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31.
32.
Riehn C Matylitsky VV Jarzeba W Brutschy B Tarakeshwar P Kim KS 《Journal of the American Chemical Society》2003,125(52):16455-16462
In this paper, we report the use of femtosecond time-resolved degenerate four-wave mixing rotationally resolved spectroscopy to obtain very accurate structural information on the symmetric top cyclohexane. Apart from highlighting the versatility of this method in determining accurate structures of large and complex molecules without dipole moment, the present study also details the comparison of the experimentally determined rotational constant B(0) with that obtained from high-level ab initio calculations. The theoretical calculations, which were carried out at both the second-order M?ller-Plesset (MP2) and coupled-cluster with single, double, and perturbative triple substitutions [CCSD(T)] levels of theory, also take into account vibrational averaging effects. A detailed investigation of the vibrational averaging effects reveals that the corrections emerge from only the six highly symmetric A(1g) modes, a justification of which is provided by an analysis of these modes. 相似文献
33.
"Bare" CeO(2)(+) ions can be prepared in the gas phase by consecutive oxidation of Ce(+) with O(2) and NO(2). The ability to activate saturated and unsaturated hydrocarbons is investigated by use of Fourier-transform ion cyclotron resonance mass spectrometry. In the reactions of CeO(2)(+) with linear and branched alkanes C-H bond activation is observed almost exclusively. In contrast, both oxygen-atom transfer and C-H bond activation processes occur when thermalized CeO(2)(+) cations react with simple alkenes and aromatic compounds. C-C bond activation is not observed at all. Insight into the structural and electronic properties of neutral CeO(2) and cationic CeO(2)(+) is provided by means of quasirelativistic density-functional and ab initio pseudopotential calculations. They reveal a (2)Sigma(u)(+) ground state for CeO(2)(+) which is best described as a linear cerium dioxide with a resonating pi bond. Finally, we discuss the influence of oxo ligands on the chemistry of the cationic CeO(n)()(+) (n = 0-2) species toward hydrocarbons. 相似文献
34.
We present a quantum-chemical analysis of the molecular structure and second- and third-order polarizabilities in a series of promising nonlinear optical (NLO) chromophores, the zwitterionic ammonio/borato diphenylpolyenes, R3N+Ph(C=C)nPhB-R3, whose synthesis has been reported recently. The molecular geometries are obtained via MP2/6-31G optimization, while the NLO properties are calculated with the INDO Hamiltonian using the sum-over-states and finite-field real-space methods. The real-space approach allows the direct evaluation of the NLO-active segments of the molecules, while the sum-over-states results illustrate the virtual excitations and charge-transfer pathways that are essential in the NLO response. Both methods highlight the remarkable and unexpected result that it is the strongly polarized phenylene groups that play the key role in generating a high NLO response. 相似文献
35.
(2S,4S)-2-(tert-Butyl)-5-oxo-1,3-dioxolan-4-acetic acid ( 1 ) was dilithiated to the enolate 2 in toluene and THF with lithium diisopropylamide (LiN(i-Pr)2) under various conditions. Deuteration experiments with 2 showed that two different stable forms of the enolate could be produced, depending on whether the deprotonation of 1 had been carried out in toluene or THF. The generated (i-Pr)2NH was coordinated to the enolate and, hence, served as a strong lipophilic solvating agent. LiN(i-Pr)2 could substitute the amine ligands of the two species to a different extent. THF was partially able to displace (i-Pr)2NH that solvated the species produced in toluene, but the coordination of the amine to the one produced in THF was quantitive. Correlations with given explanations are made. 相似文献
36.
Kammerer B Kahlich R Ufer M Laufer S Gleiter CH 《Rapid communications in mass spectrometry : RCM》2004,18(4):458-464
Phenprocoumon is a commonly used oral anticoagulant of the coumarin type, and has found extensive clinical use in the treatment of thrombophlebitis, pulmonary embolism and atrial fibrillation. In the course of a clinical study to investigate the influence of genetic polymorphisms of the CYP2C9 enzyme on phenprocoumon metabolism, we developed a new enantioselective liquid chromatography/electrospray ionisation tandem mass spectrometry (LC/MS/MS) method to quantify (R)- and (S)-phenprocoumon in human plasma. HPLC separation of the enantiomers was achieved on a Chira-Grom-2 column under isocratic conditions using a water/acetonitrile/formic acid eluent. For detection and quantification a triple-quadrupole MS system was used in the selected reaction monitoring (SRM) mode. As an internal standard the structurally homologous compound warfarin was chosen. The detector response was linear with a correlation coefficient of 0.988-0.999 for (R)-phenprocoumon and 0.989-0.999 for (S)-phenprocoumon in the investigated concentration range between 62.5 and 1000 ng/mL (per enantiomer). The limit of detection (LOD) was 12.5 ng/mL. 相似文献
37.
We explore here an approach to mimic the structures and biological functions of protein loops in small synthetic molecules, by grafting the loop of interest onto an organic template comprising a bicyclic diketopiperazine, prepared by the formal coupling of (2S,4S)-4-aminoproline (Pro(NH2)) and aspartic acid (Asp). The Fmoc-protected template 4 is used to prepare cyclo(-Ala1-Asn2-Pro3-Asn4-Ala5- Ala6-Temp-) ( 5 ) and cyclo(-Ala1-Arg2-Gly3-Asp4-Temp-) ( 6 ) (where Temp = template derived from 4 ), containing the Asn-Pro-Asn-Ala (NPNA) and Arg-Gly-Asp (RGD) motifs. The conformational properties of these molecules are studied in aqueous solution by NMR and simulated-annealing methods. The NPNA motif, an immunodominant epitope on the circumsporozoite surface protein of the malaria parasite Plasmodium falciparum, is shown to adopt a stable type-I β-turn in 5 . The template in 5 adopts a preferred conformation with Pro(NH2)χ1 ≈? ?35° and the Asp moiety χ1 ≈? 70°. A different template conformation is inferred for 6 , with Pro(NH2)χ1 ≈? 0°, but the ARGD loop appears by NMR to undergo rapid conformational averaging. Solid-phase binding assays reveal that 6 displays modest antagonist activity towards both the integrin αIIbβ3 and αvβ3 receptors. 相似文献
38.
Franz Andreas Mautner Harald Krischner Christoph Kratky 《Monatshefte für Chemie / Chemical Monthly》1988,119(11):1245-1249
[N(CH3)4]Ca(N3)3,M=240.29, was prepared from aqueous solutions of tetramethylammoniumazide with calciumazide at 298 K. The crystals are tetragonala=936.6(7) pm,c=694.7(5)pm, space group P4/nmm,Z=2, (x)=1.31Mgm–3. The crystal structure was determined by single crystal x-ray diffraction (234 Mo-K-reflections, =0.469 mm–1,R=0.064). Calcium is octahedrally coordinated to six azide groups. The octahedra are connected via azide groups to a threedimensional array with the complex ammonium ions between. The terminal nitrogen atoms of the azide groups and the methyl groups are considerably disordered. 相似文献
39.
Barbara Dogan Hans-Dieter Beckhaus Hermann Birkhofer Christoph Rüchardt 《欧洲无机化学杂志》1990,123(6):1365-1368
Effects of Substituents on the Strength of C - C Bonds, 81. - Heats of Formation and Strain of 1,1,2,2-Tetraethylethylene Glycol Dimethyl Ether and D,L .-1,2-Dimethyl-l,2-diphenylethylene Glycol Dimethyl Ether The heats of combustion of the title compounds 1 and 2 were measured calorimetrically with the result (kcal mol -1, s. d. in parentheses) ΔH°c = − 1880.1 (± 0.6) and − 2373.3 (± 1.4). The heat of vaporisation of 1 ΔHv = 14.3 (± 0.3) and the heat of sublimation of 2 ΔHsub = 27.2 (± 0.5) were derived from their temperature dependance of the vapor pressure. The latter were determined between 30 and 80°C using a flow method. The resulting standard heats of formation ΔH°t(g) = −122.4 (± 0.7) and −43.8 (±1.5) for 1 and 2 correspond to a strain enthalpy (s) of 15.9 and 8.0 kcal mol-1, respectively. The steric strain of the dimethoxyethanes 1 and 2 is about one fourth lower than the strain of the corresponding dimethylethanes 3 and 4 bearing the same substituents. Thus, a methoxy group causes less steric stress than a methyl group. 相似文献
40.
Christoph Luef Aloke Paul Jiri Vizdal Ales Kroupa Alexander Kodentsov Herbert Ipser 《Monatshefte für Chemie / Chemical Monthly》2006,137(4):381-395
Summary. The partial and integral enthalpies of mixing of liquid Bi–Sn–Zn alloys were determined at 500°C by a drop calorimetric technique
using a Calvet-type microcalorimeter. The ternary interaction parameters in the Bi–Sn–Zn system were fitted using the Redlich-Kister-Muggianu model for substitutional solutions, and isoenthalpy curves of the integral molar enthalpy of mixing at 500°C were constructed.
Furthermore, a DSC technique was used to determine the liquidus temperatures in three sections (3, 5, and 7 at.% Zn) as well
as the invariant reaction temperature of the ternary eutectic L ⇄ (Bi) + (Sn) + (Zn). The ternary eutectic reaction was found
at 135°C. 相似文献