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We study the isothermal hydrogen adsorption and reaction at the E-TEK electrode of a polymer electrolyte fuel cell with a Nafion 117 membrane by impedance spectroscopy at 30 degrees C. We find that the impedance diagram must include a Gerischer phase element. Constant phase elements are not sufficient to describe the experimental data. This means that an adsorption reaction takes place in combination with surface diffusion of hydrogen in the carbon layer located before the platinum surface, separate from the charge transfer step at the platinum particle surface. We are not able to distinguish between molecular or atomic hydrogen diffusion on carbon. We predict and find that the relaxation time of the adsorption step is independent of the applied potential. Water may also enter rate-limiting steps in the electrode reaction, but its role needs further clarification. 相似文献
14.
Song SH Dick B Zirak P Penzkofer A Schiereis T Hegemann P 《Journal of photochemistry and photobiology. B, Biology》2005,81(1):55-65
An absorption and emission spectroscopic characterisation of the combined wild-type LOV1-LOV2 domain string (abbreviated LOV1/2) of phot from the green alga Chlamydomonas reinhardtii is carried out at pH 8. A LOV1/2-MBP fusion protein (MBP=maltose binding protein) and LOV1/2 with a His-tag at the C-terminus (LOV1/2-His) expressed in an Escherichia coli strain are investigated. Blue-light photo-excitation generates a non-fluorescent intermediate photoproduct (flavin-C(4a)-cysteinyl adduct with absorption peak at 390 nm). The photo-cycle dynamics is studied by dark-state absorption and fluorescence measurement, by following the temporal absorption and emission changes under blue and violet light exposure, and by measuring the temporal absorption and fluorescence recovery after light exposure. The fluorescence quantum yield, phi(F), of the dark adapted samples is phi(F)(LOV1/2-His) approximately 0.15 and phi(F)(LOV1/2-MBP) approximately 0.17. A bi-exponential absorption recovery after light exposure with a fast (in the several 10-s range) and a slow component (in the near 10-min range) are resolved. The quantum yield of photo-adduct formation, phi(Ad), is extracted from excitation intensity dependent absorption measurements. It decreases somewhat with rising excitation intensity. The behaviour of the combined wildtype LOV1-LOV2 double domains is compared with the behaviour of the separate LOV1 and LOV2 domains. 相似文献
15.
A. V. Willi 《Helvetica chimica acta》1966,49(5):1725-1728
Second order rate constants are determined for the E2 reactions of 2,2-diphenyl-ethyl benzenesulfonates Ph2CxHCH2O · O2S–C6H4–X with CH3ONa in methyl cellosolve solution (xH = H or D, X = p-CH3O, p-CH3, H or p-NO2). The HAMMETT ? values are of the same order of magnitude as those found in the first order solvolyses of methyl, ethyl or isopropyl benzenesulfonates. The primary deuterium isotope effects kH/kD are 5.27, 5.42 and 6.70 for X = p-CH3O, H and p-NO2. The ? values as well as the increase of kH/kD with introduction of p-NO2 supply evidence for simultaneous CαO and CβH bond cleavages also in the E2 reactions of these compounds. 相似文献
16.
Alfred V. Willi 《Helvetica chimica acta》1973,56(6):2094-2098
It is suggested that the acid catalyzed hydrolyses of isobutene oxide and propene oxide proceed via rate-determining bimolecular reaction between a carbonium ion and solvent water (A2+ mechanism). The carbonium ion is formed by ring opening of the protonated epoxide, in a relatively fast preceding step. This mechanism is in agreement with all experimental facts known today. There is evidence for a similar mechanism in the acid catalyzed hydrolyses of cyclic acetals. 相似文献
17.
Yutaka Morita Manfred Hesse Hans Schmid Avijit Banerji Julie Banerji Asima Chatterjee Willi E. Oberhnsli 《Helvetica chimica acta》1977,60(4):1419-1434
Alstonia scholaris: The structure of the indole alkaloid nareline Besides the known akuammidine, picralinal, picrinine and pseudoakuammigine a new indole alkaloid called nareline (M=352) was isolated from Alstonia scholaris R. BR. , which belongs to the plant family of Apocynaceae. Its structure 2 was deduced by single crystal X-ray diffraction. 2 represents the absolute configuration. The spectroscopic data of 2 and its derivatives (Scheme 1) as well as their chemical behavior support this structure. In biogenetic sense nareline is related to the bases akuammiline ( 4 ) and picraline ( 5 ) (Scheme 2). In contrast to those the C-atom 5 is exocyclic and represents an aldehyde group which forms together with the oxygen atom of the N (4)-hydroxylamine group a cyclic half acetale. - By oxidation (CrO3/CH3COOH) of 2 the oxindol derivative 19 (oxonareline) is formed which contains a cyclic acetal as a partial structure element (Scheme 4). 相似文献
18.
Title compound 1 was synthesized by a published route which had to be modified (seven steps from readily obtainable starting materials). Characterization of 1 was achieved by spectroscopic means (FAB-MS, 1H-NMR, including 2D-COSY). Furthermore, commercially available reference material purchased for comparison, was unequivocally established to be 10 , i.e. incompletely deprotected 1 . 相似文献
19.
Günter Ehrlich Thomas Nestler Rainer Voigtmann Willi Moldenhauer 《Mikrochimica acta》1989,98(4-6):249-258
To compare concentration profiles in solids in an objective manner, a multi-dimensional generalization of the comparison of two means by Student'st-test is proposed. The approach is based on piecewise modelling the profiles using rougha priori information, estimating the model parameters and their covariance matrix and comparing the estimated parameters by use of multidimensional test variables. The piecewise modelling is treated in the most important cases in such a way that the partial functions are straight lines or cubic polynoms (splines) with continuity at all knots in each case. It enables us to compare whole profiles as well as the most relevant parts of them. Two ways of estimating the covariance matrix as a generalization of the variance estimation are discussed. The approach is useful for any kind of line profiles if rough information on the profile type is available. As an example SIMS depth-profiles of aluminum obtained from thin-layer systems after different technological heat treatments are considered. These profiles are modeled by three straight lines. 相似文献
20.
C.L. Chakrabarti S.B. Chang T.J. Huston P.C. Bertels J.T. Rogers R. Dick 《Analytica chimica acta》1985
The predictions of a theoretical model, embodied in a computer program, describing the heating characteristics of the furnace surface and the gas phase of an anisotropic pyrolytic graphite furnace heated by the capacitive discharge technique are compared with the experimental results obtained by optical pyrometry and by two-line atomic absorption spectrometry, respectively. The surface temperature gradient around the circumference of the type 1 furnace and along the optical axis of the type 3 furnace are calculated and compared with the measured temperatures. The weighted-average of the theoretically predicted gas temperature is in reasonable agreement with the effective vapour temperature measured by two-line atomic absorption method. The heating rate of the furnace does not have a significant effect on the temperature distribution of either the furnace surface or the gas phase. The effect of the difference in the temperature distribution of the type 1 and type 3 furnaces on the atomic absorption signals is also discussed. 相似文献