全文获取类型
收费全文 | 2525篇 |
免费 | 147篇 |
国内免费 | 19篇 |
专业分类
化学 | 1820篇 |
晶体学 | 6篇 |
力学 | 38篇 |
数学 | 492篇 |
物理学 | 335篇 |
出版年
2023年 | 27篇 |
2022年 | 21篇 |
2021年 | 38篇 |
2020年 | 60篇 |
2019年 | 70篇 |
2018年 | 41篇 |
2017年 | 38篇 |
2016年 | 84篇 |
2015年 | 68篇 |
2014年 | 80篇 |
2013年 | 136篇 |
2012年 | 158篇 |
2011年 | 164篇 |
2010年 | 86篇 |
2009年 | 100篇 |
2008年 | 156篇 |
2007年 | 165篇 |
2006年 | 148篇 |
2005年 | 151篇 |
2004年 | 129篇 |
2003年 | 111篇 |
2002年 | 96篇 |
2001年 | 49篇 |
2000年 | 36篇 |
1999年 | 38篇 |
1998年 | 26篇 |
1997年 | 33篇 |
1996年 | 40篇 |
1995年 | 30篇 |
1994年 | 38篇 |
1993年 | 32篇 |
1992年 | 14篇 |
1991年 | 28篇 |
1990年 | 12篇 |
1989年 | 16篇 |
1988年 | 11篇 |
1987年 | 4篇 |
1986年 | 5篇 |
1985年 | 16篇 |
1984年 | 7篇 |
1983年 | 15篇 |
1982年 | 4篇 |
1981年 | 18篇 |
1980年 | 9篇 |
1979年 | 5篇 |
1978年 | 8篇 |
1977年 | 5篇 |
1976年 | 8篇 |
1974年 | 5篇 |
1956年 | 3篇 |
排序方式: 共有2691条查询结果,搜索用时 15 毫秒
31.
32.
U.T. Mueller-Westerhoff A. Nazzal W. Prössdorf 《Journal of organometallic chemistry》1981,205(3):C21-C23
[1,1]Ferrocenophane can be prepared by reduction of 1,1′-bis(6-fulvenyl)ferrocene with complex borohydrides to give the dianion of 1,1′-bis(cyclopentadienylmethyl)ferrocene. Reaction of this dianion with ferrous chloride produces the ferrocenophane in good yield. 相似文献
33.
Prässler F Hoffmann V Schumann J Wetzig K 《Analytical and bioanalytical chemistry》1996,355(7-8):840-846
An algorithm is presented as a concept for the quantification in direct current and radiofrequency glow discharge (GD) modes for GD optical emission spectroscopy. The algorithm is divided into excitation and sputtering part and thus it is possible to distinguish between the different excitation processes and to consider equivalent sputtering crater formations in both modes. Intensity-time profiles are affected corresponding to the method by several effects. One important effect is that sputtering occurs at a single time in different depths because of curved crater bottoms, this is usually called crater effect. The main purpose is to introduce an iterative deconvolution technique which for the quantification numerically takes into account the curved sputtering crater bottom. Input data for the deconvolution technique are the calibrated mass-time profile, the partial densities of the sample constituents and the measured final shape of the sputtering crater. Using a relatively simple model for ion sputtering the deconvolution technique improves iteratively the calculated layer structure by means of information on crater formation. The mathematical handling is illustrated for the quantification of a depth profile of a multilayer sample of ten 100 nm layers. The resulting concentration-depth profile reflects excellently the real elemental distribution of the multilayer system. 相似文献
34.
35.
Summary The condensed bridged isoxazolines4 are rearranged on irradiation with a low-pressure mercury lamp exclusively into condensed derivatives of tetrahydropyridine5. The selectivity of the rearrangement is due to a stabilization of the biradical8 by the overlap of the radical-electrons with -electrons of the C=C double bond and the heterocyclic ring. Quantum yields of the photorearrangement, established from the consumption of the starting materials4, were determined.
Photochemie kondensierter Isoxazoline
Zusammenfassung Die kondensierten überbrückten Isoxazoline4 werden durch Bestrahlen mit einer Niederdruckquecksilberlampe ausschließlich zu kondensierten Tetrahydropyridinderivaten (5) umgelagert. Die Selektivität der Umlagerung beruht auf der Stabilisierung des Diradikals8 durch Überlappung der ungepaarten Elektronen mit -Elektronen der C=C-Doppelbindung und des Heterocyclus. Aus dem Verbrauch an Ausgangsmaterial (4) wurden Quantenausbeuten der Photoumlagerung bestimmt.相似文献
36.
Kubíček Vladimír Kučová Daria Císarř Prřemysl Burešová Vlasta 《Mikrochimica acta》2003,142(4):273-276
An ion-pair extraction spectrophotometry method was developed for the determination of fenpiverine bromide in tablets. To determine this substance it was necessary to find experimental conditions that would allow eliminating the influence of other components of the tablets. Attention was paid to the fact that a suitable pH of water phase was necessary to achieve high selectivity.Received December 11, 2002; accepted April 24, 2003
Published online July 28, 2003 相似文献
37.
Maurer HH Tenberken O Kratzsch C Weber AA Peters FT 《Journal of chromatography. A》2004,1058(1-2):169-181
A liquid chromatographic-mass spectrometric assay with atmospheric pressure chemical ionization (LC-APCI-MS) is presented for screening for, library-assisted identification (both in scan mode) and quantification (selected-ion mode) of the beta-blockers acebutolol, diacetolol, alprenolol, atenolol, betaxolol, bisoprolol, bupranolol, carazolol, carteolol, carvedilol, celiprolol, esmolol, labetalol, metoprolol, nadolol, nebivolol, oxprenolol, penbutolol, propranolol, sotalol, talinolol and timolol in blood plasma after mixed-mode (HCX) solid-phase extraction (SPE) and separation by reverse-phase liquid chromatography with gradient elution. The validation data were within the required limits. The assay was successfully applied to authentic plasma samples allowing confirmation of diagnosis of overdose situations as well as monitoring of patients' compliance. 相似文献
38.
The synthesis and binding properties of a new tricationic guanidiniocarbonyl pyrrole receptor 7 are described. Receptor 7 binds citrate 9 and other tricarboxylates such as trimesic acid tricarboxylate 8 with unprecedented high association constants of K(assoc) > 10(5) M(-1) in water as determined by UV and fluorescence tritration studies. According to NOESY experiments and molecular modeling calculations, the tricarboxylates are bound within the inner cavity of receptor 7 by ion pairing between the carboxylate groups and the guanidiniocarbonyl pyrrole moieties, favored by the nonpolar microenvironment of the cavity. Hence, receptor 7 can be regarded as a molecular flytrap. In the case of the aromatic tricarboxylate 8, additional aromatic interactions further strengthen the complex. The complexes with the tricarboxylates are so strong that even the presence of a large excess of competing anions or buffer salts does not significantly affect the association constant. For example, the association constant for citrate changes only from K(assoc) = 1.6 x 10(5) M(-1) in pure water to K(assoc) = 8.6 x 10(4) M(-1) in the presence of a 170-fold excess of bis-tris buffer and a 1000-fold excess of chloride. This makes 7 one of the most efficient receptors for the binding of citrate in aqueous solvents reported thus far. 相似文献
39.
Fauhl C Wittkowski R Lofthouse J Hird S Brereton P Versini G Lees M Guillou C 《Journal of AOAC International》2004,87(5):1179-1188
The aim of the present study was to provide the official wine control authorities with an internationally validated method for the determination of 3-methoxy-1,2-propanediol (3-MPD) and cyclic diglycerols (CycDs)-both of which are recognized as impurities of technical glycerol-in different types of wine. Because glycerol gives a sweet flavor to wine and contributes to its full-body taste, an economic incentive is to add glycerol to a wine to mask its poor quality. Furthermore, it is known that glycerol, depending on whether it is produced from triglycerides or petrochemicals, may contain considerable amounts of 3-MPD in the first case or CycDs in the second. However, because these compounds are not natural wine components, it is possible to detect glycerol added to wine illegally by determining the above-mentioned by-products. To this end, one of the published methods was adopted, modified, and tested in a collaborative study. The method is based on gas chromatographic/mass spectrometric analysis of diethyl ether extracts after salting out with potassium carbonate. The interlaboratory study for the determination of 3-MPD and CycDs in wine was performed in 11 laboratories in 4 countries. Wine samples were prepared and sent to participants as 5 blind duplicate test materials and 1 single test material. The concentrations covered ranges of 0.1-0.8 mg/L for 3-MPD and 0.5-1.5 mg/L for CycDs. The precision of the method was within the range predicted by the Horwitz equation. HORRAT values obtained for 3-MPD ranged from 0.8 to 1.7, and those obtained for CycDs ranged from 0.9 to 1.3. Average recoveries were 104 and 109%, respectively. 相似文献
40.
A dimethylsiloxane diluted polysiloxane side chain co-polymer with non-chiral banana-shaped mesogenic units shows an optically isotropic ferroelectric switching polar smectic C phase (SmCPF) consisting of a conglomerate of homogeneously chiral domains with opposite handedness. 相似文献