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111.
G. S. Zakharova L. Yu. Buldakova V. L. Volkov L. S. Molochnikov E. G. Kovaleva 《Russian Journal of Electrochemistry》2006,42(1):53-58
Complex vanadium and titanium oxides modified by copper ions are studied by the electrochemical and ESR methods. Oxides Cu x V2?y Ti y O5?δ·nH2O (0<y<1.33) have a layered structure and oxides Cu x Ti1?y V y O5+δ·nH2O (0<y<0.25), an anatase structure. The intercalation of cations Cu2+ into the hydrates leads to oxidation of V4+. According to ESR data, V4+ exists in the oxides in the form of VO2+ and an octahedral surround of oxygen (V4+?O6), respectively. The electroreduction of ions of d-elements and chemisorbed oxygen in the oxides is analyzed. The intercalation of cations Cu2+ alters the content of V4+ and the chemisorption ability of the oxides. Possible reasons for this phenomenon are discussed. 相似文献
112.
Yoshida T Sakakibara K Asami M Chen KH Lii JH Allinger NL 《Journal of computational chemistry》2003,24(3):319-327
The MM3 force field has been extended to deal with the lithium amide molecules that are widely used as efficient catalysts for stereoselective asymmetric synthesis. The MM3 force field parameters have been determined on the basis of the ab initio MP2/6-31G* and/or DFT (B3LYP/6-31G*, B3-PW91/6-31G*) geometry optimization calculations. To evaluate the electronic interactions specific to the lithium amides derived from the diamine molecules properly, the Lewis bonding potential term for the interaction between the lithium atom and the nonbonded adjacent electronegative atom such as nitrogen was introduced into the MM3 force field. The bond dipoles were evaluated correctly from the electronic charges on the atoms calculated by fitting to the electrostatic potential at points selected. The MM3 results on the molecular structures, conformational energies, and vibrational spectra show good agreement with those from the quantum mechanical calculations. 相似文献
113.
Alkylation of cyclohexenyl monoacetate 1 with R2Cu(CN)(MgCl)2 or RMgBr/CuCN (cat.) in Et2O produced trans 1,2-isomers 4, while arylation and alkenylation of 1 was accomplished with lithium borates 5 and a nickel cat. to afford trans 1,4-isomers 3 selectively. Furthermore, several transformations of the products were carried out to demonstrate synthetic advantages of the present reactions. 相似文献
114.
115.
Investigations of the Reaction between the [Lithium(trimethylsilyl)amido]-methyl-trimethyl-silylamino-silane Me(Me3SiNLi)(Me3SiNH)SiH and different Electrophiles The lithium silylamide Me(Me3SiNLi)(Me3SiNH)SiH 1 reacts with chlorotrimethylsilan in the nonpolar solvent n-hexane to the N-substitution product Me[(Me3Si)2N](Me3SiNH)SiH 2 and to the cyclodisilazane [Me(Me3SiNH)Si—N(SiMe3)]2 3 nearly in same amounts. The reaction of 1 with chlorotrimethylstannane gives besides small amounts of the cyclodisilazane 3 the N-substitution product Me[(Me3Si)(Me3Sn)N](Me3SiNH)SiH 4 . By the reaction of 1 with trimethylsilyltriflate the cyclodisilazane 3 is obtained as the main product. Furthermore 2 and the cyclodisilazane 5 are formed. Ethylbromide shows no reaction with 1 under the same conditions. These results indicate the existence of an equilibrium of the lithium silylamide 1 , the silanimine Me(Me3SiNH)Si?N(SiMe3) and lithium hydride. 相似文献
116.
Chih-Wei HuangMuthian Shanmugasundaram Hao-Ming ChangChien-Hong Cheng 《Tetrahedron》2003,59(20):3635-3641
An efficient method for the preparation of various monosubstituted arylallenes, disubstituted allenes and alkenylallenes via palladium-catalyzed coupling of allenylstannanes with aryl iodides or alkenyl iodides is described. The coupling reaction was carried out in the presence of Pd(PPh3)4 and LiCl using DMF as solvent. The possible role of LiCl in this coupling process is discussed based on the 119Sn NMR studies. 相似文献
117.
Preparation of poly(propylene carbonate)/organo-vermiculite nanocomposites via direct melt intercalation 总被引:2,自引:0,他引:2
Intercalated nanocomposites comprised of poly(propylene carbonate) (PPC) and organo-vermiculite (OVMT) was first prepared via direct melt compounding of the alkali-vermiculite intercalated host with PPC in a twin rotary mixer. The dispersion and morphologies of OVMT within PPC were investigated by X-ray diffraction and transmission electron microscopic techniques. The results revealed the formation of intercalated-exfoliated vermiculite sheets in the PPC matrix. Because of the thermally sensitive nature of PPC, thermal degradation occurred during the melt compounding. The degradation led to a deterioration of the mechanical properties of the nanocomposites. Tensile test showed that the yield strength and modulus of the nanocomposites decrease with increasing vermiculite content. The degradation mechanism was discussed according to the results of GPC and TGA measurements. 相似文献
118.
Posudievskii O. Yu. Kurys' Ya. I. Biskulova S. A. Malinovskii Yu. K. Pokhodenko V. D. 《Theoretical and Experimental Chemistry》2002,38(5):278-282
The possibility of the production of nanocomposites based on V2O5 and conducting polymers by direct intercalation of macromolecules of secondary doped polyaniline into the interlayer galleries of nanoparticles of aqueous V2O5 sol was demonstrated for the first time. The driving force of the intercalation process is substitution of the protons present in the galleries of the V2O5 by a polyaniline chain carrying a positive charge. 相似文献
119.
Li2Br(NH2): The First Ternary Alkali Metal Amide Halide The pseudobinary system LiNH2/LiBr was investigated by X-ray methods. The crystal structure of the compound Li2Br(NH2) was solved by single crystal data: Li2Br(NH2): Pnma, Z = 8, a = 12.484(2) Å, b = 7.959(1) Å, c = 6.385(1) Å, Z(Fo) with (Fo)2 ≧ 3σ(Fo)2 = 348, Z (parameter) = 51, R/Rw = 0.019/0.021 Li2Br(NH2) crystallizes in a new type of structure. To one another isolated chains of [Li2Li4/2(NH2)22+] show the motif of closest rod packing. They are connected via bromide ions in a distorted cubic primitive arrangement. 相似文献
120.
Javid T Safarov 《The Journal of chemical thermodynamics》2003,35(12):1929-1937
The (p,ρ,T) and (ps,ρs,Ts) properties of {(1−x)CH3OH + xLiBr} over a wide range of state parameters are reported for the first time. The experiments were carried out in a constant volume piezometer over a temperature range from 298.15 K to 398.15 K, at 0.08421, 0.13617, 0.19692, 0.23133 and 0.26891 mole fractions and from atmospheric pressure up to 60 MPa. The experimental uncertainties are ΔT=±3 mK for temperature, Δp=±5·10−2 MPa for high pressure and Δp=±5·10−4 MPa for atmospheric pressure, Δρ=±3·10−2 kg · m−3 for density. An equation of state was derived for correlation of the experimental data of the solutions. 相似文献