applied Mathematics》2010,233(9):2387-2394
A new four-point implicit block multistep method is developed for solving systems of first-order ordinary differential equations with variable step size. The method computes the numerical solution at four equally spaced points simultaneously. The stability of the proposed method is investigated. The Gauss-Seidel approach is used for the implementation of the proposed method in the PE(CE)m mode. The method is presented in a simple form of Adams type and all coefficients are stored in the code in order to avoid the calculation of divided difference and integration coefficients. Numerical examples are given to illustrate the efficiency of the proposed method. 相似文献
19.
The Newton method is one of the most used methods for solving nonlinear system of equations when the Jacobian matrix is nonsingular. The method converges to a solution with Q-order two for initial points sufficiently close to the solution. The method of Halley and the method of Chebyshev are among methods that have local and cubic rate of convergence. Combining these methods with a backtracking and curvilinear strategy for unconstrained optimization problems these methods have been shown to be globally convergent. The backtracking forces a strict decrease of the function of the unconstrained optimization problem. It is shown that no damping of the step in the backtracking routine is needed close to a strict local minimizer and the global method behaves as a local method. The local behavior for the unconstrained optimization problem is investigated by considering problems with two unknowns and it is shown that there are no significant differences in the region where the global method turn into a local method for second and third order methods. Further, the final steps to reach a predefined tolerance are investigated. It is shown that the region where the higher order methods terminate in one or two iteration is significantly larger than the corresponding region for Newton’s method. 相似文献
20.
A piezoelectric quartz crystal coated with methyltrioctylphosphonium dimethylphosphate was found to be a good detector for phosgene in air. The coating is sensitive to phosgene in the μg 1?1 range and has a reasonably long lifetime. The response curve is linear over the concentration range 5–140 μg 1?1. The coated crystal can be used for more than six weeks without significant loss in sensitivity, provided that high ammonia concentrations are not encountered. 相似文献