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91.
A kinetic study on the basic hydrolysis of cephaloridine at pD= 10.5 was carried out by using the 1H? NMR technique. Epimerization at H7, a nucleophilic attack of hydroxyl ion on the β-lactam carbonyl group followed by the release of the pyridine molecule, and isomerization of the double bond at position 3 in the dihydrothiazine ring were the major reactions observed. Based on the results obtained, it should be emphasized that the presence of a pyridine group at 3′ results in a slightly increased formation constant for the exo methylene compound relative to other cephalosporins with different substituents at that position. The activation energy for the epimerization constant and the cleavage of the β-lactam ring at pD 10.5 was 21.2 kcal/mol. © 1993 John Wiley & Sons, Inc. 相似文献
92.
J. Ramírez-Muñoz 《Analytica chimica acta》1975,78(2):431-438
Two colorimetric methods based on the formation of molybdenum blue (the tin(II)and ascorbic acid methods) have been adapted for the routine automatic determination of phosphate in water samples. Repeatability and linearity of both methods in discrete-sample automatic analysis are satisfactory. Some water samples were analyzed by both methods to compare final analytical results. An analytical rate of 60 readings per hour can be obtained. 相似文献
93.
G. García-Muoz J. Iglesias M. Lora-Tamayo R. Madroero M. Stud 《Journal of heterocyclic chemistry》1969,6(1):5-8
From the reaction of benzotriazoles with 2,3-dihydro-4H-pyrane and 2-acetoxymethyl-3,4-dihydro-2H-pyrane the corresponding 1-(2-tetrahydropyranyl)benzotriazole and cis-and trans-1-(6-acetoxymethyl-2-tetrahydropyranyl)benzotriazole derivatives were obtained. The structures and conformations of these compounds were confirmed by UV and NMR spectra. 相似文献
94.
The self-deconvolution of L23VV Auger spectra of SiO2 and Al2O3 has been carried out. The transition density functions obtained are compared with the local density of states (LDOS) of the valence band near the surface, as given by other techniques (XPS, UPS, XES) and also by theory. A fair agreement in the number and peak positions of valence band is produced. These compounds with MgO constitute an oxide series of increasing ionicity and the effects of initial hole localization in the transition density function are discussed. 相似文献
95.
This article reviews the most relevant chemical and structural aspects that influence the spin-crossover phenomenon (SCO). Special attention is focussed on the recent development of SCO coordination polymers. The different approaches currently being explored in order to achieve multifunctionality in SCO materials are discussed. 相似文献
96.
Efficient and accurate integration of stochastic (partial) differential equations with multiplicative noise can be obtained through a split-step scheme, which separates the integration of the deterministic part from that of the stochastic part, the latter being performed by sampling exactly the solution of the associated Fokker-Planck equation. We demonstrate the computational power of this method by applying it to the most absorbing phase transitions for which Langevin equations have been proposed. This provides precise estimates of the associated scaling exponents, clarifying the classification of these nonequilibrium problems, and confirms or refutes some existing theories. 相似文献
97.
We apply the nonperturbative renormalization group method to a class of out-of-equilibrium phase transitions (usually called "parity-conserving" or, more properly, "generalized voter" class) which is out of the reach of perturbative approaches. We show the existence of a genuinely nonperturbative fixed point, i.e., a critical point that does not seem to be Gaussian in any dimension. 相似文献
98.
R. Jimnez M. Villar M. Cueto E. Grueso J. Illanes J. I. Cobrian F. Cantn I. Villa J. M. Snchez S. Maza J. M. Muoz C. Muoz R. Prado‐Gotor 《国际化学动力学杂志》2004,36(7):410-415
The base‐catalyzed linkage isomerization of [Co(NH3)5‐ONO]2+ to the nitro [(NH3)5Co‐NO2]2+ form is studied in various isodielectric water–cosolvent mixtures (methanol, ethanol, tert‐butyl alcohol, and 2‐propanol) at 298 K. In all cases, except for methanol–water mixtures, the rate constants increase with the proportion of cosolvent. Medium effects have been rationalized by using a multiparameter regression of solvent parameters which rationalizes the results obtained, including water–methanol mixtures. The experimental data, k2, in fact, are well correlated through the following equation: where A, B, and Gexc are the acidity parameter, the basicity parameter, and the excess Gibbs free energy of the mixture, respectively. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 410–415, 2004 相似文献
99.
M.O. Ramírez D. Jaque J.A. Sanz García L.E. Bausá J.E. Muñoz Santiuste 《Applied physics. B, Lasers and optics》2003,77(6-7):621-623
An optimization of the laser action performance from a diode-pumped Yb3+-doped LiNbO3:MgO crystal has been carried out. In this sense, efficient laser action at 1.06 m when pumping with a fiber-coupled laser diode at 980 nm has been demonstrated, achieving laser slope efficiencies as high as 74%. The influence of output mirror transmittance on both pumping threshold and laser slope efficiency has been investigated, and the parameters of relevance in laser dynamics (emission cross section and optical losses) have been determined. Under the experimental conditions leading to maximum slope efficiency, the pump power at threshold was 300mW, and the pump-to-laser conversion efficiency was 40%. PACS 42.55.Xi; 42.55.Rz; 42.60.Lh 相似文献
100.
A prototype calix[4]arene-based receptor for carbohydrate recognition containing peptide and phosphate binding groups 总被引:2,自引:0,他引:2
Segura M Bricoli B Casnati A Muñoz EM Sansone F Ungaro R Vicent C 《The Journal of organic chemistry》2003,68(16):6296-6303
A novel class of macrobicyclic receptors for carbohydrate recognition based on upper rim, peptide-bridged calix[4]arenes has been designed and synthesized. Receptor 12, in which a charged phosphate group cooperates with peptide hydrogen-bonding donor and acceptor groups in the binding process, is the most efficient and selective in the complexation of simple carbohydrate derivatives. The selectivity observed is toward beta-glucoside 13a, which is better bound (DeltaG degrees = 19.6 kJ mol(-)(1)) compared to the corresponding alpha anomer 13b (DeltaG degrees = 17.0 kJ mol(-)(1)) and to the beta-galactoside 13c (DeltaG degrees = 17.7 kJ mol(-)(1)) in CDCl(3). A substantial drop in the stability constant is observed by esterification of the phosphate group in the host 12 or by alkylation of the OH groups in the 2 and 3 positions in the beta-glucoside and beta-galactoside derivatives. On the basis of a careful analysis of the (1)H NMR data available, a binding mode of the beta-octylglucoside 13a to receptor 12 is proposed. 相似文献