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171.
Summary. This review reveals that, in contrast to the general opinion, the aqueous speciation of nickel is poorly known. Besides the
fairly well established first hydrolysis constant, data are scarce and only poor estimates can be derived for higher Ni hydrolysis
constants from a few solubility studies. The situation is even worse in the case of aqueous carbonate complexes. No reliable
experimental study has been published so far and almost all numbers reported in thermodynamic databases are unacceptable estimates.
In this review we scrutinise all these published estimates and propose expectation ranges of nickel carbonate complex stability
through correlation with other known thermodynamic constants. Solubility constants for a few simple nickel solids are known
or have been estimated from thermochemical data. However, none of these simple solids is of geochemical relevance at ambient
conditions. Based on field evidence, classes of solids are identified which potentially govern nickel concentrations in ground
and surface waters. Recent spectroscopic data indicate that magnesium clay minerals and layered double hydroxides are the
most prominent candidates for nickel-bearing solids at ambient conditions.
Corresponding author. E-mail: wolfgang.hummel@psi.ch
Dedicated to the memory of Prof. Rolf Grauer
Received January 14, 2003; accepted January 24, 2003
Published online May 15, 2003 相似文献
172.
Pure rotational transitions of the weakly bound complex He-N(2)O and three minor isotopomers (He-(14)N(15)NO, He-(15)N(14)NO, and He-(15)N(15)NO) were measured in the frequency region from 6 to 20 GHz. Predictions for the microwave transition frequencies were based on the infrared work by Tang and McKellar [J. Chem. Phys. 117, 2586 (2002)]. In the case of (14)N containing isotopomers, nuclear quadrupole hyperfine structure of the rotational transitions was observed and analyzed. The resulting spectroscopic parameters were used to determine geometrical and dynamical information about the complex. An ab initio potential energy surface was calculated at the coupled cluster level of theory with single and double excitations and perturbative inclusion of triple excitations. This surface was constructed using the augmented correlation consistent polarized valence triple zeta basis set for all atoms with the inclusion of bond functions for the van der Waals bond. Bound state calculations were done to determine the energies of low-lying rovibrational levels that are supported by the potential energy surface. The resulting transition energies agree with the experimental values to 1% or better. 相似文献
173.
The new compounds YNi2P2 and LnNi2P2 (Ln = La, Ce, Pr, Nd, Sm, Tb, Dy, Ho, Er, Tm) were prépared by sintering the elemental components in silica tubes. Well-developed crystals were obtained using tin as a flux. They crystallize with the ThCr2Si2 (CeGa2Al2)-type structure which was refined from single-crystal X-ray data for EuNi2P2 to a conventional R value of 0.049 for 118 unique structure factors. While the P atoms in formally isotypic EuCo2P2 are isolated from each other, they form pairs in EuNi2P2. This results in a different ratio and an entirely different bonding situation. A comparison of cell volumes shows that Eu in EuNi2P2 has an intermediate valence. 相似文献
174.
Kayed A. Abu Safieh Ahmad M. Abu Mahthieh Mustafa M. El-Abadelah Mikdad T. Ayoub Wolfgang Voelter 《Monatshefte für Chemie / Chemical Monthly》2007,138(2):157-160
Summary. A novel method for the synthesis of a new series of 5-substituted 1,3-dimethyl pyrazolo[4,3-e][1,2,4]triazines is described. The new synthetic strategy is based on the classical Bischler 1,2,4-benzotriazine synthesis. This approach involves the preparation of 5-hydrazinopyrazole from 5-chloro-1,3-dimethyl-4-nitropyrazole
followed by acylation and nitro group reduction to form the corresponding 4-amino-3-(acylhydrazino)pyrazoles. Intramolecular
oxidative cyclization of the latter derivatives, using polyphosphoric acid, produced the respective target pyrazolotriazines. 相似文献
175.
Kayed A. Abu Safieh Ahmad M. Abu Mahthieh Mustafa M. El-Abadelah Mikdad T. Ayoub Wolfgang Voelter 《Monatshefte für Chemie / Chemical Monthly》2007,21(9):157-160
A novel method for the synthesis of a new series of 5-substituted 1,3-dimethyl pyrazolo[4,3-e][1,2,4]triazines is described. The new synthetic strategy is based on the classical Bischler 1,2,4-benzotriazine synthesis. This approach involves the preparation of 5-hydrazinopyrazole from 5-chloro-1,3-dimethyl-4-nitropyrazole
followed by acylation and nitro group reduction to form the corresponding 4-amino-3-(acylhydrazino)pyrazoles. Intramolecular
oxidative cyclization of the latter derivatives, using polyphosphoric acid, produced the respective target pyrazolotriazines. 相似文献
176.
Ananya Banik Theodosios Famprikis Michael Ghidiu Saneyuki Ohno Marvin A. Kraft Wolfgang G. Zeier 《Chemical science》2021,12(18):6238
The development of high-performance inorganic solid electrolytes is central to achieving high-energy- density solid-state batteries. Whereas these solid-state materials are often prepared via classic solid-state syntheses, recent efforts in the community have shown that mechanochemical reactions, solution syntheses, microwave syntheses, and various post-synthetic heat treatment routines can drastically affect the structure and microstructure, and with it, the transport properties of the materials. On the one hand, these are important considerations for the upscaling of a materials processing route for industrial applications and industrial production. On the other hand, it shows that the influence of the different syntheses on the materials'' properties is neither well understood fundamentally nor broadly internalized well. Here we aim to review the recent efforts on understanding the influence of the synthetic procedure on the synthesis – (micro)structure – transport correlations in superionic conductors. Our aim is to provide the field of solid-state research a direction for future efforts to better understand current materials properties based on synthetic routes, rather than having an overly simplistic idea of any given composition having an intrinsic conductivity. We hope this review will shed light on the underestimated influence of synthesis on the transport properties of solid electrolytes toward the design of syntheses of future solid electrolytes and help guide industrial efforts of known materials.Influence of synthesis and processing on the nature of ultimate product and the ionic transport properties of superionic conductors. 相似文献
177.
Gerhard Buchbauer Johanna Gabmeier Ernst Haslinger Wolfgang Robien Harald Steindl 《Helvetica chimica acta》1985,68(1):231-235
Synthesis and Reactions of the Bicyclo[6.4.0]dodecane-3-carboxylic Acid Derivatives The synthesis and some consecutive reactions of the compounds 5-8 , derivatives of bicyclo[6.4.0]dodecane-3-carboxylic acid ( 1 ), are described. The esters 7 and 8 can be obtained by Baeyer-Villiger oxidation of 2-hydroxy-8-methyltricyclo[7.3.1.02,7]tridecan-13-one ( 4 ) and subsequent hydrolysis of the lactone 5 . The structure and configuration of these compounds has been evaluated by spectroscopic techniques (mainly 2D-NMR methods). The formation of 7 via 1,2-H shift and subsequent isomerization to 8 has been studied. The esters 11 and 13 are formed stereospecifically from 7 and 8 . 相似文献
178.
α-Diazo phosphonates with a conjugated 1,3-diene unit are synthesised by the Bamford-Stevens reaction ( →→). They undergo [4+2]-cycloadditions with the dienophile to form the tetrahydrotriazolopyridazines , which possess an unchanged diazo group. In contrast, dimethyl acetylenedicarboxylate () reacts exclusively with the diazo dipole of to yield the 3H-pyrazoles , which rearrange to by sigmatropic PO-shifts and hydrolyse to form . The diazo compound isomerises to the pyrazole when heated in benzene. 相似文献
179.
Heinrich Hillig Hendrik Küper Wolfgang Riepe Hans Peter Ritter 《Analytica chimica acta》1979,112(2):123-132
Automation of a mass spectrometer—computer system makes it possible to process up to 30 samples without attention after sample loading. An automatic sample changer introduces the samples successively into the ion source by means of a direct inlet probe. A process control unit determines the operation sequence. Computer programs are available for the hardware support, system supervision and evaluation of the spectrometer signals. The most essential precondition for automation — automatic evaporation of the sample material by electronic control of the total ion current — is confirmed to be satisfactory. The system operates routinely overnight in an industrial laboratory, so that day work can be devoted to difficult analytical problems. The cost of routine analyses is halved. 相似文献
180.
Optimal control simulation is applied to the cis-trans photoisomerization of retinal in rhodopsin within a two-dimensional, two-electronic-state model with a conical intersection [S. Hahn and G. Stock, J. Phys. Chem. B 104, 1146 (2000)]. For this case study, we investigate coherent control mechanisms, in which laser pulses work cooperatively with a conical intersection that acts as a "wave-packet cannon." Optimally designed pulses largely consist of shaping subpulses that prepare a wave packet, which is localized along a reaction coordinate and has little energy in the coupling mode, through multiple electronic transitions. This shaping process is shown to be essential for achieving a high target yield although the envelopes of the calculated pulses depend on the local topography of the potential-energy surfaces around the conical intersection and the choice of target. The control mechanisms are analyzed by considering the motion of reduced wave packets in a nuclear configuration space as well as by snapshots of probability current-density maps. 相似文献