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971.
Devillers CH Dime AK Cattey H Lucas D 《Chemical communications (Cambridge, England)》2011,47(6):1893-1895
Regioselective meso-functionalization of the totally unsubstituted magnesium(II) porphine was performed by controlled potential electrolysis with pyridine and triphenylphosphine as nucleophiles leading to the original pyridinium and phosphonium substituted derivatives, respectively. The crystallographic structure of the latter is described as the only meso-phosphonium porphyrin reported to date. 相似文献
972.
Murat Taş Seval Çamur Yalçın Kılıç 《Journal of Thermal Analysis and Calorimetry》2011,103(3):995-1000
The complexes were synthesized by the reaction between sodium salt of p-aminosalicylic acid (PAS) and Cu(II) for 1 and corresponding ethylenediamine (en) or its derivatives for 2–6. The complexes were characterized by using elemental analyses, FT-IR, UV–Vis, magnetic moment measurements, and thermal analyses
techniques. In complex 1[Cu2(PA)4(H2O)2], two Cu(II) ions were found as bridged by four μ-O:O′ p-aminosalicylato (PA) ligands, forming a cage structure, and two aqua ligands to form dinuclear square-pyramidal geometry
around Cu(II) ions. In the complexes 2–6, the PA (anionic form of p-aminosalicylic acid) coordinated to Cu(II) ions as monodentate manner by using its oxygen atom of deprotonated carboxylic
acid and ethylenediamine derivatives coordinated to the Cu(II) ions in bidentate manner to form mononuclear octahedral complexes
[Cu(PA)2(L)2] (L = ethylendiamine, N,N-dimethylethylendiamine, N,N′-dimethylethylendiamine, N,N,N′,N′-tetramethylethylendiamine, and 1,3-propanediamine, for complexes 2, 3, 4, 5, and 6, respectively). In all the complexes OH and NH2 groups of PA ligands were not coordinated to metals. 相似文献
973.
Julen Ibarretxe Gabriël Groeninckx Vincent B. F. Mathot 《Journal of Thermal Analysis and Calorimetry》2011,106(1):285-298
In samples containing a volatile phase, quite often the evaporation of the volatile substance during heating causes appreciable
curvature of the DSC heat flow rate signal as function of temperature, making it difficult to quantify thermal transitions
and reorganization phenomena occurring in the same temperature range. This is the case for e.g. polyamide–water, polyamide–alcohol,
and polypropylene–water systems, thus complicating the study of polymer crystallization, melting, and metastability by DSC.
In this study, maleic anhydride-grafted polypropylene particles of sub-micrometer diameters dispersed in water are discussed.
These samples show, upon cooling from the melt, different degrees of extra supercooling in crystallization and several phenomena
in the subsequent heating, like reorganization of a crystalline phase into another one, perfecting of crystallites, and melting.
All these phenomena are difficult to analyze quantitatively due to the mentioned curvature of the DSC trace. In this article
two methods, the “Reference” and “Extrapolation from the melt” methods, are described to correct for the influence of evaporation
on the DSC heat flow rate signal and for the baseline signal, enabling the discussion of the transitions by way of the excess
heat flow rate as function of temperature. 相似文献
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977.
Dr. Gaël Rouillé Mathias Steglich Dr. Cornelia Jäger Prof. Dr. Friedrich Huisken Prof. Dr. Thomas Henning Gabriele Theumer Dr. Ingmar Bauer Prof. Dr. Hans‐Joachim Knölker 《Chemphyschem》2011,12(11):2131-2137
We report on the characterization of dibenzo[cde,opq]rubicene (C30H14). The molecule was studied in solution at room temperature with absorption spectroscopy in the visible (vis) and ultraviolet (UV) wavelength ranges, and with emission spectroscopy. The infrared (IR), visible, ultraviolet, and vacuum ultraviolet (VUV) absorption spectra of a thin film were measured also at room temperature. In addition, the UV/vis absorption spectrum was measured at cryogenic temperatures using the matrix isolation spectroscopy technique. The interpretation of spectra was supported by theoretical calculations based on semiempirical and ab initio models, as well as on density functional theory. Finally, the results of the laboratory study were compared with interstellar spectra. 相似文献
978.
Deschamps M Fayon F Cadars S Rollet AL Massiot D 《Physical chemistry chemical physics : PCCP》2011,13(17):8024-8030
Measuring internuclear distances through dipolar interaction is a major challenge for solid-state nuclear magnetic resonance (NMR) spectroscopy. Obtaining reliable interatomic distances provides an access to the local structure in ordered or disordered solids. We show that at magic angle spinning (MAS) frequencies larger than ca. 50 kHz, some of the three-spin terms of the homogeneous homonuclear dipolar Hamiltonian can be used to promote the creation of double-quantum coherences between neighbouring (1)H or (19)F spins without using dipolar recoupling pulse sequences in the Dipolar Homonuclear Homogeneous Hamiltonian (DH(3)) double-quantum/single-quantum correlation experiment. This makes it possible to probe inter-nuclear spatial proximity with limited risk of probe or sample damage from radio-frequency (RF) irradiation, and is fully appropriate for fast repetition rate offering sensitivity gains in favourable cases. Experimental demonstrations are supported by multi-spin numerical simulations, which points to new possibilities for the characterization of spin-system geometries. 相似文献
979.
Vérot M Rota JB Kepenekian M Le Guennic B Robert V 《Physical chemistry chemical physics : PCCP》2011,13(14):6657-6661
The chemical control of magnetic and conduction properties for organic radicals is mainly based on t, the resonance integral, and U, the on-site repulsion, used in the Hubbard model. A qualitative analysis based on the competition between the kinetic and the Coulomb contribution, and the expression of the magnetic exchange coupling suggests that U should be roughly 800 cm(-1) while the resonance integral |t| should be 200 cm(-1) to reach bifunctionality. Ab initio wavefunction-based calculations allowed us to quantitatively measure those quantities for several organic materials considered as 1D systems starting from their reported crystal structures. The extraction of t and U parameters from the exchange coupling constants between neighbouring radicals allowed us to anticipate a possible metallic behaviour. Finally, the impact of chemical changes in the constitutive units is measured to rationalize the macroscopic behaviour modifications. It is shown that the intriguing regime characterized by simultaneous itinerant and localized electrons might be achieved by molecular engineering. 相似文献
980.
Sakko A Galambosi S Inkinen J Pylkkänen T Hakala M Huotari S Hämäläinen K 《Physical chemistry chemical physics : PCCP》2011,13(24):11678-11685
We report non-resonant inelastic X-ray scattering experiments of several gaseous samples in the inner-shell excitation energy range. The experimental near-edge spectra from all the K-edges of N(2), N(2)O, and CO(2) including the momentum transfer dependence are presented. The results are analyzed using density functional theory calculations that accurately reproduce the experimental spectral features. We observe vibrational effects in the measured spectrum and in the calculations the atomic motion is modeled using the Franck-Condon approximation and the linear coupling model. Our findings show that vibrational effects cannot be neglected in the analysis of high resolution inelastic X-ray scattering spectroscopy. The results also support the validity of the transition potential approximation for calculating core excited state potential energy surfaces. 相似文献