全文获取类型
收费全文 | 4658篇 |
免费 | 229篇 |
国内免费 | 20篇 |
专业分类
化学 | 3235篇 |
晶体学 | 22篇 |
力学 | 99篇 |
数学 | 640篇 |
物理学 | 911篇 |
出版年
2024年 | 6篇 |
2023年 | 48篇 |
2022年 | 65篇 |
2021年 | 98篇 |
2020年 | 138篇 |
2019年 | 133篇 |
2018年 | 91篇 |
2017年 | 73篇 |
2016年 | 218篇 |
2015年 | 159篇 |
2014年 | 189篇 |
2013年 | 258篇 |
2012年 | 386篇 |
2011年 | 491篇 |
2010年 | 231篇 |
2009年 | 144篇 |
2008年 | 313篇 |
2007年 | 322篇 |
2006年 | 293篇 |
2005年 | 274篇 |
2004年 | 191篇 |
2003年 | 124篇 |
2002年 | 110篇 |
2001年 | 44篇 |
2000年 | 32篇 |
1999年 | 30篇 |
1998年 | 22篇 |
1997年 | 19篇 |
1996年 | 43篇 |
1995年 | 35篇 |
1994年 | 30篇 |
1993年 | 34篇 |
1992年 | 29篇 |
1991年 | 9篇 |
1990年 | 8篇 |
1989年 | 11篇 |
1987年 | 6篇 |
1986年 | 10篇 |
1985年 | 13篇 |
1984年 | 8篇 |
1983年 | 10篇 |
1982年 | 16篇 |
1981年 | 7篇 |
1980年 | 7篇 |
1979年 | 15篇 |
1978年 | 9篇 |
1977年 | 11篇 |
1976年 | 11篇 |
1974年 | 8篇 |
1973年 | 34篇 |
排序方式: 共有4907条查询结果,搜索用时 15 毫秒
101.
Roselis A. Landaeta Aponte Andreas Luxenburger Scott A. Cameron Alex Weymouth-Wilson Richard H. Furneaux Lawrence D. Harris Benjamin J. Compton 《Molecules (Basel, Switzerland)》2022,27(7)
Bile acid receptors have been identified as important targets for the development of new therapeutics to treat various metabolic and inflammatory diseases. The synthesis of new bile acid analogues can help elucidate structure–activity relationships and define compounds that activate these receptors selectively. Towards this, access to large quantities of a chenodeoxycholic acid derivative bearing a C-12 methyl and a C-13 to C-14 double bond provided an interesting scaffold to investigate the chemical manipulation of the C/D ring junction in bile acids. The reactivity of this alkene substrate with various zinc carbenoid species showed that those generated using the Furukawa methodology achieved selective α-cyclopropanation, whereas those generated using the Shi methodology reacted in an unexpected manner giving rise to a rearranged skeleton whereby the C ring has undergone contraction to form a novel spiro–furan ring system. Further derivatization of the cyclopropanated steroid included O-7 oxidation and epimerization to afford new bile acid derivatives for biological evaluation. 相似文献
102.
103.
The presence of alkyl ether fuel oxygenates in drinking water supplies has raised public health concerns because of possible adverse health effects from chronic exposure to these compounds. To enable large exposure studies exploring possible relationships between chronic exposure to alkyl ether fuel oxygenates and health effects, we developed an improved analytical method, using headspace solid-phase microextraction coupled with capillary gas chromatography and mass spectrometry. This method quantifies trace levels of methyl tertiary-butyl ether, ethyl tertiary-butyl ether, di-isopropyl ether, and tertiary-amyl methyl ether in tap water. The method achieves detection limits of less than 0.025 microg/L for all analytes and linear ranges of three orders of magnitude in the measurement of the alkyl ether fuel oxygenates in 5-mL tap water samples. The relative percentage of recoveries of the alkyl ether fuel oxygenates ranged from 97% to 105%. The relative standard deviation ranged from 2% to 6%. Methyl tertiary-butyl ether was detected in samples of tap water taken from geographically diverse regions of the United States. The improved throughput and sensitivity of this method will enable large epidemiologic field studies of the prevalence and magnitude of exposure to alkyl ether fuel oxygenates in the general population. 相似文献
104.
The presence of water molecules plays an important role in the accuracy of ligand-protein docking predictions. Comprehensive docking simulations have been performed on a large set of ligand-protein complexes whose crystal structures contain water molecules in their binding sites. Only those water molecules found in the immediate vicinity of both the ligand and the protein were considered. We have investigated whether prior optimization of the orientation of water molecules in either the presence or absence of the bound ligand has any effect on the accuracy of docking predictions. We have observed a statistically significant overall increase in accuracy when water molecules are included during docking simulations and have found this to be independent of the method of optimization of the orientation of water molecules. These results confirm the importance of including water molecules whenever possible in a ligand-protein docking simulation. Our findings also reveal that prior optimization of the orientation of water molecules, in the absence of any bound ligand, does not have a detrimental effect on the improved accuracy of ligand-protein docking. This is important, given the use of docking simulations to predict the binding modes of new ligands or drug molecules. 相似文献
105.
Hsieh S Miller BJ Södergren AH Kjaergaard HG 《The journal of physical chemistry. A》2007,111(25):5415-5421
We have recorded vapor-phase photoacoustic spectra of cyclopropane, ethylene oxide, and ethylene sulfide in the third, fourth, and fifth CH-stretching overtone regions. We have used a harmonically coupled anharmonic oscillator local mode model to facilitate analysis of the spectra. Fermi resonance between the CH-stretching and HCH-bending vibrations is essential to explain the observed wide and multistructured CH-stretching overtone bands. A number of weak combination bands can account for the remaining experimental features observed to the blue of the CH-stretching regions. We have reassigned the fundamental spectra of these three-membered rings. 相似文献
106.
Pettus BJ Kroesen BJ Szulc ZM Bielawska A Bielawski J Hannun YA Busman M 《Rapid communications in mass spectrometry : RCM》2004,18(5):577-583
Normal-phase high-performance liquid chromatography (NP-HPLC) coupled to atmospheric pressure ionization mass spectrometry (APCI-MS) allows quantitative analysis of endogenous ceramide and dihydroceramide species from crude lipid extracts. Qualitative information for the species comes from observation of differences in chromatographic and mass spectrometric behavior between species (Pettus et al. Rapid Commun. Mass Spectrom. 2003; 17: 1017-1026). Quantitative analysis is achieved by (1) use of a synthetic internal standard as an extraction and injection control, (2) lack of salt adduction, ion suppression, or other matrix effects in APCI mode, and (3) consistent fragmentation and ionization of external standards across the physiologically relevant concentration range found in endogenous lipid samples. Application to the analysis and quantitation of ceramide and dihydroceramide from various cell lines is demonstrated. The results from APCI-MS analysis corroborate and enhance information acquired from use of the diacylglycerol kinase assay for total ceramide measurement. This technique readily allows simultaneous quantitation of ceramide and dihydroceramide species. 相似文献
107.
B Busch N Ueberschaar Y Sugimoto C Hertweck 《Journal of the American Chemical Society》2012,134(30):12382-12385
The course of the enigmatic iterative use of a polyketide synthase module was deduced from targeted domain inactivation in the aureothin assembly line. Mutational analyses revealed that the N-terminus of AurA is not involved in the iteration process, ruling out an ACP-ACP shuttle. Furthermore, an AurA(KS°, ACP°)-AurA(AT(0)) heterodimer proved to be nonfunctional, whereas aureothin production was restored in a ΔaurA mutant complemented with AurA(KS°)-AurA(ACP°). This finding supports a model according to which the ACP-bound polyketide intermediate is transferred back to the KS domain on the opposite PKS strand. 相似文献
108.
Guerrouache M Mahouche-Chergui S Chehimi MM Carbonnier B 《Chemical communications (Cambridge, England)》2012,48(60):7486-7488
A monolith surface with alkyne functionality was reacted with cysteamine through radical-mediated thiol-yne addition reaction providing a hydrophilic and chelating interface. Photochemical initiation affords spatial control over the reaction site and further site-specific immobilisation of gold nanoparticles. 相似文献
109.
Dieter Hauchecorne Dr. Roman Szostak Dr. Wouter A. Herrebout Prof. Benjamin J. van der Veken Prof. 《Chemphyschem》2009,10(12):2105-2115
The formation of weakly bound molecular complexes between dimethyl ether (DME) and the trifluoromethyl halides CF3Cl, CF3Br and CF3I dissolved in liquid argon and in liquid krypton is investigated, using Raman and FTIR spectroscopy. For all halides evidence is found for the formation of C? X???O halogen‐bonded 1:1 complexes. At higher concentrations of CF3Br, a weak absorption due to a 1:2 complex is also observed. Using spectra recorded at temperatures between 87 and 125 K, the complexation enthalpies for the complexes are determined to be ?6.8(3) kJ mol?1 (DME?CF3Cl), ?10.2(1) kJ mol?1 (DME?CF3Br), ?15.5(1) kJ mol?1 (DME?CF3I), and ?17.8(5) kJ mol?1 [DME(?CF3Br)2]. Structural and spectral information on the complexes is obtained from ab initio calculations at the MP2/ 6‐311++G(d,p) and MP2/6‐311++G(d,p)+LanL2DZ* levels. By applying Monte Carlo free energy perturbation calculations to account for the solvent influences, and statistical thermodynamics to estimate the zero‐point vibrational and thermal influences, the ab initio complexation energies are converted into complexation enthalpies for the solutions in liquid argon. The resulting values are compared with the experimental data deduced from the cryosolutions. 相似文献
110.
Bahadur V Mishchenko L Hatton B Taylor JA Aizenberg J Krupenkin T 《Langmuir : the ACS journal of surfaces and colloids》2011,27(23):14143-14150
The prevention and control of ice accumulation has important applications in aviation, building construction, and energy conversion devices. One area of active research concerns the use of superhydrophobic surfaces for preventing ice formation. The present work develops a physics-based modeling framework to predict ice formation on cooled superhydrophobic surfaces resulting from the impact of supercooled water droplets. This modeling approach analyzes the multiple phenomena influencing ice formation on superhydrophobic surfaces through the development of submodels describing droplet impact dynamics, heat transfer, and heterogeneous ice nucleation. These models are then integrated together to achieve a comprehensive understanding of ice formation upon impact of liquid droplets at freezing conditions. The accuracy of this model is validated by its successful prediction of the experimental findings that demonstrate that superhydrophobic surfaces can fully prevent the freezing of impacting water droplets down to surface temperatures of as low as -20 to -25 °C. The model can be used to study the influence of surface morphology, surface chemistry, and fluid and thermal properties on dynamic ice formation and identify parameters critical to achieving icephobic surfaces. The framework of the present work is the first detailed modeling tool developed for the design and analysis of surfaces for various ice prevention/reduction strategies. 相似文献