全文获取类型
收费全文 | 2610篇 |
免费 | 108篇 |
国内免费 | 29篇 |
专业分类
化学 | 1727篇 |
晶体学 | 27篇 |
力学 | 62篇 |
数学 | 462篇 |
物理学 | 469篇 |
出版年
2023年 | 20篇 |
2022年 | 18篇 |
2021年 | 89篇 |
2020年 | 58篇 |
2019年 | 61篇 |
2018年 | 47篇 |
2017年 | 50篇 |
2016年 | 115篇 |
2015年 | 84篇 |
2014年 | 103篇 |
2013年 | 161篇 |
2012年 | 158篇 |
2011年 | 156篇 |
2010年 | 107篇 |
2009年 | 110篇 |
2008年 | 149篇 |
2007年 | 155篇 |
2006年 | 139篇 |
2005年 | 119篇 |
2004年 | 110篇 |
2003年 | 93篇 |
2002年 | 65篇 |
2001年 | 47篇 |
2000年 | 44篇 |
1999年 | 39篇 |
1998年 | 39篇 |
1997年 | 26篇 |
1996年 | 19篇 |
1995年 | 28篇 |
1994年 | 28篇 |
1993年 | 20篇 |
1992年 | 24篇 |
1991年 | 22篇 |
1990年 | 22篇 |
1989年 | 19篇 |
1988年 | 16篇 |
1987年 | 10篇 |
1986年 | 19篇 |
1985年 | 25篇 |
1984年 | 19篇 |
1983年 | 12篇 |
1982年 | 11篇 |
1981年 | 10篇 |
1980年 | 11篇 |
1979年 | 6篇 |
1977年 | 11篇 |
1974年 | 5篇 |
1967年 | 5篇 |
1962年 | 4篇 |
1961年 | 4篇 |
排序方式: 共有2747条查询结果,搜索用时 15 毫秒
21.
The copper(II) complex [Cu(sat)], where Hsat is salicylidene-2-aminothiazole (bidentate Schiff - base), was studied in variety of solvents. In the solid state, the complex is black. It has been characterized by elemental analysis, solubility in common solvents, molar conductivity, and ultraviolet (UV) and visible (Vis) spectroscopy. The complex is easily soluble in common solvents such as chloroform, dimethylformamide, dimethyl sulfoxide, and 1,4-dioxane. The known crystal structure of similar compounds shows planar coordination geometry for the copper center. Combined multitechnique experiments have been applied to confirm the structure of the complex in solutions. The molar conductivities indicate their nonelectrolyte properties in all these solvents. The spectroscopic measurements were used to study the coordination properties of donoratoms and their bonding abilities. 相似文献
22.
Böcking T Kilian KA Hanley T Ilyas S Gaus K Gal M Gooding JJ 《Langmuir : the ACS journal of surfaces and colloids》2005,21(23):10522-10529
Surface modification with oligo(ethylene oxide) functionalized monolayers terminated with reactive headgroups constitutes a powerful strategy to provide specific coupling of biomolecules with simultaneous protection from nonspecific adsorption on surfaces for the preparation of biorecognition interfaces. To date, oligo(ethylene oxide) functionalized monolayer-forming molecules which can be activated for attachment of biomolecules but which can selectively form monolayers onto hydrogen terminated silicon have yet to be developed. Here, self-assembled monolayers (SAMs) containing tetra(ethylene oxide) moieties protected with tert-butyl dimethylsilyl groups were formed by thermal hydrosilylation of alkenes with single-crystal Si(111)-H. The protection group was used to avoid side reactions with the hydride terminated silicon surface. Monolayer formation was carried out using solutions of the alkene in the high-boiling-point solvent 1,3,5-triethylbenzene. The protecting group was removed under very mild acidic conditions to yield a free hydroxyl functionality, a convenient surface moiety for coupling of biological entities via carbamate bond formation. The chemical composition and structure of the monolayers before and after deprotection were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray reflectometry. To demonstrate the utility of this surface for covalent modification, two reagents were compared and contrasted for their ability to activate the surface hydroxyl groups for coupling of free amines, carbonyl diimidazole (CDI), and disuccinimidyl carbonate (DSC). Analysis of XP spectra before and after activation by CDI or DSC, and after subsequent reaction with glycine, provided quantitative information on the extent of activation and overall coupling efficiencies. CDI activated surfaces gave poor coupling yields under various conditions, whereas DSC mediated activation followed by aminolysis at neutral pH was found to be an efficient method for the immobilization of amines on tetra(ethylene oxide) modified surfaces. 相似文献
23.
24.
25.
Dobrochna Matkowska Maciej Gola Marcin ?nie?ek Piotr Cmoch Krzysztof Staliński 《Journal of organometallic chemistry》2007,692(10):2036-2045
A series of triorganotin hydrides and diorganotin dihydrides containing the optically active 2-(4-isopropyl-2-oxazolinyl)-5-phenyl ligand have been characterized by means of the multinuclear low-temperature NMR investigations, the results of which are discussed. In the corresponding organotin hydrides values of the 1J(1H-117/119Sn) couplings appeared to be temperature dependent, supporting an axial/equatorial position of the hydrogen attached to the tin. 相似文献
26.
The effect of initial concentration of tetrachloromethane and trichloromethane on their conversion in gliding discharge was determined. The conversion of CCl4 and CHCl3 was carried out in air containing 20 or 8000 ppm of water vapor. The flow rate of the air containing 1.2, 2.5, or 6.0 vol% of CCl4 or CHCl3 was 200 Nl/h. The amount of tetrachloromethane and trichloromethane reacted was determined for a constant value of specific energy which was varied with 2.0 and 4.0 VAh/Nl. The amounts of CCl4 and CHCl3 reacted were a linear function of the initial concentration of these compounds in the inlet gas. The results obtained have shown that water vapor present in the air has a favorable effect on the conversion of tetrachloromethane and trichloromethane in gliding discharge. 相似文献
27.
Colin F. Chignell Ann G. Motten Robert H. Sik Carol E. Parker Krzysztof Reszka 《Photochemistry and photobiology》1994,59(1):5-11
The photochemistry of 5,5-dimethyl-l-pyrroline N -oxide (DMPO) has been studied in benzene, cyclohexane and aqueous buffer solutions (pH 7.4) by means of electron paramagnetic resonance (EPR) and the spin trapping technique. Ultraviolet irradiation of DMPO in aqueous buffer with unfiltered UV radiation from a Xe arc lamp results in photoionization of the spin trap and the generation of the DMPO cation radical, DMPO+ . The aqueous electron, eaq − , was trapped by DMPO and detected as the DMPO/H adduct. The DMPO+ - reacted with the water to yield the DMPO/OH adduct. Ultraviolet irradiation of DMPO in nitrogen-saturated benzene gave an unidentified carbon-centered DMPO adduct that was replaced by hydroperoxyl and alkoxyl adducts of DMPO when oxygen was present. Experiments employing 17 O2 gas indicated that the oxygen in the DMPO alkoxyl adduct was derived from molecular oxygen. However, UV irradiation of DMPO in cyclohexane yielded the cyclohexyl and cyclohexyloxyl adducts of DMPO in nitrogen-saturated and air-saturated solutions, respectively. These observations suggest that in aprotic solvents UV irradiation of DMPO generates a carbon-centered radical (R− ), derived from the trap itself, which in benzene reacts with oxygen to yield an alkoxyl radical (RO− ), possibly via a peroxyl radical (ROO− ) intermediate. In cyclohexane R− abstracts a hydrogen atom from the solvent to yield the cyclohexyl radical in the absence of oxygen and the cyclohexyloxyl radical in the presence of oxygen. These findings indicate that when DMPO is used as a spin trap in studies employing short-wavelength UV radiation (λ < 300 nm) the photochemistry of DMPO cannot be ignored. 相似文献
28.
The General Rate model has been developed and solved to describe protein adsorption in an expanded bed. The model takes into account axial and local variation of particle size distribution (PSD), external and intra-particle mass transfer resistances, and dispersion in liquid phase. The influence of PSD on breakthrough profiles has been analysed. The simulation results show that for a significantly high expanded bed the lower part of the breakthrough curve profiles, calculated for local particle size distribution (LPSD) and for axial average particle size distribution (APSD) are very similar. However, the upper part of breakthrough profiles calculated for LPSD approaches inlet concentration much more slowly than those calculated for APSD. The retention times of the lower part of uptake curves calculated with average particle diameter are constantly shorter than those obtained from LPSD. For the calculation of the dynamic capacity (DC), the LPSD can be replaced by APSD for large expanded bed heights. Using breakthrough profiles calculated for average particle size, DC values are constantly underestimated. 相似文献
29.
Adam S. Plaziak Jaroslaw Spychala Hanna Wjtowicz Jerzy J. Langer Halina Thiel-Pawlicka Krzysztof Golankiewicz 《Journal of mass spectrometry : JMS》1992,27(11):1293-1298
Ortho-. meta- and para-isomers of N-(pyrimidin-4-yl)aminobenzoic acid and their methyl esters were investigated by electron impact mass Spectrometry. Their fragmentation was found to be strongly dependent on the position of the substituent in the aminobenzoic moiety. Two different kinds of ortho effect were studied and confirmed with the aid of deuterium-labelled derivatives. 相似文献
30.
Jolanta Obniska Krzysztof Kaminski Agnieszka Dzierzawska-Majewska 《Journal of fluorine chemistry》2006,127(3):417-425
A series of N-phenyl- and N-benzyl-2-azaspiro[4.4]nonane- and [4.5]decane-1,3-diones containing a fluoro or trifluoromethyl substituents at the aryl ring was synthesized and tested for their anticonvulsant activity in the maximal electroshock (MES) and subcutaneous metrazole (sc.Met) tests. Among them, the most active were N-benzyl derivatives with fluoro and trifluoromethyl substituents especially at position-2 of the aryl moiety. The introduction of the phenyl ring at the imide nitrogen atom resulted in less active compounds. The results obtained showed that incorporation of fluoro or trifluoromethyl substituents increased the anticonvulsant activity in comparison to respective chloro, methoxy or methyl analogues. Crystallographically obtained conformation for one active and two inactive derivatives with trifluoromethyl substituents at position-2 or -3 of phenyl ring were initially used for molecular electrostatic potentials (MEP) calculation. The MEP distribution at carbonyl oxygen atoms was different for active and inactive molecules. 相似文献