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121.
122.
Berthet JC Thuéry P Dognon JP Guillaneux D Ephritikhine M 《Inorganic chemistry》2008,47(15):6850-6862
Addition of 1 or 2 molar equiv of Rbtp [Rbtp = 2,6-bis(5,6-dialkyl-1,2,4-triazin-3-yl)pyridine; R = Me, Pr ( n )] to UO 2(OTf) 2 in anhydrous acetonitrile gave the neutral compounds [UO 2(OTf) 2(Rbtp)] [R = Me ( 1), ( n )Pr ( 2)] and the cationic complexes [UO 2(Rbtp) 2][OTf] 2 [R = Me ( 3), Pr ( n ) ( 4)], respectively. No equilibrium between the mono and bis(Rbtp) complexes or between [UO 2(Rbtp) 2][OTf] 2 and free Rbtp in acetonitrile was detected by NMR spectroscopy. The crystal structures of 1 and 3 resemble those of their terpyridine analogues, and 3 is another example of a uranyl complex with the uranium atom in the unusual rhombohedral environment. In the presence of 1 molar equiv of Rbtp in acetonitrile, UO 2(NO 3) 2 was in equilibrium with [UO 2(NO 3) 2(Rbtp)] and the formation of the bis adduct was not observed, even with an excess of Rbtp. The X-ray crystal structures of [UO 2(NO 3) 2(Rbtp)] [R = Me ( 5), Pr ( n ) ( 6)] reveal a particular coordination geometry with seven coordinating atoms around the UO 2 fragment. The large steric crowding in the equatorial girdle forces the bidentate nitrate ligands to be almost perpendicular to the mean equatorial plane, inducing bending of the UO 2 fragment. The dinuclear oxo compound [U(CyMe 4btbp) 2(mu-O)UO 2(NO 3) 3][OTf] ( 7), which was obtained fortuitously from a 1:2:1 mixture of U(OTf) 4, CyMe 4btbp, and UO 2(NO 3) 2 [CyMe 4btbp = 6,6'-bis-(3,3,6,6-tetramethyl-cyclohexane-1,2,4-triazin-3-yl)-2,2'-bipyridine] is a very rare example of a mixed valence complex involving covalently bound U (IV) and U (VI) ions; its crystal structure also exhibits a seven coordinate uranyl moiety, with one bidentate nitrate group almost parallel to the UO 2 fragment. The distinct structural features of [UO 2(kappa (2)-NO 3) 2(Mebtp)], with its high coordination number and a noticeable bending of the UO 2 fragment, and of [UO 2(kappa (2)-NO 3)(kappa (1)-NO 3)(terpy)], which displays a classical geometry, were analyzed by Density Functional Theory, considering the bonding energy components and the molecular orbitals involved in the interaction between the uranyl, nitrate, and Mebtp or terpy moieties. The unusual geometry of the Mebtp derivative with the seven coordinating atoms around the UO 2 fragment was found very stable. In both the Mebtp and terpy complexes, the origin of the interaction appears to be primarily steric (Pauli repulsion and electrostatic); this term represents 62-63% of the total bonding energy while the orbital term contributes to about 37-38%. 相似文献
123.
Pichon C Dolbecq A Mialane P Marrot J Rivière E Sécheresse F 《Dalton transactions (Cambridge, England : 2003)》2008,(1):71-76
Two new insoluble transition metal substituted phosphotungstates, (C2N2H10)11[{(B-alpha-PW9O34)Fe3(OH)3}4(PO4)4Fe].38H2O(1) and K4(C2N2H10)12[(alpha-PW10Fe2O39)4].30H2O(2), have been isolated by the hydrothermal reaction of [A-alpha-PW9O34]9-, Fe(III) ions and ethylenediamine. Compound 1 has a tetrahedral symmetry and contains a Fe13 core built from the assembly of four Fe(III) trisubstituted [B-alpha-PW9O34]9- anions around a central disordered iron ion via four phosphato ligands. The anion in 2 can be described as a square of disubstituted [PW10O37]9- anions linked by Fe(III)-O-Fe(III) bridges. Magnetic measurements performed on 1 and 2 have shown the occurrence of antiferromagnetic interactions between the iron ions and have allowed the coupling constants between the magnetic centers to be determined. 相似文献
124.
Heck vinylation of 2-bromo-6-methyl-3-substituted pyridines using η3-allylpalladium chloride dimer/P(o-Tol)3 complex/toluene and dimethylacetamide (DMA) as co-solvent with methyl acrylate is reported. Electronic and steric effects were investigated engaging diversely 2-bromo-3,6-disubstituted pyridines. As application, a new synthesis of the 6-methyl cyclopenta[b]pyridinone building-block connecting Heck vinylation, alkene reduction and Dieckmann condensation is described. 相似文献
125.
Figueredo G Chalchat JC Chalard P Ozcan MM Al Juhaimi FY 《Natural product research》2012,26(19):1852-1856
The essential oils of sage leaves (Salvia aucheri Bentham var. canescens Boiss. & Heldr.), growing wild in South Anatolia, were extracted by hydrodistillation and analysed by GC and GC-MS. The percentage yields of the essential oils from sage leaves harvested at different years were 1.0%, 1.3%, 1.3%, 1.0%, 1.4%, 1.5% and 1.2%, respectively. In this study, 1,8-cineole, camphre, camphene α-pinene and β-pinene were identified as the major components of sage leaves collected at different periods. The main constituents of sage oil collected over the years were 1,8-cineole (35.01-48.06%), camphre (13.58-23.92%), camphene (6.77-8.82%), α-pinene (5.79-8.54%) and β-pinene (4.32-6.28%). 相似文献
126.
Ibarra IA Yang S Lin X Blake AJ Rizkallah PJ Nowell H Allan DR Champness NR Hubberstey P Schröder M 《Chemical communications (Cambridge, England)》2011,47(29):8304-8306
The metal-organic frameworks NOTT-400 and NOTT-401, based on a binuclear [Sc(2)(μ(2)-OH)(O(2)CR)(4)] building block, have been synthesised and characterised; the desolvated framework NOTT-401a shows a BET surface area of 1514 m(2) g(-1) with a total H(2) uptake of 4.44 wt% at 77 K and 20 bar. 相似文献
127.
128.
Sb4Te3 and Sb8Te9 are members of the homology (Sb2Te3)m.(Sb2)n, with structures consisting of Sb2- and Sb2Te3-type slabs stacked along [001]; electrical conductivity and thermopower are reported for several members of this family. 相似文献
129.
Cover Picture: Densely Packed Hydrophobic Clustering: Encapsulated Valerates Form a High‐Temperature‐Stable {Mo132} Capsule System (Angew. Chem. Int. Ed. 23/2016) 下载免费PDF全文
130.
A europium probe for the ratiometric detection of potassium in water is presented. This probe demonstrates high sensitivity, with an affinity for K(+) in the mM range, and high selectivity for K(+) over Na(+), Ca(2+), Mg(2+) and Li(+). The long luminescence lifetime of the probe and its large Stokes shift further enable accurate determination of the concentration of K(+) in complex aqueous media. 相似文献