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31.
Contrary to an earlier report, lithiation of tris(trimethylsilyl)methane followed by carbonation does not yield the acid (Me3Si)3CCO2H, (I), if an alkali extraction step is included in the work up; the product is actually the acid (Me3Si)2CHCO2H, (II). The acid (I) can be obtained if the alkali extraction is omitted. Separate experiments have confirmed that (I) is rapidly converted into (II) by aqueous or methanolic base. 相似文献
32.
Metal-organic frameworks with exceptionally high capacity for storage of carbon dioxide at room temperature 总被引:4,自引:0,他引:4
Metal-organic frameworks (MOFs) show high CO2 storage capacity at room temperature. Gravimetric CO2 isotherms for MOF-2, MOF-505, Cu3(BTC)2, MOF-74, IRMOFs-11, -3, -6, and -1, and MOF-177 are reported up to 42 bar. Type I isotherms are found in all cases except for MOFs based on Zn4O(O2C)6 clusters, which reveal a sigmoidal isotherm (having a step). The various pressures of the isotherm steps correlate with increasing pore size, which indicates potential for gas separations. The amine functionality of the IRMOF-3 pore shows evidence of relatively increased affinity for CO2. Capacities qualitatively scale with surface area and range from 3.2 mmol/g for MOF-2 to 33.5 mmol/g (320 cm3(STP)/cm3, 147 wt %) for MOF-177, the highest CO2 capacity of any porous material reported. 相似文献
33.
Baudron SA Batail P Rovira C Canadell E Clérac R 《Chemical communications (Cambridge, England)》2003,(15):1820-1821
Neutral pi-conjugated molecules and their radical cations co-exist in [(EDT-TTF-CONHMe+*)4(EDT-TTF-CONHMe0)2] [Re6Se8(CN)6]4- (CH3CN)2(CH2Cl2)2 whose crystal structure reveals that, upon one-electron oxidation, an activation of the N-H and C-H hydrogen bond donor ability is coupled to a deactivation of the hydrogen bond acceptor character of the carbonyl oxygen atom: this is expressed in the supramolecular hydrogen bond pattern and, ultimately, into charge localisation and partition in the solid state. 相似文献
34.
Teresa M V D Pinho e Melo Cláudia S J Lopes António M d'A Rocha Gonsalves Ana M Beja José A Paix?o Manuela R Silva Luiz Alte da Veiga 《The Journal of organic chemistry》2002,67(1):66-71
Nucleophilic substitution reactions of 2-halo-2H-azirines 1a, 1b, 1d, and 1e with potassium phthalimide and aniline allowed the preparation of new substituted 2H-azirines 2-5. The reactions of 2-bromo-2H-azirine 1a with methylamine led to the synthesis of alpha-diimines 7 and 8. 2-Halo-2H-azirines were also established as building blocks for the synthesis of a range of heterocyclic compounds, namely, quinoxalines 10a-10d, 3-oxazoline 14, and 2H-[1,4]oxazines 18 and 20. X-ray crystal structures of alpha-diimine 7, 3-oxazoline 14, and 2H-[1,4]oxazine 18 are reported. 相似文献
35.
Massue J Bellec N Chopin S Levillain E Roisnel T Clérac R Lorcy D 《Inorganic chemistry》2005,44(24):8740-8748
The reaction of tris(alkylthio)tetrathiafulvalene thiolates with 3-chloro-2,4-pentanedione affords tetrathiafulvalene (TTF) moieties substituted by the acetylacetone function (TTFSacacH), precursors of novel redox-active ligands: the acetylacetonate ions (TTFSacac). These TTFSacacHs have been characterized by X-ray diffraction analyses, and similar trends have been observed, such as a TTF core almost planar and the acetylacetone substituent located in a plane almost perpendicular to the plane formed by the TTF core. Their chelating ability has been demonstrated by the formation of the corresponding M(TTFSacac)2(pyridine)2 complexes in the presence of M(II)(OAc)2.H2O (M = Ni2+, Zn2+). These complexes with TTFSacac moieties, Ni(TTFSacac)2(pyridine)2, 6b, and Zn(TTFSacac)2(pyridine)2, 7b, have been characterized by X-ray diffraction analyses, showing in all structures the metal(II) center chelated by two TTFacac units in the equatorial plane and the octahedral coordination geometry around the metal completed by two axial pyridine ligands. Cyclic voltammetry and UV-visible-near infrared spectroscopic measurements have evidenced a sizable interaction between the two electroactive ligands and the stabilization of a mixed-valence state in the one-electron oxidized complexes. 相似文献
36.
37.
Résumé L'analyse de coupes lourdes (huile de distillation sous vide et huile issue du séparateur à chaud) provenant de l'hydroliquéfaction
catalytique du charbon a été réalisée par mise en ouvre de différentes techniques chromatographiques. L'identification des
principales structures résulte de l'application de la chromatographie par couplage de transfert de charge en mode HPLC et
des spectroscopies UV et de masse.
Donotor-acceptor complex chromatography —Application to analysis of coal liquefaction products by HPLC
Summary A Vacuum gas oil and the corresponding residue of a coal liquefaction product were investigated by means of HPLC and MS. Nearly a complete identification was performed by chromatographic, UV-spectroscopic methods and MS.
相似文献
38.
A new Cu(II) complex, [Cu(3)(dcp)(2)(H(2)O)(4)](n), with the ligand 3,5-pyrazoledicarboxylic acid monohydrate (H(3)dcp) has been prepared by hydrothermal synthesis, and it crystallizes in the monoclinic space group P2(1)/c with a = 11.633(2) A, b = 9.6005(14) A, c = 6.9230(17) A, beta = 106.01(2) degrees, and Z = 2. In the solid state structure of [Cu(3)(dcp)(2)(H(2)O)(4)](n), trinuclear [Cu(3)(dcp)(2)(H(2)O)(4)] repeating units in which two dcp(3-) ligands chelate the three Cu(II) ions with the central Cu(II) ion, Cu(1) (on an inversion center), link to form infinite 2D sheets via syn-anti equatorial-equatorial carboxylate bridges between Cu(2) atoms in adjacent trimers. These layers are further linked by syn-anti axial-equatorial carboxylate bridging between Cu(1) atoms in adjacent sheets resulting in the formation of a crystallographic 3D network. A detailed analysis of the magnetic properties of [Cu(3)(dcp)(2)(H(2)O)(4)](n) reveals that the dcp(3-) ligand acts to link Cu(II) centers in three different ways with coupling constants orders of magnitude apart in value. In the high temperature region above 50 K, the dominant interaction is strongly antiferromagnetic (J/k(B) = -32 K) within the trimer units mediated by the pyrazolate bridges. Below 20 K, the trimer motif can be modeled as an S = 1/2 unit. These units are coupled to their neighbors by a ferromagnetic interaction mediated by the syn-anti equatorial-equatorial carboxylate bridge. This interaction has been estimated at J(2D)/k(B) = +2.8 K on the basis of a 2D square lattice Heisenberg model. Finally, below 3.2 K a weak antiferromagnetic coupling (J(3D)/k(B) = -0.1 K) which is mediated by the syn-anti axial-equatorial carboxylate bridges between the 2D layers becomes relevant to describe the magnetic (T, H) phase diagram of this material. 相似文献
39.
Three new linear compounds of the type Co(3)(dpa)(4)X(2), where dpa is the anion of di(2-pyridyl)amine and X is NCS(-) (5), CN(-) (6), and N(CN)(2)(-) (7), have been prepared, and their structures and magnetic behavior have been studied. In all of them, including three different solvates of 5, the Co(3) chains are symmetrical with Co-Co distances of ca. 2.31-2.32 A. The appearance of four lines in the (1)H NMR spectra of the three compounds is also consistent with a symmetrical structure in solution. For all compounds, the magnetic behavior is quite similar with mu(eff) of ca. 1.9-2.0 micro(B) at temperatures between 1.8 and 200 K. As the temperature increases, the effective moments increase gradually, but since saturation is not reached, even at 400 K, the high-spin state cannot be assigned. 相似文献
40.
Traces of nitrogen can be determined in uranium by reductive fusion in vacuum or in a current of helium. The two methods gave similar results, and these were confirmed by the Kjeldahl method. The excellent agreement between the values obtained made it possible to establish a reference standard. 相似文献