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941.
Changes in the properties of CO adsorbed at saturation coverages on Pt(100) induced by subsequent coadsorption of fixed amounts of D2O at 105 K in ultrahigh vacuum (UHV) were monitored by time-resolved infrared reflection absorption spectroscopy (tr-IRAS). The linear- and bridge-bonded CO stretching features were found to change in intensity and shift toward lower energies as a function of time at fixed CO and D2O coverages. Also observed was the development of multiple features in both CO spectral regions depending on the amount of D2O on the surface. These findings indicate that, under the conditions of these experiments, the interfacial dynamics are relatively slow, on the order of minutes, involving a gradual rearrangement of adsorbed CO and D2O on the surface to yield surface solvated CO, as has been suggested in the literature (Kizhakevariam et al. J. Chem. Phys. 1994, 100, 6750). This factor should be considered when comparing, quantitatively, shifts induced by water coadsorption with CO on Pt single crystals in UHV with CO adsorption on the same surfaces in electrochemical environments. 相似文献
942.
Owens TM Ludwig BJ Fosnacht DR Bartolin JM Homann N Wells NJ Orr BG Banaszak Holl MM 《Langmuir : the ACS journal of surfaces and colloids》2004,20(26):11422-11427
Chemisorbed monolayers of octylgermane (C8H17GeH3) on gold have been formed by vapor deposition in ultrahigh vacuum. The monolayer has been characterized by X-ray photoelectron and reflection absorption infrared spectroscopies (XPS and RAIRS) and scanning tunneling microscopy (STM). XPS data indicate the monolayer can be oxidized by exposure to ozone. STM images exhibit a complex pattern which can be modeled as strain-mediated spinodal decomposition. 相似文献
943.
Daniel Ammann Ren Bissig Marc Güggi Ern Pretsch Wilhelm Simon Irving J. Borowitz Louis Weiss 《Helvetica chimica acta》1975,58(6):1535-1548
The preparation of a series of non-cyclic, uncharged ligands able to selectively complex alkali and alkaline earth metal cations is described. These molecules are designed to be used as carriers for cations through membranes. Some of the compounds show high Ca2+ and Na+ selectivity, respectively, in liquid membrane electrodes. 相似文献
944.
In the present work, corrosion resistance of surface-coated galvanized steel was quantitatively determined by an analysis
of the alternating current (AC) impedance spectra measured on the salt-spray-tested specimen. To evaluate the corrosion resistance
of the surface-coated galvanized steel, AC impedance spectroscopy was performed on the salt-spray-tested specimen previously
exposed to salt-sprayed corrosive environment. From the analysis of the impedance spectra, the area fraction transient of
white rust θ
2(t) was theoretically derived from the equivalent circuit equation by using two fitting parameters. The values of the two fitting
parameters were determined by fitting the empirical transient equations to the area fraction of the resin coating layer and
to the total resistance obtained from the impedance spectra measured, respectively. From the analyses of θ
2(t) for four kinds of surface-coated galvanized steels with various resin coating layers, it is indicated that as the values
of the two fitting parameters decrease in the order of CP, GI, OD and OM (commercial trade names) specimens, the corrosion
resistance increases in that order as well. Furthermore, from the quantitative comparison of the two fitting parameters with
the polarization resistance of the upper resin coating layer R
p determined from the potentiodynamic polarization curve, it is suggested that the two fitting parameters decrease in value
as well with increasing R
p. 相似文献
945.
Rollie J. Myers 《Journal of solution chemistry》2007,36(3):395-403
We have measured the second acid dissociation constant, K
2a
, at several ionic strengths for hydrogen telluride (H2Te) using the Charge Transfer to Solvent (CTTS) uv spectra of its anions HTe− and Te2−. Since it is produced in our solutions, we have also determined the spectra of Te2
2− both in the uv and in the visible regions. At 25 ∘C, K
2a
= (1.28 ± 0.02) × 10−12 by extrapolation to zero ionic strength. Its value at an ionic strength equal to 0.5 mol.dm-3 was estimated to be (8.7 ± 0.2) × 10−12. The solution thermodynamics of these species are also discussed and comparisons are made to related acids. 相似文献
946.
The reactivity of [MoS(4)](2-) (1) toward PMe(3) was explored in the presence and absence of proton donors. Whereas MeCN solutions of (Et(4)N)(2)[MoS(4)] and PMe(3) are stable, in the presence of H(2)S such solutions catalyze formation of H(2) and SPMe(3). Addition of NH(4+) to such solutions afforded MoS(2)(PMe(3))(4) (2), which can be prepared directly from (NH(4))(2)[1]. Compound 2 is reactive toward thiols via a process proposed to involve the initial dissociation of one PMe(3) ligand, a hypothesis supported by the relative inertness of trans-MoS(2)(dmpe)(2). Benzene solutions of 2 react with EtSH to give Mo(2)(mu-S)(mu-SH)(PMe(3))(4)(SEt)(3) (3Et). Analogous reactions with thiocresol (MeC(6)H(4)SH) and H(2)S gave Mo(2)(mu-S)(mu-SH)(PMe(3))(4)(SR)(3) (R = tol, H). Crystallographic analyses of 3Et, 3H, and 3tol indicate dinuclear species with seven terminal ligands and a Mo(2)(mu-SR)(mu-S) core (r(Mo)(-)(Mo) = 2.748(1) A). From reaction mixtures leading to 3Et from 2, we obtained the intermediate Mo(IV)(2)(mu-S)(2)(SEt)(4)(PMe(3))(2) (4), an edge-shared bis(trigonal pyramidal) structure. Compounds 3H and 3Et react further with H(2)S to give Mo(4)(mu(2)-S)(4)(mu(3)-S)(2)(PMe(3))(6)(SH)(2) (5H) and Mo(4)(mu(2)-S)(4)(mu(3)-S)(2)(PMe(3))(6)(SEt)(2) (5Et), respectively. Analogously, W(4)(mu(2)-S)(4)(mu(3)-S)(2)(PMe(3))(6)(SH)(2) was synthesized from a methanol solution of (NH(4))(2)WS(4) with H(2)S and PMe(3). A highly accurate crystallographic analysis of (NH(4))(2)MoS(4) (R(1) = 0.0193) indicates several weak NH.S interactions. 相似文献
947.
Naomi Masuda Yatsuhisa Nagano T. Kimura 《Journal of Thermal Analysis and Calorimetry》2005,81(3):533-535
Summary The standard molar enthalpy of formation of methyl methylthiomethyl sulfoxide, CH3(CH3SCH2)SO, at T=298.15 K in the liquid state was determined to be -199.4±1.5 kJ mol-1 by means of oxygen rotating-bomb combustion calorimetry. 相似文献
948.
The efficient Fmoc solid-phase peptide synthesis of the 37-residue human Amylin and its amyloidogenic 8-37 fragment was achieved using pseudoproline (oxazolidine) dipeptide derivatives. Syntheses of hAmylin(8-37) using Fmoc amino acids produced only traces of the desired peptide. Incorporation of pseudoproline dipeptides produced the desired product with high yield and allowed for the synthesis of the full length peptide. The crude material was pure enough to allow formation of the Cys-2 to Cys-7 disulfide by air oxidation. [Structure: see text] 相似文献
949.
Tormos JR Wiley KL Seravalli J Nachon F Masson P Nicolet Y Quinn DM 《Journal of the American Chemical Society》2005,127(42):14538-14539
Secondary beta-deuterium kinetic isotope effects have been measured as a function of substrate concentration for recombinant human butyrylcholinesterase-catalyzed hydrolysis of acetyl-L3-thiocholine (L = 1H or 2H). The isotope effect on V/K is inverse, D3V/K = 0.93 +/- 0.03, which is consistent with conversion of the sp2 hybridized carbonyl carbon of the scissile ester bond of the E + A reactant state to a quasi-tetrahedral structure in the acylation transition state. In contrast, the isotope effect on Vmax under conditions of substrate activation is markedly normal, D3(betaVmax) = 1.29 +/- 0.06, an observation that is consistent with accumulation of a tetrahedral intermediate as the reactant state for catalytic turnover. Generally, tetrahedral intermediates for nonenzymatic ester hydrolyses are high-energy steady-state intermediates. Apparently, butyrylcholinesterase displays an unusual ability to stabilize such intermediates. Hence, the catalytic power of cholinesterases can largely be understood in terms of their ability to stabilize tetrahedral intermediates in the multistep reaction mechanism. 相似文献
950.
The enthalpy change of formation of the reaction of hydrous dysprosium chloride with ammonium pyrrolidinedithiocarbamate (APDC) and 1,10-phenanthroline (o-phen?H2O) in absolute ethanol at 298.15 K has been determined as (-16.12 ± 0.05) kJ?mol-1 by a microcalormeter. Thermodynamic parameters (the activation enthalpy, the activation entropy and the activation free energy), rate constant and kinetics parameters (the apparent activation energy, the pre-exponential constant and the reaction order) of the reaction have also been calculated. The enthalpy change of the solid-phase reaction at 298.15 K has been obtained as (53.59 ± 0.29) kJ?molt-1 by a thermochemistry cycle. The values of the enthalpy change of formation both in liquid-phase and solid-phase reaction indicated that the complex could only be synthesized in liquid-phase reaction. 相似文献