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91.
A tetra L-prolinylmethyl derivative of a tetra-sulfonated calix[4]resorcarene (1) is an effective chiral NMR solvating agent for water-soluble compounds with phenyl, pyridyl, bicyclic aromatic, or indole rings. These aromatic compounds form host-guest complexes with the calix[4]resorcarene in water. Complexation of substrates with the calix[4]resorcarene is likely promoted by hydrophobic effects, and bicyclic substrates have association constants with the calix[4]resorcarene larger than those of similar phenyl-containing compounds. Aromatic resonances of the substrates show substantial upfield shifts because of shielding from the aromatic rings of the calix[4]resorcarene, and several resonances in the 1H NMR spectra typically exhibit enantiomeric discrimination. The extent of enantiomeric discrimination depends in part on interactions of the substituent groups of the substrates with the prolinylmethyl groups of the calix[4]resorcarene. The effectiveness of a calix[4]resorcarene prepared from N-methyl-L-alanine (2) as a chiral NMR discriminating agent is compared to the L-prolinylmethyl derivative. 相似文献
92.
Quadrupole mass spectrometry has been employed to characterize the ionic species in the discharges of pure CH4, CH4/H2, and CH4/Ar systems. For pure methane, the major positive ions in the discharge at low pressure (e.g., 0.15 torr) are CH
3
+
, C2H
3
+
, CH
2
+
, C2H
2
+
, CH
4
+
, C2H
4
+
, and C2H
5
+
at high pressure (e.g., 0.5 torr) the major ions are CH
3
+
, C2H
3
+
, C2H
5
+
, C3H
3
+
, C H3H
7
+
, C4H
7
+
, C5H
7
+
, C6H
5
+
, and C7H
7
+
. The relative abundances of C1 ions decrease with increasing pressure, whereas those of higher-order ions increase with pressure. For 5% CH4 + 95% H2 mixture, in addition to those sampling from the pure methane plasma at the lower pressure, H
n
+
ions have also been detected. For 5% CH4 +95% Ar mixture, the principal ions are CH
3
+
, CH
2
+
, CH+, CH
5
+
, Ar+, and ArH+; the ions containing more than two carbon atoms are negligible. In these discharges, the CH
3
+
and C2H
3
+
are the most important positive ions in C1 and C2 ions, respectively. The ions detected are believed to come from the sheath between the electrode and the luminous plasma, and have high kinetic energy. An ion-molecule reaction mechanism is proposed which can well explain the observed main features of ionic products.Died June 1, 1991. 相似文献
93.
A. Michel T. Van Hoang B. Perrin Marie France Llauro 《Polymer Degradation and Stability》1981,3(2):107-119
It has been possible to explain the mechanisms of stabilisation and of the synergistic effects of the β-diketone derivatives claimed in a patent as new stabilisers for improving the efficiency of those recipes based upon zinc and calcium soaps in the prevention of the initial discoloration of poly(vinyl chloride).Using chlorohexene as a model compound for allylic chloride structures and benzoylacetone as a model compound for enolised β-diketone derivatives, it has been shown that the benzoylacetone can substitute allylic chlorine atoms through a C-alkylation reaction which takes place only in the presence of ZnCl2 as catalyst. This reaction drastically changes the percentage of the enol and causes the appearance of two bands at 1720 cm?1 and 1680 cm?1 in the infra-red spectrum due to the ketonic structures During the processing of the PVC on a rolling mill at 180°C in the presence of zinc and calcium stearates and benzoylacetone there is grafting of the ketone derivative through a C-alkylation reaction. There is a closed parallelism between the influence of the benzoylacetone on the dehydrochlorination of the chlorohexene and on the accumulation of chloride ions in the polymer matrix in the presence of zinc and calcium stearate. The synergistic effect of the benzoylacetone in the prevention of the initial discoloration is related to the substitution reaction through a C-alkylation which takes place only in the presence of zinc stearate which generates ZnCl2 which, in turn, acts as a catalyst for both the C-alkylation and dehydrochlorination. 相似文献
94.
Weawkamol Leelapornpisit Minh‐Tan Ton‐That Florence Perrin‐Sarazin Kenneth C. Cole Johanne Denault Benoit Simard 《Journal of Polymer Science.Polymer Physics》2005,43(18):2445-2453
The effect of different concentrations of single‐walled carbon nanotubes (SWNTs) on the nonisothermal crystallization kinetics, morphology, and mechanical properties of polypropylene (PP) matrix composites obtained by melt compounding was investigated by means of X‐ray diffraction, differential scanning calorimetry, optical and scanning electron microscopy, and dynamic mechanical thermal analysis. Microscopy showed well‐dispersed nanotube ropes together with small and large aggregates. The modulus was found to increase by about 75% at a level of 0.5 wt % nanotubes. The SWNTs displayed a clear nucleating effect on the PP crystallization, favoring the α crystalline form rather than the β form. The crystallization kinetics analysis showed a significant increase in activation energy on incorporating nanotubes. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2445–2453, 2005 相似文献
95.
C. Bavoux F. Vocanson M. Perrin R. Lamartine 《Journal of inclusion phenomena and macrocyclic chemistry》1995,22(2):119-130
A new method is described for the synthesis of isolatedp-tert-butyldihomooxacalix[4]arene (CALO) with a 24% yield. The ability of CALO to form complexes in the solid state with small neutral molecules has been studied; the potential guests were common solvents bearing various chemical functions. The powder obtained after evaporation of the solvent has been characterized by the X-ray powder diffraction technique. Analysis of the patterns shows the non-complexation of linear alkanes and alcohols, but formation of complexes when the guest is cyclic or when it bears an amine or a ketone function. As illustration of the possible arrangement of molecules in complexes, the structure of the 1:2 complex with tetrahydrofuran (THF) is presented: the crystals are monoclinic, space groupP21/c,a=9.459(2) Å,b=17.286(2) Å,c=30.469(6) Å, =92.52(2)o,V=4977(2) Å3,Z=4,D
c=1.099 Mg m–3, =1.54178 Å, =5.6 cm–1,R=0.086 for 3590 reflections withF>4 (F); one of the THF molecules is inside the cavity of the macrocycle, while the other, in the interhost space, exhibits disorder. In the CALO molecule, three out of the fourtert-butyl groups are disordered which may induce the disorder of the THF molecule.
Supplementary Data: relating to this article are deposited with the British Library: Supplementary Publication No. Sup. 82191 (29 pages). 相似文献
96.
Alnouti Y Lewis SR White CA Bartlett MG 《Rapid communications in mass spectrometry : RCM》2005,19(4):503-508
A simple liquid chromatography/tandem mass spectrometry (LC/MS/MS) method has been developed and validated for the simultaneous determination of zidovudine (AZT) and lamivudine (3TC) in rat plasma, amniotic fluid, placental, and fetal tissues. Samples were processed by acetonitrile precipitation. Chromatography was performed using a C18 column (5 microm, 150 x 3.9 mm i.d). The mobile phase consisted of 30% methanol and 7.5 mM ammonium acetate (pH 6.5). The method was validated in the range of 0.05-25 microg/mL for both 3TC and AZT in the four biological matrices. Finally, the method was applied to a study involving fetal transport following co-administration of these compounds at a dose of 25 mg/kg each in a pregnant rat. 相似文献
97.
Choi JH Lucas D Koshland CP Sawyer RF 《The journal of physical chemistry. B》2005,109(50):23905-23910
The photochemical interaction of 193 nm light with polystyrene nanospheres is used to produce particles with a controlled size and morphology. Laser fluences from 0 to 0.14 J/cm2 at 10 and 50 Hz photofragment nearly monodisperse 110 nm spherical polystyrene particles. The size distributions before and after irradiation are measured with a scanning mobility particle sizer (SMPS), and the morphology of the irradiated particles is examined with a transmission electron microscope (TEM). The results show that the irradiated particles have a smaller mean diameter ( approximately 25 nm) and a number concentration more than an order of magnitude higher than nonirradiated particles. The particles are formed by nucleation of gas-phase species produced by photolytic decomposition of nanospheres. A nondimensional parameter, the photon-to-atom ratio (PAR), is used to interpret the laser-particle interaction energetics. 相似文献
98.
99.
Chlorine trioxide, Cl(2)O(6), reacts with Au metal, AuCl(3), or HAuCl(4).nH(2)O to yield the well-defined chloryl salt, ClO(2)Au(ClO(4))(4). The crystal and molecular structure of ClO(2)Au(ClO(4))(4) was solved by a Rietveld analysis of powder X-ray diffraction data. The salt crystallizes in a monoclinic cell, space group C2/c, with cell parameters a = 15.074(5), b = 5.2944(2), and c = 22.2020(2) A and beta = 128.325(2) degrees. The structure displays discrete ClO(2)(+) ions lying in channels formed by Au(ClO(4))(4)(-) stacks. Au is located in a distorted square planar environment: Au-O = 1.87 and 2.06 A. [ClO(4)] groups are monodentate with ClO(b) = 1.53 and ClO(t) = 1.39 A (mean distances; O(b), oxygen bonded to Au; O(t), free terminal oxygen). A full vibrational study of the Au(ClO(4))(4)(-) anion is supported by DFT calculations. 相似文献
100.
Two- or three-component aza Diels-Alder reactions of Danishefsky's diene with imines or aldehydes and amines in water took place smoothly under neutral conditions in the presence of a catalytic amount of an alkaline salt such as sodium triflate to afford dihydro-4-pyridones in high yields. 相似文献