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941.
Alexander Kane Ren-Fan Shao Joseph E Maclennan Lixing Wang David M Walba Noel A Clark 《Chemphyschem》2007,8(1):170-174
We demonstrate, both theoretically and experimentally, that it is possible to use an electric field to drive the formation of macroscopic chiral (conglomerate) domains from an initially homogeneous fluid racemate. Field-induced segregation is exhibited in a fluid smectic liquid-crystal phase of a racemic mesogen, wherein enantiomerically-enriched domains are readily identifiable by their chiral electro-optical response. The sharp field-generated boundaries that form between opposite-handed domains broaden by diffusion in the absence of field, but reform rapidly if the field is switched on again, providing unambiguous evidence for the field-driven physical separation of enantiomers. A mean-field model successfully describes the steady-state and the dynamic evolution of conglomerate formation. 相似文献
942.
García F Hopkins AD Kowenicki RA McPartlin M Tesa Y 《Dalton transactions (Cambridge, England : 2003)》2004,(14):2051-2052
The reaction of (Me(3)Si)(3)SiK[middle dot]18-crown-6 with SbCl(3)(3 : 1 equiv.) provides a simple route to the title complex [(Me(3)Si)(3)SiSb](4). The potassium base initially acts as a nucleophile and then as a coupling agent, forming Sb-Sb bonds. 相似文献
943.
Molybdenum is extracted as the thiocyanate complex with the quaternary long-chain aliphatic amine Aliquat 336 in chloroform, followed by evaporation of the solvent, dissolution in MIBK, and atomic-absorption spectroscopy. The method is simple, rapid and sensitive, with few interference problems for the determination of the Mo content of soils and sediments in the range 0.1-1.0 ppm with a relative standard deviation better than 5% when 1-g samples are used. Quantitative extraction from large volumes of aqueous solution has also been confirmed, allowing the determination of Mo in natural waters in the ppM range. 相似文献
944.
Alexander Marunkov Nikolai Chekalin Jonas Enger Ove Axner 《Spectrochimica Acta Part B: Atomic Spectroscopy》1994,49(12-14)
A laser-induced fluorescence in graphite furnace (LIF-GF) set-up has been equipped with an intensified CCD detector (ICCD) that enables simultaneous multichannel detection of large wavelength regions. The main advantages of such a system in comparison with conventional photomultiplier detection are: simultaneous detection of several fluorescence wavelengths for easy characterization of excitation and fluorescence spectra and for an increase of the absolute sensitivity and spectral selectivity; simultaneous monitoring of background signals, such as those due to matrix interferences, blackbody radiation and scattered laser light; decrease of the susceptibility to radio-frequency pick-ups emitted from the pump laser due to the delayed read-out procedure; time-resolved studies of fluorescence spectra for improved elemental selectivity or for studies of atomization processes, and a possibility to perform two-dimensional imaging of height distributions of atomization and, in combination with an imaging spectrometer, diffusion processes in the furnace. The first work on LIF-GF with ICCD detection has been performed on Ni. The most sensitive and versatile excitation and detection wavelengths have been identified. Detection limits in water solutions by the LIF-GF technique have been improved by two orders of magnitude and are found to be 0.015 pg with ICCD and 0.01 pg using a photomultiplier at the most sensitive excitation and detection wavelengths. Nickel in
concentrations has been detected in aqueous standard reference samples with sodium concentrations ranging from
to % (riverine water and estuarine water) with good accuracy and precision. The Ni contents of standard riverine and estuarine water were determined to 1.00 ± 0.11 and 0.75 ± 0.07 ng/ml, respectively. The certified concentrations are 1.03 ± 0.10 and 0.743 ± 0.078
. 相似文献
945.
Khlobystov AN Brett MT Blake AJ Champness NR Gill PM O'Neill DP Teat SJ Wilson C Schröder M 《Journal of the American Chemical Society》2003,125(22):6753-6761
A series of structurally related binuclear metallacycles [Cd(NO(3))(2)L](2), where L is an angular exo-bidentate ligand, have been synthesized. Each metallacycle contains two coordinatively unsaturated, chiral metal centers within a single molecule, and the assembly of these metallacycles into polymeric framework structures has been studied systematically for the first time. Stereoselective homochiral association of [Cd(NO(3))(2)L](2) leads to the formation of helical coordination polymers, whereas meso type association results in nonhelical chain structures. The type of stereoselective aggregation depends on the conditions of self-assembly as well as on ligand functionality. Both helical and nonhelical polymeric complexes have been isolated for the metallacycle [Cd(NO(3))(2)(2,4'-pyacph)](2) (2,4'-pyacph = 2,4'-(4-ethynylphenyl)bipyridyl). Homochiral association results in the formation of helical [Cd(NO(3))]( infinity ) chains which link the binuclear [Cd(NO(3))(2)(2,4'-pyacph)](2) metallacycles into racemic two-dimensional sheets which contain both P and M [Cd(NO(3))]( infinity ) helices. In contrast, meso-association leads to the formation of nonhelical one-dimensional chains. It is shown that the product of homochiral association is predominately formed at room temperature and that of meso-association is generated at elevated temperatures. Thus, it may be concluded that the homochiral association appears to be energetically less favorable than the meso-association, a conclusion that has been confirmed by theoretical calculations of the crystal lattice energy. Several high-yield syntheses of bipyridyl-type ligands used for metallacyclic assembly are also reported. 相似文献
946.
Horseradish peroxidase catalyzed grafting of acrylamide (AM) onto Kevlar fibers has been studied. The modified fiber has been characterized with scanning electron microscopy (SEM), elemental analysis and the grafting yield. From the SEM micrographs, the surface of the grafted Kevlar fiber is rougher than that of the untreated fiber, and the elemental analysis indicated that the nitrogen content of the treated fibers is higher than that of the untreated fiber. All the results suggested that AM must have been grafted onto the Kevlar surface through HRP-mediated radical initiated grafting reaction. The probably mechanism of HRP catalyzed grafting of AM onto Kevlar surface is proposed. 相似文献
947.
Mikhail S. Novikov Alexander F. Khlebnikov Elena S. Sidorina Rafael R. Kostikov 《Journal of fluorine chemistry》1998,90(2):1553-119
2-Fluoropyrroles were synthesised via 1,3-dipolar cycloaddition of iminiodifluoromethanides derived from corresponding imines and difluorocarbene to dimethyl acetylenedicarboxylate. 相似文献
948.
Taw FL Mueller AH Bergman RG Brookhart M 《Journal of the American Chemical Society》2003,125(32):9808-9813
Cationic Rh(III) complex [Cp(PMe(3))Rh(SiPh(3))(CH(2)Cl(2))]BAr(4)' (1) activates the carbon-carbon bond of aryl and alkyl cyanides (R-CN, where R = Ph, (4-(CF(3))C(6)H(4)), (4-(OMe)C(6)H(4)), Me, (i)Pr, (t)Bu) to produce complexes of the general formula [Cp*(PMe(3))Rh(R)(CNSiPh(3))]BAr(4)'. With the exception of the (t)BuCN case, every reaction proceeds at room temperature (t(1/2) < 1 h for aryl cyanides, t(1/2) < 14 h for alkyl cyanides). A general mechanism is presented on the basis of (1) an X-ray crystal structure determination of an intermediate isolated from the reaction involving 4-methoxybenzonitrile and (2) kinetic studies performed on the C-C bond cleavage of para-substituted aryl cyanides. Initial formation of an eta(1)-nitrile species is observed, followed by conversion to an eta(2)-iminoacyl intermediate, which was observed to undergo migration of R (aryl or alkyl) to rhodium to form the product [Cp*(PMe(3))Rh(R)(CNSiPh(3))]BAr(4)'. 相似文献
949.
Zhivka J. Simeonova Kiril B. Gavazov Alexander V. Alexandrov 《Central European Journal of Chemistry》2006,4(2):258-265
The formation of a new ternary ion-associate complex of vanadium(V) with 2,3-dihydroxynaphthalene and iodonitrotetrazolium
chloride with a composition ratio of 1:2:1 is reported. The complex is quantitatively extracted from water into chloroform.
The molar absorptivity (ɛ) of the extract at λ
max=340 nm is 2.5 × 104 dm3/mol cm, and Beer’s law is obeyed for concentrations ranging from 0.1 to 0.9 μg/cm3 V(V). The following constants are determined: the extraction constant, the association constant, the distribution constant,
and the recovery factor. The effects of foreign ions and reagents are studied. A selective and sensitive method is developed
for determination of vanadium in steels. 相似文献
950.