全文获取类型
收费全文 | 1215篇 |
免费 | 60篇 |
国内免费 | 3篇 |
专业分类
化学 | 1019篇 |
晶体学 | 7篇 |
力学 | 23篇 |
数学 | 98篇 |
物理学 | 131篇 |
出版年
2023年 | 7篇 |
2022年 | 33篇 |
2021年 | 50篇 |
2020年 | 40篇 |
2019年 | 45篇 |
2018年 | 46篇 |
2017年 | 35篇 |
2016年 | 59篇 |
2015年 | 57篇 |
2014年 | 38篇 |
2013年 | 84篇 |
2012年 | 78篇 |
2011年 | 102篇 |
2010年 | 55篇 |
2009年 | 50篇 |
2008年 | 78篇 |
2007年 | 84篇 |
2006年 | 60篇 |
2005年 | 67篇 |
2004年 | 55篇 |
2003年 | 34篇 |
2002年 | 30篇 |
2001年 | 20篇 |
2000年 | 14篇 |
1999年 | 9篇 |
1998年 | 7篇 |
1997年 | 7篇 |
1996年 | 9篇 |
1995年 | 4篇 |
1993年 | 4篇 |
1992年 | 1篇 |
1991年 | 1篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1986年 | 1篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有1278条查询结果,搜索用时 265 毫秒
211.
Oleg N. Shishilov Tatiana A. Stromnova Andrei V. Churakov Lyudmila G. Kuz’mina Judith A.K. Howard 《Journal of organometallic chemistry》2009,694(9-10):1453-1458
The reaction of palladium carbonyl carboxylates Pd6(CO)6(RCOO)6 with gaseous nitrogen monoxide was investigated. These clusters were found to promote the NO disproportionation into N2 and NO2 under mild conditions. The reaction is accompanied with the oxidation of coordinated carbon monoxide. These processes result in unusual eight-nuclear palladium carboxylate clusters Pd8(CO)4(NO2)4(RCOO)8. 相似文献
212.
Eutimio G. Fernández Rodolfo Valdés Yenisley Medina José A. Montero Alejandro Figueroa Williams Ferro Yarysel Guevara Tatiana Álvarez Andrés Tamayo Regla M. Somoza Leonardo Canaán-Haden Jorge L. López 《Chromatographia》2009,70(7-8):1179-1183
Sepharose CL-4B and Sepharose CL-2B with immobilized CB.Hep-1 monoclonal antibody were compared for studying the matrix efficiency in the immunopurification of the recombinant hepatitis B surface antigen (rHBsAg). The elution capacities of both matrices were similar over eight chromatographic cycles, significant differences were only observed in the first purification cycles. A high percentage of the adsorbed rHBsAg was not eluted from both matrices. The rHBsAg purity was not affected by matrix characteristics (pore size and percentage of agarose) and differences between Sepharose CL-4B and Sepharose CL-2B do not provoke differences in the antibody released from the matrices under defined experimental conditions. 相似文献
213.
Ionel Popescu Adriana Urda Tatiana Yuzhakova Ioan-Cezar Marcu Jozsef Kovacs Ioan Sandulescu 《Comptes Rendus Chimie》2009,12(9):1072-1078
Unsupported and γ-Al2O3-supported Ba and Pb titanate catalysts were prepared, characterized and studied in the combustion of methane, as a test reaction for VOCs’ catalytic combustion. They present good catalytic activities, and after dispersion (5%) on γ-Al2O3 the specific activity of the supported perovskite phase increased 25 and 30 times, respectively, compared with the unsupported samples. PbTiO3/γ-Al2O3 shows the best catalytic properties among the tested samples. 相似文献
214.
Alexander S. Romanov Joseph M. Mulroy Mikhail Yu. Antipin Tatiana V. Timofeeva 《Acta Crystallographica. Section C, Structural Chemistry》2009,65(11):m431-m435
The compounds tricarbonyl(η5‐1‐iodocyclopentadienyl)manganese(I), [Mn(C5H4I)(CO)3], (I), and tricarbonyl(η5‐1‐iodocyclopentadienyl)rhenium(I), [Re(C5H4I)(CO)3], (III), are isostructural and isomorphous. The compounds [μ‐1,2(η5)‐acetylenedicyclopentadienyl]bis[tricarbonylmanganese(I)] or bis(cymantrenyl)acetylene, [Mn2(C12H8)(CO)6], (II), and [μ‐1,2(η5)‐acetylenedicyclopentadienyl]bis[tricarbonylrhenium(I)], [Re2(C12H8)(CO)6], (IV), are isostructural and isomorphous, and their molecules display inversion symmetry about the mid‐point of the ligand C[triple‐bond]C bond, with the (CO)3M(C5H4) (M = Mn and Re) moieties adopting a transoid conformation. The molecules in all four compounds form zigzag chains due to the formation of strong attractive I...O [in (I) and (III)] or π(CO)–π(CO) [in (I) and (IV)] interactions along the crystallographic b axis. The zigzag chains are bound to each other by weak intermolecular C—H...O hydrogen bonds for (I) and (III), while for (II) and (IV) the chains are bound to each other by a combination of weak C—H...O hydrogen bonds and π(Csp2)–π(Csp2) stacking interactions between pairs of molecules. The π(CO)–π(CO) contacts in (II) and (IV) between carbonyl groups of neighboring molecules, forming pairwise interactions in a sheared antiparallel dimer motif, are encountered in only 35% of all carbonyl interactions for transition metal–carbonyl compounds. 相似文献
215.
Paul Tongwa Tiffany L. Kinnibrugh Geetha R. Kicchaiahgari Victor N. Khrustalev Tatiana V. Timofeeva 《Acta Crystallographica. Section C, Structural Chemistry》2009,65(4):o155-o159
The molecules of the title compounds, C16H15NOS2, (I), and C16H13Br2NOS2, (II), are E,E‐isomers and consist of an extensive conjugated system, which determines their molecular geometries. Compound (I) crystallizes in the monoclinic space group P21/c. It has one thiophene ring disordered over two positions, with a minor component contribution of 0.100 (3). Compound (II) crystallizes in the noncentrosymmetric orthorhombic space group Pca21 with two independent molecules in the unit cell. These molecules are related by a noncrystallographic pseudo‐inversion center and possess very similar geometries. The crystal packings of (I) and (II) have a topologically common structural motif, viz. stacks along the b axis, in which the molecules are bound by weak C—H...O hydrogen bonds. The noncentrosymmetric packing of (II) is governed by attractive intermolecular Br...Br and Br...N interactions, which are also responsible for the very high density of (II) (1.861 Mg m−3). 相似文献
216.
Viktor A. Tafeenko Stanislav I. Gurskiy Andrey N. Baranov Tatiana V. Kaisarova Leonid A. Aslanov 《Acta Crystallographica. Section C, Structural Chemistry》2009,65(2):m52-m55
The structures of three salts of 3‐cyano‐4‐dicyanomethylene‐5‐oxo‐4,5‐dihydro‐1H‐pyrrol‐2‐olate with alkali metals (Na, K and Rb) are related to their luminescence properties. The Rb salt, rubidium(I) 3‐cyano‐4‐dicyanomethylene‐5‐oxo‐4,5‐dihydro‐1H‐pyrrol‐2‐olate, Rb+·C8HN4O2−, is isomorphous with the previously reported potassium salt. For the Na compound, sodium(I) 3‐cyano‐4‐dicyanomethylene‐5‐oxo‐4,5‐dihydro‐1H‐pyrrol‐2‐olate dihydrate, Na+·C8HN4O2−·2H2O, two independent sodium ions, located on inversion centers, are coordinated by four water molecules each and additionally by two cyano groups for one and two carbonyl groups for the other. The luminescence spectra in solution are unaffected by the nature of the cation but vary strongly with the dielectric constant of the solvent. In the solid state, the emission maxima vary with structural features; the redshift of the maximum luminescence varies inversely with the distance between the stacked anions. 相似文献
217.
Bussery-Honvault B Launay JM Korona T Moszynski R 《The Journal of chemical physics》2006,125(11):114315
Nonadiabatic theory of molecular spectra of diatomic molecules is presented. It is shown that in the fully nonadiabatic framework, the rovibrational wave functions describing the nuclear motions in diatomic molecules can be obtained from a system of coupled differential equations. The rovibrational wave functions corresponding to various electronic states are coupled through the relativistic spin-orbit coupling interaction and through different radial and angular coupling terms, while the transition intensities can be written in terms of the ground state rovibrational wave function and bound rovibrational wave functions of all excited electronic states that are electric dipole connected with the ground state. This theory was applied in the nearly exact nonadiabatic calculations of energy levels, line positions, and intensities of the calcium dimer in the A (1)Sigma(u) (+)(1 (1)S+1 (1)D), c (3)Pi(u)(1 (3)P+1 (1)S), and a (3)Sigma(u) (+)(1 (3)P+1 (1)S) manifolds of states. The excited state potentials were computed using a combination of the linear response theory within the coupled-cluster singles and doubles framework for the core-core and core-valence electronic correlations and of the full configuration interaction for the valence-valence correlation, and corrected for the one-electron relativistic terms resulting from the first-order many-electron Breit theory. The electric transition dipole moment governing the A (1)Sigma(u) (+)<--X (1)Sigma(g) (+) transitions was obtained as the first residue of the frequency-dependent polarization propagator computed with the coupled-cluster method restricted to single and double excitations, while the spin-orbit and nonadiabatic coupling matrix elements were computed with the multireference configuration interaction wave functions restricted to single and double excitations. Our theoretical results explain semiquantitatively all the features of the observed Ca(2) spectrum in the A (1)Sigma(u) (+)(1 (1)S+1 (1)D), c (3)Pi(u)(1 (3)P+1 (1)S), and a (3)Sigma(u) (+)(1 (3)P+1 (1)S) manifolds of states. 相似文献
218.
Self-organization of 3,5-dihydroxybenzylalcohol (DHBA) based dendrimers of generations 0-3 (G0-G3) on bare and functionalized single crystal silicon (Si/SiO2) surfaces has been examined. The underlying monolayer plays a significant role in the supramolecular assembly leading to ordered structures of DHBA (G0) and generation 1-3 (G1-G3) dendrimers at interfaces. Ordered hyperbranched structures are formed on surfaces containing self-assembled monolayers with complimentary features to the assembling molecules, whereas no such organized assemblies are observed on unfunctionalized surfaces. 相似文献
219.
Mitkina TV Sokolov MN Naumov DY Kuratieva NV Gerasko OA Fedin VP 《Inorganic chemistry》2006,45(17):6950-6955
The unprecedented selective encapsulation of trans-[Co(en)2Cl2]+ from the mixture of trans and cis isomers into the cavity of macrocyclic cavitand cucurbit[8]uril (C48H48N32O16, CB[8]) leads to the inclusion compound {trans-[Co(en)2Cl2]@CB[8]}Cl.17H2O (1). Single-crystal X-ray analysis, 1H NMR, and ESI-MS spectra confirm the formation of host-guest complex 1 in both solid state and solution. The geometry of the complex cation alters significantly upon inclusion, which causes appreciable hypsochromic shifts of the absorption bands of the guest complex. According to TGA data, inclusion of trans-[Co(en)2Cl2]+ dramatically stabilizes the complex toward thermal decomposition. Encapsulation of trans-[Co(en)2Cl2]+ into the CB[8] cavity also increases the stability of the metal complex toward isomerization into the cis form. The supramolecular adduct {cis-[Co(en)2(H2O)2](CB[8])6}Cl3.ca109.5H2O (2) was isolated only after prolonged heating of an aqueous solution of 1 at 120 degrees C in an evacuated tube; it was characterized by X-ray crystallography, IR, and elemental analysis. 相似文献
220.
A method for the determination of Ag, Cd, Cu, Pb and Tl in fuel alcohol by isotope dilution electrothermal vaporization inductively coupled plasma mass spectrometry (ID ETV-ICP-MS) is proposed. The analytes were separated in two groups: Ag and Cu were determined without modifier and Cd, Pb and Tl with the use of Pd as chemical modifier. The employed ETV operational conditions were pyrolysis temperature of 800 °C for Cd, Pb and Tl and of 900 °C for Ag and Cu and vaporization temperature of 2400 °C for both groups. Seven common, one with additive and one anhydrous fuel ethanol samples were analyzed. The spiked and reference isotopes were, respectively, 109Ag and 107Ag, 112Cd and 111Cd, 63Cu and 65Cu, 206Pb and 208Pb and 203Tl and 205Tl. The added amounts of the enriched isotope material were the same for all samples: 4.6 ng of 109Ag, 5 ng of 112Cd, 21.1 ng of 63Cu, 9 ng of 206Pb and 0.21 ng of 203Tl. The blank was bi-distilled ethanol, acidified with 0.3% (v/v) nitric acid, as the samples. The limits of detection (LODs) were calculated as three times the standard deviation of the concentrations in the blank (n = 10) and were, in μg L−1, for Ag: 0.02, for Cd: 0.08, for Cu: 0.1, for Pb: 0.05 and for Tl: 0.001. The obtained concentrations in the samples were in agreement with those obtained by external calibration (EC), according to the paired t-test. The isotope dilution (ID) showed to be a robust, fast and simple calibration technique for the analysis of fuel ethanol. 相似文献