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901.
Extraction of nitric, perchloric, and hydrochloric acid by N,N-dibutyl diethyl carbamyl phosphonate in carbon tetrachloride was investigated. The data obtained are treated in terms of stepwise neutralization of the acid with the formation of species y · HA and y · 2HA in the organic phase, where y stands for the extractant and HA for the acid. The equilibrium constants, K?1 and K?2 for nitric acid were found to equal 0.24 ± 0.02 and 0.017 ± 0.005, respectively. In case of HClO4 and HCl K?1 were found to equal 0.031 ± 0.003 and 0.0039 ± 0.0005, respectively. A third phase was observed when extraction of HClO4 was performed using acid concentration higher than 3.5 molar. The preference for partition of different acids was discussed on the light of the competition of the proton between the acid anion, water and the basic extractant as well as the degree of the ionization of different acids. 相似文献
902.
In situ soft X-ray studies of ethylene oxidation mechanisms and intermediates on the Pt(111) surface
Burnett DJ Gabelnick AM Fischer DA Marsh AL Gland JL 《The journal of physical chemistry. B》2005,109(12):5659-5666
In situ studies of ethylene oxidation on Pt(111) have been performed using a powerful combination of fluorescence yield soft X-ray methods for temperatures up to 600 K and oxygen pressures up to 0.01 Torr. Absolute carbon coverages have been determined both in steady-state and dynamic catalytic conditions on the Pt(111) surface. Fluorescence yield near-edge spectroscopy (FYNES) and temperature-programmed fluorescence yield near-edge spectroscopy (TP-FYNES) experiments above the carbon K edge were used to identify the structure and bonding of the dominant surface species during oxidation. TP-FYNES experiments of preadsorbed ethylene coverages in oxygen pressures up to 0.01 Torr indicate a stable intermediate is formed over the 215-300 K temperature range. By comparing the intensity of the C-H sigma resonance at the magic angle with the intensity in the carbon continuum, the stoichiometry of this intermediate has been determined explicitly. Based on calibration with known C-H stoichiometries, the intermediate has a C(2)H(3) stoichiometry for oxygen pressures up to 0.01 Torr, indicating oxydehydrogenation occurs before skeletal oxidation. FYNES spectra at normal and glancing incidences were performed to characterize the structure and bonding of this intermediate. Using FYNES spectra of ethylene, ethylidyne, and acetylene as reference standard, this procedure indicates the oxidation intermediate is tri-sigma vinyl. Thus, oxidation of ethylene proceeds through a vinyl intermediate, with oxydehydrogenation preceding skeletal oxidation. 相似文献
903.
Evidence is given that, when solutions of diene monomers and anthracene in tetrahydrofuran are reacted with alkali metal and subsequently titrated with linking agents such as alkyl dihalides, copolymers are formed; they contain the 9,10-dihydroanthracene adduct and the diene in the same proportion as in the original solution. The structures of these copolymers have been elucidated by NMR spectroscopy and the mechanism of formation is discussed. 相似文献
904.
Hydrofluoro ethers (HFES) are considered to be an ideal cleaning solvent in applications like vapor degreasing and wet cleaning. It is also a good solvent replacement for CFCs (chlorofluorocarbons), HCFCs (hydrochlorofluorocarbons), HFCs (hydrofluorocarbons) and chlorinated solvents because they have a short atmospheric lifetime and low global warming potential. Based upon their properties, hydrofluoro ethers are ideally suited for the demands of the electronics industry. However, the electronics industry requires these solvents to have high purity, especially in the area of residual anions. This paper will present information on an extraction methodology for the transfer of anions from the hydrofluoro ether to water. Then, an analytical method utilizing ion chromatography that is capable of detection of 10 anions (fluoride, acetate, formate, chloride, nitrite, bromide, nitrate, sulfate, oxalate, and phosphate) in the part per billion level will be demonstrated. 相似文献
905.
Ovine luteinizing hormone. VI. Analysis of the misclassification errors in the separation of intrapituitary isohormones by chromatofocusing. 总被引:1,自引:0,他引:1
Luteinizing hormone (LH) in extracts of the ovine (o) anterior pituitary gland elutes as eight or more distinct peaks when analyzed by chromatofocusing on pH 10.5-7 gradients [Keel et al., Biol. Reprod., 36 (1987) 1102]. In order to examine the efficacy of this approach to identify the distinct charge isomers of oLH, a pool of pituitary extracts was de-salted by flow dialysis and chromatofocused on a pH 10.5-7 gradient. The immunoreactive oLH eluted in nine distinct peaks which were coded with letters beginning with the most basic form. The fractions corresponding to each peak were pooled, dialyzed and lyophilized. Each peak was then re-chromatofocused on a pH 10.5-7 gradient except for the immunoreactive oLH eluting in peak A' because of the small amount present in this peak. Each peak, except for F and H, also consisted of a small percentage of immunoreactive oLH associated with adjacent peaks. This was plausible because chromatofocusing does not generally yield baseline resolution of peaks. Peak H eluted in a broad manner and was contaminated with significant amounts of isohormones F, G and Z. In contrast, peaks B, E, F, G and Z almost completely eluted in the anticipated regions. Thus, it appears that analysis of oLH charge isomers by chromatofocusing yields minimal misclassification errors and that the misclassification errors observed are associated with molecular forms which comprise a relatively small percentage of the oLH in pituitary extracts. 相似文献
906.
R. A. Lukaszew H. Bellavigna R. Cretella M. Denari C. Noutary 《Journal of Radioanalytical and Nuclear Chemistry》1989,136(3):211-217
A photoplate calibration procedure is suggested for spark source mass spectrometry /SSMS/ with photoplate detection. The technique uses the Churchill two-line method applied to the two stable isotopes of copper. The calibration curve thus obtained is split into fragments and each fragment is approximated by a polynomial. The method was applied for the quantitative determination of Hf as impurity in zirconium sponge obtained from a pilot plant dedicated to the depletion of the hafnium content in zirconium by fractional crystallization. 相似文献
907.
908.
Coordination Compounds of Aminoacridine-N-oxides with Thiocyanates of the 3d Metals . Reactions of thiocyanates of the 3d metals with selected aminoacridine-N-oxides in homogeneous dilutions of N,N-dimethylformamide form compounds of the type [M(AAcNO)a(DMF)b(NCS)2] · cDMF and [M′(AAcNO)d(DMF)e(NCS)3] · fDMF, M = Mn2+, Co2+, Ni2+, Cu2+, Zn2+; M′ = Cr3+, Fe3+; AAcINO = 3,6-diamino-2,7-dimethylacridin-N-oxide, AAcIINO = 3,6-bis(dimethylamino)acridin-N-oxide, AAcIIINO = 2-ethoxy-6,9-diaminoacridin-N-oxide; a = 1, 2, 3, 4; b = 0, 1; c = 0, 1, 2, 3; d = 1, 2, 3; e = 0, 1, 2; f = 0, 1, 2, 3. The complexes are characterized by IR (4000–200 cm?1) and UV-VIS spectra in solutions and solids and by EPR and conductivity investigations. 相似文献
909.
The Raman spectrum of NH4Cl has been studied as a function of temperature and pressure close to the multicritical point at which the λ-transition changes from first to second order. Variations in the intensities of appropriate bands have been used to calculate the critical exponents for the order parameter. By varying the temperature at fixed pressures of zero, 3.0 k bar and 1.5 k bar, exponent values of β = 0.154 ± 0.012, β = 0.33 ± 0.06 and β = 0.26 ± 0.06 have been obtained for the first-order, second-order and multicritical regions respectively.Our first-order exponent value is close to that observed by previous workers, our second-order value is close to that predicted by the three dimensional Ising model, and our multicritical value is close to that predicted by mean field theory. 相似文献
910.
The structure and stereochemistry of the cyclopentenolones obtained by condensation of dialkyl ketones with benzil have been studied by NMR spectroscopy. These enolones were converted into cyclopentenones and cyclopentadienes. Alkyl-substituted cyclopentadienes required phenyllithium to effect their conversion by toluenesulphonyl azide into diazo-cyclopentadienes; otherwise piperidine sufficed as base catalyst.2,3,4-Triphenyldiazocyclopentadiene was simply procured by reaction of the condensation product of benzil and phenylacetone with toluenesulphonylhydrazone followed by alkali. Cyclohexyl- and methoxy-triphenylcyclopentadienes were prepared by photolytic decomposition of diazotriphenylcyclopentadiene in cyclohexane or methanol respectively. 相似文献