全文获取类型
收费全文 | 496篇 |
免费 | 27篇 |
专业分类
化学 | 397篇 |
晶体学 | 4篇 |
力学 | 11篇 |
数学 | 60篇 |
物理学 | 51篇 |
出版年
2023年 | 4篇 |
2022年 | 3篇 |
2021年 | 17篇 |
2020年 | 13篇 |
2019年 | 18篇 |
2018年 | 7篇 |
2017年 | 9篇 |
2016年 | 14篇 |
2015年 | 21篇 |
2014年 | 16篇 |
2013年 | 28篇 |
2012年 | 37篇 |
2011年 | 36篇 |
2010年 | 20篇 |
2009年 | 28篇 |
2008年 | 44篇 |
2007年 | 26篇 |
2006年 | 40篇 |
2005年 | 19篇 |
2004年 | 27篇 |
2003年 | 11篇 |
2002年 | 9篇 |
2001年 | 2篇 |
1997年 | 5篇 |
1996年 | 4篇 |
1995年 | 7篇 |
1994年 | 3篇 |
1993年 | 3篇 |
1992年 | 4篇 |
1991年 | 2篇 |
1990年 | 2篇 |
1984年 | 3篇 |
1981年 | 2篇 |
1978年 | 4篇 |
1975年 | 2篇 |
1974年 | 3篇 |
1973年 | 2篇 |
1969年 | 1篇 |
1966年 | 1篇 |
1964年 | 1篇 |
1933年 | 1篇 |
1931年 | 1篇 |
1930年 | 4篇 |
1928年 | 1篇 |
1886年 | 2篇 |
1883年 | 2篇 |
1882年 | 1篇 |
1881年 | 2篇 |
1870年 | 1篇 |
1869年 | 1篇 |
排序方式: 共有523条查询结果,搜索用时 28 毫秒
11.
12.
Aromatic nitro compounds are readily reduced by SnCl2, 2 H2O in alcohol or ethyl acetate or by anhydrous SnCl2 in alcohol where other reducible or acid sensitive groups such as aldehyde, ketone, ester, cyano, halogen and O-benzyl remain unaffected. 相似文献
13.
The modulational instability of traveling waves is often thought to be a crucial point in the mechanism of transition to space-time disorder and turbulence. The aim of this paper is to study the effect of spatiotemporal modulations on some dynamics u(0)(x,t), which may occur as an instability process when a control parameter varies, for instance. We analyze the properties of the modulated dynamics of the form g(1)(x)g(2)(t)u(0)(x,t) compared to those of the reference dynamics u(0)(x,t), using operator theory. We show that, if the reference dynamics is invariant under some space-time symmetry in the sense of Ref. [J. Nonlinear Sci. 2, 183 (1992)], the modulation has the effect of either deforming this symmetry or breaking it, depending on whether the corresponding operator remains unitary or not. We also demonstrate that the smallest Euclidean space containing the modulated dynamics has a dimension smaller than or equal to the smallest Euclidean space containing u(0)(x,t). The previous results are then applied to the case of modulated uniformly traveling waves. While the spatiotemporal translation invariance of the wave never persists in the presence of a modulation, the existence of a spatiotemporal symmetry depends on the resonance of the Fourier sidebands due to the modulation. In case of nonresonance, a spatiotemporal symmetry exists and is explicitly determined. In this situation, the modulated wave and the carrier wave have the same spectrum (up to a normalization factor), the same entropy, and the spatial (resp., temporal) two-point correlation is deformed only by the spatial (resp., temporal) modulation. (c) 1995 American Institute of Physics. 相似文献
14.
The synthesis of 3-acetylcyclohexanones , , has been realized by conjugate addition of lithiated cyanohydrin ether to 2-cyclohexenones , , in THF-HMPA, even if 3-substituted. 3-benzoylcyclohexanones , , are obtained from and , , in THF with excellent yields. 相似文献
15.
Graff JN McElhaney AE Basu P Gruhn NE Chang CS Enemark JH 《Inorganic chemistry》2002,41(10):2642-2647
Complexes of the form (Tp*)MoOCl(p-OC(6)H(4)X) and (Tp*)MoO(p-OC(6)H(4)X)(2) (Tp* = hydrotris(3,5-dimethyl-1-pyrazolyl)borate and X = OEt, OMe, Et, Me, H, F, Cl, Br, I, and CN) were examined by electrochemical techniques and gas-phase photoelectron spectroscopy to probe the effect of the remote substituent (X) on electron-transfer reactions at the oxomolybdenum core. Cyclic voltammetry revealed that all of these neutral Mo(V) compounds undergo a quasireversible one-electron oxidation (Mo(VI)/Mo(V)) and a quasireversible one-electron reduction (Mo(V)/Mo(IV)) at potentials that linearly depend on the electronic influence (Hammett sigma(p) parameter) of X. The first ionization energies for (Tp*)MoO(p-OC(6)H(4)X)(2) (X = OEt, OMe, H, F, and CN) were determined by photoelectron spectroscopy. A nearly linear correlation was found for the Mo(VI)/Mo(V) oxidation potentials in solution and the gas-phase ionization energies. Calculated heterogeneous electron-transfer rate constants show a slight systematic dependence on the substituent. 相似文献
16.
Lourdes Infantes MaryF. Mahon Louise Male PaulR. Raithby SimonJ. Teat Jürgen Sauer Nadine Jagerovic Jos Elguero Sam Motherwell 《Helvetica chimica acta》2003,86(4):1205-1221
The structures of six new tetrazines have been determined and their molecular packing has been compared to the supermolecular architecture observed in related carboxylic acid dimers. In the tetrazines, covalent N? N bonds are considered to replace the intermolecular O? H???O hydrogen bonds of the carboxylic acids. In the systems investigated, it is apparent that, in the majority of cases, the covalent six‐membered ring of the tetrazine is an appropriate replacement for the carboxylic acid synthon. This apparent interplay between molecular and supramolecular units may have applications in the crystal engineering of new materials. 相似文献
17.
Terhi Oja Petri Tähtinen Nadine Dreiack Pekka Mäntsälä Jarmo Niemi Mikko Metsä-Ketelä Karel D. Klika 《Tetrahedron: Asymmetry》2012,23(9):670-682
Two new pairs of stereoisomeric alnumycin As, A2 {(2)-(1R,1′RS,4′SR,5′SR)} and A3 {(2)-(1R,1′RS,4′SR,5′RS)}, are described. Similar to alnumycin A1 {(2)-(1R,1′RS,4′RS,5′SR)}, each of these naturally occurring compounds is also a pair of C-1 inverse epimers. The relative configurations of the dioxane ring sidechains were assigned on the basis of 1H NMR NOE contacts and molecular modeling using density functional theory (DFT) at the M06-2X/6-31G(d) level of theory. The absolute configurations of C-1 and the determination of inverse epimeric relationships were achieved by experimental electronic circular dichroism (ECD) measurements, with both aspects confirmed by using the chiral derivatizing agent (CDA) Mosher′s acid chloride {α-methoxy-α-trifluorophenylacetyl chloride (MTPACl)} to effect enantiodifferentiation. The absolute configurations of the dioxane ring using the CDA could only be effected in the case of alnumycin A1, the results of which were in agreement with previous assignments. The dioxane ring conformational mobility and the likely interaction between the MTPA groups coupled with the structural novelty of the diols in the dioxane ring with respect to CDA analysis precluded an absolute configuration assignment for alnumycins A2 and A3 based on empirical comparisons or by computational analysis of through-space NMR shieldings (TSNMRS) emanating from the phenyl groups of the MTPA moieties. 相似文献
18.
Nadine Monika Francke Frederic Schneider Knut Baumann Heike Bunjes 《Molecules (Basel, Switzerland)》2021,26(5)
In this study, the general processability of cannabidiol (CBD) in colloidal lipid carriers was investigated. Due to its many pharmacological effects, the pharmaceutical use of this poorly water-soluble drug is currently under intensive research and colloidal lipid emulsions are a well-established formulation option for such lipophilic substances. To obtain a better understanding of the formulability of CBD in lipid emulsions, different aspects of CBD loading and its interaction with the emulsion droplets were investigated. Very high drug loads (>40% related to lipid content) could be achieved in emulsions of medium chain triglycerides, rapeseed oil, soybean oil and trimyristin. The maximum CBD load depended on the type of lipid matrix. CBD loading increased the particle size and the density of the lipid matrix. The loading capacity of a trimyristin emulsion for CBD was superior to that of a suspension of solid lipid nanoparticles based on trimyristin (69% vs. 30% related to the lipid matrix). In addition to its localization within the lipid core of the emulsion droplets, cannabidiol was associated with the droplet interface to a remarkable extent. According to a stress test, CBD destabilized the emulsions, with phospholipid-stabilized emulsions being more stable than poloxamer-stabilized ones. Furthermore, it was possible to produce emulsions with pure CBD as the dispersed phase, since CBD demonstrated such a pronounced supercooling tendency that it did not recrystallize, even if cooled to −60 °C. 相似文献
19.
Nadine Hovnanian Liliane G. Hubert-pfalzgraf 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4)
Abstract Phosphorus ylides are known to form σ-metal-carbon bonds of unusual stability. Bis(cyclopentadienyl)niobium derivatives offer a general synthetic approach to niobium phosphorus ylide complexes, the first to be reported. 相似文献
20.
Nadine Schaefer Benjamin Peters Peter Schmidt Andreas H. Ewald 《Analytical and bioanalytical chemistry》2013,405(1):247-258
In the context of driving ability diagnostics in Germany, administrative cutoffs for various drugs and pharmaceuticals in urine have been established. Two liquid chromatography–tandem mass spectrometry methods for simultaneous detection and quantification of amphetamines, designer amphetamines, benzoylecgonine, benzodiazepines, opiates, and opioids in urine were developed and validated. A 500-μL aliquot of urine was diluted and fortified with an internal standard solution. After enzymatic cleavage, online extraction was performed by an ion-exchange/reversed-phase turbulent flow column. Separation was achieved by using a reversed-phase column and gradient elution. For detection, a Thermo Fisher TSQ Quantum Ultra Accurate Mass tandem mass spectrometer with positive electrospray ionization was used, and the analytes were measured in multiple-reaction monitoring mode detecting two transitions per precursor ion. The total run time for both methods was about 15 min. Validation was performed according to the guidelines of the Society of Toxicological and Forensic Chemistry. The results of matrix effect determination were between 78 % and 116 %. The limits of detection and quantification for all drugs, except zopiclone, were less than10?ng/mL and less than 25 ng/mL, respectively. Calibration curves ranged from 25 to 200 ng/mL for amphetamines, designer amphetamines, and benzoylecgonine, from 25 to 250 ng/mL for benzodiazepines, from 12.5 to 100 ng/mL for morphine, codeine, and dihydrocodeine, and from 5 to 50 ng/mL for buprenorphine and norbuprenorphine. Intraday and interday precision values were lower than 15 %, and bias values within?±?15 % were achieved. Turbulent flow chromatography needs no laborious sample preparation, so the workup is less time-consuming compared with gas chromatography–mass spectrometry methods. The methods are suitable for quantification of multiple analytes at the cutoff concentrations required for driving ability diagnostics in Germany. 相似文献