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31.
The alkyl (aryl)-bishydroxymethylphosphines react with primary amines to give the title compounds. With optically active amines optically active phosphines are formed. 相似文献
32.
Woods M Zhang S Ebron VH Sherry AD 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(19):4634-4640
The lanthanide(III) complexes of three tetraamide DOTA bearing pyridyl, phenolic and hydroxypyridyl substituents have been studied by NMR, luminescence and cyclic voltammetry. The relaxivity profiles of the gadolinium complexes of the pyridyl and phenolic ligands were flat and essentially the same between pH 2 and 8. The hydroxypyridyl ligand, however, exhibited two regions of enhanced relaxivity. The small relaxivity enhancement (25 %) at lower pH (pH 2-4) has been attributed to an increase in the prototropic exchange of the coordinated water molecule while the slightly larger enhancement (84 %) at higher pH (pH 6-9) reflects deprotonation of the ligand amide protons. Deprotonation of the amides results in the formation of an intramolecular acid-base pair interaction with the phenolic protons and this, in turn, causes a highly organized second hydration sphere to come into effect, thereby increasing the relaxivity. The water relaxivity of the Gd(3+)-hydroxypyridyl complex is further enhanced upon binding to serum albumin. 相似文献
33.
Paul Von Ragu Schleyer Andrzej Sawaryn Alan E. Reed Pavel Hobza 《Journal of computational chemistry》1986,7(5):666-672
Electron correlation corrections have a considerable influence on the relative stabilities of lithium isocyanide ( 1 ), lithium cyanide ( 2 ), and the bridged form, 3 . While Hartree-Fock theory finds 1 to be most stable and 3 not to be a minimum, MP2/6-31G* optimization indicates 3 to be the global minimum. At higher levels employing full fourth-order Møller-Plesset theory and a quadruply split valence and polarized basis set (MP4STDQ/6-311+G*), 2 is only about 2 kcal/mol less stable than 1 and 3 , which are indicated to have nearly the same energy. LiNC thus is similar to C(Na)N and C(K)N, both of which are known to prefer T-shaped (bridged) structures in the gas phase. However, to an even greater extent than formerly realized, rotation of the lithium cation around the cyanide anion nucleus should be practically free. ΔH (LiCN) = 32.8 kcal/mol is estimated from the calculated lithium cation affinity of 151.2 kcal/mol. In addition, we find at the MP4SDTQ/6-31+G*//MP2/6-31G* level that the bridged form of NaCN is favored by 2–3 kcal/mol over the corresponding linear forms, which have nearly the same energy. 相似文献
34.
The title compounds are synthesized by Michael-type additions of optically active alcohols to the corresponding PO-activated vinylderivatives. 相似文献
35.
Charles W. Stewart C. A. Von Frankenberg 《Journal of Polymer Science.Polymer Physics》1967,5(3):623-631
The thermodynamic properties of amorphous polyethylene are calculated from a model based on the method of significant structures. The motion of a molecule as a whole is described by the motion of segments, each segment moving independently of all others. It is assumed that on melting, holes appear in the solid lattice and the segments can move into these vacancies, obtaining some gaslike degrees of freedom. The complete frequency distribution for polyethylene is used for the solidlike degrees of freedom, while a corrected classical partition function is used for the gaslike degrees of freedom. The calculated thermodynamic properties are in reasonable agreement with experimentally determined values, assuming each gaslike segment to consist of 20 CH2 groups. 相似文献
36.
Synthesis, Crystal Structure and Spectroscopic Properties of the Cluster Anions [(Mo6Br )X ]2? with Xa = F, Cl, Br, I The tetrabutylammonium (TBA), tetraphenylphosphonium (TPP) and tetraphenylarsonium (TPAs) salts of the octa-μ3-bromo-hexahalogeno-octahedro-hexamolybdate(2?) anions [(Mo6Br)X]2? (Xa = F, Cl, Br, I) are synthesized from solutions of the free acids H2[(Mo6Br)X] · 8 H2O with Xa = Cl, Br, I. The crystal structures show systematic stretchings in the Mo? Mo bond length and a slight compression of the Bri8 cube in the Fa to Ia series. The cations do not change much. The i.r. and Raman spectra show at 10 K almost constant frequencies of the (Mo6Bri8) cluster vibrations, whereas all modes with Xa ligand contribution are characteristically shifted. The most important bands are assigned by polarization measurements and the force constants are derived from normal coordinate analysis. The 95Mo nmr signals are shifted to lower field with increasing electronegativity of the Xa ligands. The fluorine compound shows a sharp 19F nmr singlet at ?184.5 ppm. 相似文献
37.
On the Synthesis of Sulfonated Derivatives of 2,3-Dimethylaniline and 3,4-Dimethylaniline Baking the hydrogensulfate salt of 2,3-dimethylaniline ( 1 ) or of 3,4-dimethylaniline ( 2 ) led to 4-amino-2,3-dimethylbenzenesulfonic acid ( 4 ) and 2-amino-4,5-dimethylbenzenesulfonic acid ( 5 ), respectively (Scheme 1). The sulfonic acid 5 was also obtained by treatment of 2 with sulfuric acid or by reaction of 2 with amidosulfuric acid. 3-Amino-4,5-dimethylbenzenesulfonic acid ( 3 ) and 5-Amino-2,3-dimethylbenzenesulfonic acid ( 6 ) were prepared by sulfonation of 1,2-dimethyl-3-nitrobenzene ( 9 ) to 3,4-dimethyl-5-nitrobenzenesulfonic acid ( 11 ) and of 1,2-dimethyl-4-nitrobenzene ( 10 ) to 2,3-dimethyl-5-nitrobenzenesulfonic acid ( 12 ), respectively, with subsequent Béchamp reduction (Scheme 1). Preparations of 2-amino-3,4-dimethylbenzenesulfonic acid ( 7 ) and of 6-amino-2,3-dimethylbenzenesulfonic acid ( 8 ) were achieved by the sulfur dioxide treatment of the diazonium chlorides derived from 3,4-dimethyl-2-nitroaniline ( 24 ) and from 2,3-dimethyl-6-nitroaniline ( 31 ) to 3,4-dimethyl-2-nitrobenzenesulfonyl chloride ( 29 ) and 2,3-dimethyl-6-nitrobenzenesulfonyl chloride ( 32 ), respectively, followed by hydrolysis to 3,4-dimethyl-2-nitrobenzenesulfonic acid ( 30 ) and 2,3-dimethyl-6-nitrobenzenesulfonic acid ( 33 ), and final reduction (Scheme 3). Compound 7 was also synthesized by reaction of 4-chloro-2,3-dimethylaniline ( 23 ) with amidosulfuric acid to 2-amino-5-chloro-3,4-dimethylbenzenesulfonic acid ( 20 ) and subsequent hydrogenolysis (Scheme 2). 4′-Bromo-2′, 3′-dimethyl-acetanilide ( 13 ) and 4′-chloro-2′, 3′-dimethyl-acetanilide ( 14 ) on treatment with oleum yielded 5-acetylamino-2-bromo-3,4-dimethylbenzenesulfonic acid ( 17 ) and 5-acetylamino-2-chloro-3,4-dimethylbenzenesulfonic acid ( 18 ), respectively. Their structures were proven by hydrolysis to 5-amino-2-bromo-3,4-dimethylbenzenesulfonic acid ( 21 ) and 5-amino-2-chloro-3,4-dimethylbenzenesulfonic acid ( 22 ), followed by reductive dehalogenation to 3 . 相似文献
38.
The synthesis of dimetallic olefin complexes of the type L1M1C7H7M2L2 (M1 = Fe, Co, Rh; M2 = Rh, Ir, Pd; L1 = CO, C5H5; L2 = diene, allyl, P(OR)3) is described. The fluxional structures were investigated by 13C-, 57Fe- and 103Rh-NMR.-spectroscopy, and a cisoid dimetallic coordination, including a (metal, metal)-bond, can be deduced for the C7H7-ring. 57Fe- and 103Rh-chemical shifts give indications for the charge distribution in the 34e-complexes. The homodimetallic complex (Cp)Rh(tropone)Rh(Cp) ( 13 , Cp = cyclopentadienyl) and the corresponding 2-methoxytropone complex 14 were synthesized in addition to the above mentioned complexes. A fluxional bis(1-3-η-allyl)-coordination of the two Rh-atoms was derived from the temperature-dependent 13C-NMR.-spectra. A spin simulation of the (Cp)-multiplets of 12 and 13 yields information about (Rh, Rh)-spin-coupling which amounts to ≈5 Hz at 30°. 相似文献
39.
Paul Von Ragué Schleyer José Walkimar De M. Carneiro 《Journal of computational chemistry》1992,13(8):997-1003
The closely related Cs ( 1 ) and C2v ( 3 ) structures of CH have been reinvestigated at many ab initio levels using MP2/6-31G** and MP2/6-311 + + G(2df, 2pd) geometries. The largest basis sets employed were 6-311G(3df, 2p), 6-311 + + G(3df, 3pd), and the Dunning “correlation consistent” polarized triple-split valence basis set (cc-pVTZ). Electron correlation was probed at the MP4 level, but the QCISD method was also used with the largest basis sets. While electron correlation favors 3 over 1 by about 2 kcal/mol, the correlated relative energies with all basis sets employed range from 0.36–1.03 kcal/mol in favor of 1 . The best estimate of this difference, 0.86 kcal/mol, is essentially identical with the (scaled) zero-point energy difference, 0.84 kcal/mol, favoring 3 over 1 . These results indicate that 1 and 3 have almost exactly the same energy at 0 K. Our best value for the dissociation energy of CH is 42.0 kcal/mol [QCISD(T)/6-311 + + G(3df, 3pd)//MP2(fu)/6-311 + + G(2df, 2pd), corrected to 298 K], which agrees very well with the experimental value. © 1992 by John Wiley & Sons, Inc. 相似文献
40.
S. M. Pershin A. F. Bunkin V. L. Golo 《Journal of Experimental and Theoretical Physics》2012,115(6):1008-1011
We consider the dynamics of H2O monomers in channels of icelike structures using the model of 1D rotator (i.e., a particle with one translational and one rotational degree of freedom). The effect of the channel walls on the motion of the particle is simulated by the interaction of the dipole moment of the particle with a periodic electric field. In this model, the following four regimes of motion are possible: (i) reflection of the particle from the inlet of the channel; (ii) single passage through the channel with a fixed phase; (iii) passage of the particle through the channel after multiple reflections in the channel from its inlet to its outlet; and (iv) reverse motion of the particle after its stay in the channel and multiple reflections from the inlet and outlet. These regimes indicate the possibility of existence of H2O monomers in the form of particles trapped in the channels of icelike formations. 相似文献