全文获取类型
收费全文 | 2696篇 |
免费 | 105篇 |
国内免费 | 5篇 |
专业分类
化学 | 1960篇 |
晶体学 | 16篇 |
力学 | 53篇 |
数学 | 338篇 |
物理学 | 439篇 |
出版年
2023年 | 32篇 |
2022年 | 41篇 |
2021年 | 68篇 |
2020年 | 78篇 |
2019年 | 70篇 |
2018年 | 60篇 |
2017年 | 69篇 |
2016年 | 103篇 |
2015年 | 105篇 |
2014年 | 137篇 |
2013年 | 212篇 |
2012年 | 203篇 |
2011年 | 181篇 |
2010年 | 129篇 |
2009年 | 118篇 |
2008年 | 146篇 |
2007年 | 143篇 |
2006年 | 103篇 |
2005年 | 85篇 |
2004年 | 58篇 |
2003年 | 51篇 |
2002年 | 62篇 |
2001年 | 37篇 |
2000年 | 19篇 |
1999年 | 22篇 |
1998年 | 31篇 |
1997年 | 15篇 |
1996年 | 12篇 |
1995年 | 13篇 |
1994年 | 18篇 |
1993年 | 13篇 |
1992年 | 15篇 |
1991年 | 15篇 |
1990年 | 21篇 |
1989年 | 21篇 |
1988年 | 12篇 |
1987年 | 21篇 |
1986年 | 18篇 |
1985年 | 12篇 |
1984年 | 12篇 |
1983年 | 12篇 |
1982年 | 12篇 |
1981年 | 17篇 |
1980年 | 16篇 |
1979年 | 16篇 |
1978年 | 18篇 |
1977年 | 14篇 |
1976年 | 11篇 |
1975年 | 12篇 |
1972年 | 12篇 |
排序方式: 共有2806条查询结果,搜索用时 15 毫秒
31.
Falkenhagen J Jancke H Krüger RP Rikowski E Schulz G 《Rapid communications in mass spectrometry : RCM》2003,17(4):285-290
Liquid chromatography in combination with spectroscopic methods like matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) or nuclear magnetic resonance (NMR) spectroscopy is a powerful method to characterize silsesquioxanes and silsesquioxane mixtures. As new examples, the formation of silsesquioxyl-substituted silsesquioxanes [(n-octyl)(7)(SiO(1.5))(8)](2)O and [(n-octyl)(7)(SiO(1.5))(8)O](2)[(n-octyl)(6)(SiO(1.5))(8)] as well as the cage rearrangement of octa-[(n-heptyl)silsesquioxane] to larger structures [(n-heptyl)SiO(1.5))](n) up to n=28 are shown. 相似文献
32.
π-electron energies and bond orders of benzenoid hydrocarbons with up to five fused hexagons have been considered by the simple
Bond Orbital Resonance Theory (BORT) approach. The corresponding ground states were determined according to four BORT models.
In the first three models a diagonalisation of the Hückel-type Hamiltonian was performed in the bases of Kekulé, of Kekulé
and mono-Claus and of Kekulé and Claus resonance structures, respectively. In the fourth model a simple BORT ansatz was used.
According to this ansatz, the ground state is a linear combination of the positive Kekulé structures, all with equal coefficients.
It was shown that π-electron energies and bond orders obtained by these models correlate much better with the PPP energies
and bond orders than with the Hückel energies and bond orders. This indicates that a simple BORT approach is quite reliable
in predicting the more sophisticated PPP results. Concerning the relative performance of the four BORT models, the best results
were obtained with the BORT ansatz. The performance deteriorates with the expansion of the basis set. This is attributed to
the fact that in these models the improvement of the basis set is not accompanied with the corresponding improvement of the
Hamiltonian. Comparing the BORT-ansatz bond orders with the Pauling bond orders, it was shown that BORT-ansatz bond orders
correlate much better with the PPP bond orders.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
33.
The kinetics of the thermal decomposition of solid complexes of the type Ni(NCS)2L2 (L=pyridine,β-picoline and quinoline), of pseudooctahedral configuration, were studied by using isothermal methods, on the basis of losses of weight, in the temperature range 90–191?. The most suitable reaction order for all the complexes under investigation was found to ben=2/3, i.e. the total decomposition rate is determined by the chemical process proper. The calculated values ofE a(in kcal · mole?1) decrease in the following order: Ni(NCS)2py2 (29.4)>Ni(NCS)2(β-pic)2 (27.6)>Ni(NCS)2Q2 (24.3). With increasing volume of the ligand L the reaction rate also increases, and this suggests that the reaction proceeds by dissociative activation. For all the investigated complexes it was found that δH>E A; this may be explained by a several-step mechanism and the complex Ni(NCS)2L is then considered an intermediate. 相似文献
34.
František Kvasnička Rudolf Ševčík Michal Voldřich Jana Krátká 《Central European Journal of Chemistry》2004,2(3):417-424
A simple and rapid capillary zone electrophoresis (CZE) method for the determination of aristolochic acid (AA) in dietary
supplements and selected herbs is described. A clear separation of AA from other sample constituents was achieved within 5
minutes without any sample clean up. A mixture of 20 mM-morpholinethanesulphonic acid+10 mM-BisTrisPropane+0.2% hydroxyethylcelullose
in 10% methanol serves as a background electrolyte. The linearity, accuracy, intra-assay and detection limit of the developed
method are 200–6000 ng/mL, 95–103%, 3.5%, and 50 ng/ml, respectively. Ease of use, sufficient sensitivity and low running
cost are the most important attributes of the CZE method. The proposed CZE method was compared with HPLC. 相似文献
35.
EPR study has shown that the anticancer agent vanadocene dichloride (Cp2VCl2) interacts with carbonate contained in physiological solutions. Chelate complex Cp2VO2CO (|A(iso)(51V)| = 175.1 MHz, g(iso) = 1.9861) is the only paramagnetic species formed in the range about the physiological pH (5.5-11.0). The super-hyperfine coupling (|a(iso)(13C)| = 24.1 MHz) was evidenced at measurements using 13C labelled carbonate. The structure of carbonate complex was validated by comparison of observed and theoretical calculated HFC tensors (at the density functional level of theory). 相似文献
36.
37.
38.
J. Bujdák H. Slosiariková B. Číčel 《Journal of inclusion phenomena and macrocyclic chemistry》1992,13(4):321-327
Reduced charge montmorillonites (RCM) were prepared using lithium thermal treatment. The sorption of octylammonium (OA), dodecylammonium (DDA) and hexadecylammonium ions (HDA) on differently charged samples were studied. The amounts of DDA and HDA sorbed on each RCM exceed the cation exchange capacity (CEC) but that of OA exceeds only the CEC of samples with the lowest CEC. The sorption is affected not only by the layer charge but also by the formation of collapsed interlayer spaces in the lowest charged montmorillonites. X-ray measurements confirmed the decrease of the layer charge after lithium thermal treatment and the layer charge heterogeneity in RCMs. 相似文献
39.
Nadica Ivošević DeNardis Vera Žutić Vesna Svetličić Ranieri Urbani 《Electroanalysis》2007,19(4):473-478
In situ amperometric characterization of an aggregating system in terms of molecular adsorption and single microparticle interactions at the electrode interface is demonstrated using a model system: alginate/Ca(II) in an aqueous electrolyte solution. Recording of chronoamperometric curves of oxygen reduction at the dropping mercury electrode is designed for detection of dip‐shaped signals of individual gel microparticles. By addition of Ca(II) decrease of alginate adsorption is accompanied by appearance of signals indicating vesicle type association of alginate molecules and microparticles of gel phase. AFM imaging provided evidence of initial stage in calcium alginate gel formation. 相似文献
40.
Wolfgang A. Herrmann Martina Flöel Cornelia Weber John L. Hubbard Adolf Schäfer 《Journal of organometallic chemistry》1985,286(3):369-397
The eighteen new μ-alkylidene ruthenium complexes 5a–r and 5t are very easily and cleanly obtained along the diazoalkane or the hydrazone routes that involve treatment of the dinuclear, metal-metal doubly bonded precursor compound [(η5-C5H5)Ru(μ-NO)]2 (3) either with the diazoalkanes oxidizing agent (e.g., MnO2), with the respective hydrazones. Similarly, sulfur dioxide adds cleanly to the RuRu double bond of 3, thus giving the complex (μ-SO2)[(η5-C5H5)Ru(NO)]2 (5s). Regardless of the nature of the carbene bridge ligands, the dimetallacyclopropanes exhibit, in contrast to their iron analogues, exclusively terminal nitrosyl ligands. cis/trans-Isomerism with predominating amounts of the trans-isomers is observed for the derivatives that display unsymmetrically substituted carbene bridges.Treatment of the μ-methylene- and μ-ethylidene complexes (μ-CH2)[(η5-C5H5)Ru(NO)]2 (5a) and (μ-CHCH3)[(η5-C tetrafluoroboric acid or trifluoromethanesulfonic acid in diethyl ether yields, at ambient temperature, quantitatively the ionic complexes 6a,b and 7a,b, respectively, which were shown by 1H NMR spectroscopy to contain metal-metal bridging hydrogen functionalities. The reaction of hydrogen bromide with 5a under the same conditions gives the neutral bromo(methyl) complex 6d. This latter compound results from the isolable ionic intermediate of composition [(μ-CH2)(μ-H){(η5C5H5)Ru(NO)}2]+Br? (6c), which reaction stems from the nucleophilicity of the halide ion present in 6c. 相似文献