全文获取类型
收费全文 | 5180篇 |
免费 | 305篇 |
国内免费 | 48篇 |
专业分类
化学 | 3832篇 |
晶体学 | 47篇 |
力学 | 118篇 |
综合类 | 1篇 |
数学 | 467篇 |
物理学 | 1068篇 |
出版年
2023年 | 23篇 |
2022年 | 19篇 |
2021年 | 90篇 |
2020年 | 85篇 |
2019年 | 110篇 |
2018年 | 82篇 |
2017年 | 71篇 |
2016年 | 176篇 |
2015年 | 157篇 |
2014年 | 192篇 |
2013年 | 319篇 |
2012年 | 358篇 |
2011年 | 398篇 |
2010年 | 268篇 |
2009年 | 229篇 |
2008年 | 329篇 |
2007年 | 279篇 |
2006年 | 284篇 |
2005年 | 285篇 |
2004年 | 229篇 |
2003年 | 216篇 |
2002年 | 187篇 |
2001年 | 127篇 |
2000年 | 111篇 |
1999年 | 56篇 |
1998年 | 44篇 |
1997年 | 56篇 |
1996年 | 55篇 |
1995年 | 44篇 |
1994年 | 43篇 |
1993年 | 58篇 |
1992年 | 53篇 |
1991年 | 42篇 |
1990年 | 39篇 |
1989年 | 51篇 |
1988年 | 28篇 |
1987年 | 26篇 |
1986年 | 30篇 |
1985年 | 29篇 |
1984年 | 21篇 |
1983年 | 19篇 |
1982年 | 17篇 |
1981年 | 27篇 |
1980年 | 16篇 |
1979年 | 18篇 |
1978年 | 12篇 |
1977年 | 21篇 |
1976年 | 19篇 |
1975年 | 12篇 |
1974年 | 20篇 |
排序方式: 共有5533条查询结果,搜索用时 15 毫秒
141.
Fry BG Wickramaratna JC Hodgson WC Alewood PF Kini RM Ho H Wüster W 《Rapid communications in mass spectrometry : RCM》2002,16(6):600-608
Death adders (genus Acanthophis) are unique among elapid snakes in both morphology and venom composition. Despite this genus being among the most divergent of all elapids, the venom has been historically regarded as relatively quite simple. In this study, liquid chromatography/mass spectrometry (LC/MS) analysis has revealed a much greater diversity in venom composition, including the presence of molecules of novel molecular weights that may represent a new class of venom component. Furthermore, significant variation exists between species and populations, which allow for the LC/MS fingerprinting of each species. Mass profiling of Acanthophis venoms clearly demonstrates the effectiveness of this technique which underpins fundamental studies ranging from chemotaxonomy to drug design. 相似文献
142.
Pyrolysis-gas chromatography was applied to the characterization of ground beef and soy protein isolate and its mixtures at the 50, 30 and 10% levels. A cryogenic trap pyrolysis mode was employed and the volatile pyrolysates were analysed by a high-resolution capillary gas chromatograph. Two phenolic derivatives, o-methoxy- and dimethoxyphenol, as well as 2,3-dithiabutane are uniquely observed at a large concentration in the soy pyrolysate. Quantification of these characteristic compounds allow the estimation of the level of soy inclusion in the mixture. This approach effectively denotes soy addition up to the 10% level in comminuted beef. 相似文献
143.
S. Unterricker Kim Jung Ho W. Stolz D. Degering 《Journal of Radioanalytical and Nuclear Chemistry》1988,122(2):271-278
The underground radiation conditions in the mining district of Freiberg and in a rock salt environment of the Werra district were investigated. In a salt mine a very low natural activity level can be found. For selection of proper shielding materials a low-level -spectrometer and an optimum sample geometry must be used. The photopeak differences between sample and blank are small in most cases. Considerable differences can be found in the continuous background below 0.7 MeV. 相似文献
144.
Two novel heptadentate ligands, pentaaza macrocycles with two pendant xpyridyl and phenol groups, were prepared and the crystal structure of the manganese(II) complex of N,N′-bis(2-pyridylmethyl)-pentaaza macrocycle revealed a pentagonal bipyramidal geometry. 相似文献
145.
De Angelis AA Nevzorov AA Park SH Howell SC Mrse AA Opella SJ 《Journal of the American Chemical Society》2004,126(47):15340-15341
High-resolution solid-state NMR spectra can be obtained from uniformly (15)N-labeled membrane proteins in magnetically aligned bicelles. Fast uniaxial diffusion about the axis of the bilayer normal results in single-line spectra that contain the orientational information necessary for protein structure determination. 相似文献
146.
147.
Electrogenerated chemiluminescence (ECL) of six new ethyne-based acridine derivatives (1-6) has been studied. The new acridine derivatives were synthesized by cross-coupling of 9-chloroacridine and corresponding donor-substituted phenylethynes under modified Sonogashira conditions. The donor groups were varied in the order of increasing steric hindrance and donor strength at the donor site. The solution phase photophysical properties and ECL of these compounds were studied comparatively in acetonitrile solvent. The UV-Visible spectra of compounds 1-5 exhibit closely the same maxima. Density functional theory (DFT) has been invoked to analyze and understand the unexpected UV-Visible absorption behavior. Compounds with weak electron donors produce excimer ECL irrespective of steric hindrance at the donor site, while the compound with a stronger donor gives rise to ECL that is blue-shifted with respect to its photoluminescence spectrum. All except one of these compounds also exhibit solid state fluorescence which may be useful for solid state devices such as organic light emitting diodes (OLEDs) and as laser dyes. The observed properties are discussed with reference to the structure of the compounds synthesized. 相似文献
148.
Liquid-phase microextraction of protein-bound drugs under non-equilibrium conditions 总被引:1,自引:0,他引:1
Recently, we introduced an inexpensive and disposable hollow fiber-based device for liquid-phase microextraction (LPME) where ionic analytes typically were extracted and preconcentrated from 1-4 mL aqueous samples (such as plasma and urine) through an organic solvent immobilized in the pores of a polypropylene hollow fiber and into a 10-25 microL volume of acceptor phase present inside the lumen of the hollow fiber. Subsequently, the acceptor phase was directly subjected to the final analysis by a chromatographic or electrophoretic method. In the present work, attention was focused on LPME of the basic drugs amphetamine, pethidine, promethazine, methadone and haloperidol characterized by substantial differences in the degree of protein binding. Drug-protein interactions in plasma resulted in reduced recoveries and substantially increased extraction times compared with extraction of the drugs from a pure water matrix. However, by addition of 5-50% methanol to the plasma samples, recoveries were comparable with LPME from water samples and ranged between 75 and 100%. The addition of methanol was found not to speed up the LPME process and extractions from plasma were performed in 45 min to reach equilibrium. Because approximately 55-70% of the final analyte concentrations were achieved within the initial 10 min of the LPME process, validation was accomplished after 10 and 45 min of LPME. In general, the results with 10 and 45 min were almost comparable, with precision data in the range 1.2-11.1% (RSD) and with linearity in the concentration range 20-1000 ng mL(-1) (r = 0.999). In conclusion, excellent LPME results may be achieved in a short time under non-equilibrium conditions with a minor loss of sensitivity. In cases of drug-protein interactions, methanol may be added to ensure a high extraction recovery. 相似文献
149.
The 1,2-diphcnylethyl radical and derivatives were generated from photolysis of tran-f-stilbene and its derivatives 1–13 with secondary amines as quenchers. The 1,2-diphenylelhyl radicals that escaped from the solvent cage were trapped by 2-methyl-2-nitrosopropane (MNP) and were detected by the HPLCEPR method. The yield of the spin adduct is greater for tertiary amines. The smaller yields of the spin adduct formed from secondary amines are ascribed to greater reactivities of the 1,2-diphenylethyl and dialkylamino radicals within the solvent cage. 相似文献
150.
A synthesis and stereochemistry confirmation of a constituent recently isolated from the whole plant Isodon excisus is reported. An enantioselective catalytic boron-mediated reduction of an α-bromoketone was utilized in the key synthetic transformation. The methodology described herein was also used for the synthesis of the natural product's enantiomer and several derivatives. In addition, the compounds were evaluated for inhibitory activity in a caspase induction assay. The natural product was found to be devoid of activity, but several derivatives had moderate inhibitory activity (EC50<1 μM). 相似文献