全文获取类型
收费全文 | 3592篇 |
免费 | 96篇 |
国内免费 | 8篇 |
专业分类
化学 | 2866篇 |
晶体学 | 24篇 |
力学 | 40篇 |
数学 | 173篇 |
物理学 | 593篇 |
出版年
2022年 | 21篇 |
2021年 | 30篇 |
2020年 | 43篇 |
2019年 | 61篇 |
2018年 | 37篇 |
2017年 | 22篇 |
2016年 | 58篇 |
2015年 | 50篇 |
2014年 | 77篇 |
2013年 | 163篇 |
2012年 | 149篇 |
2011年 | 211篇 |
2010年 | 73篇 |
2009年 | 95篇 |
2008年 | 179篇 |
2007年 | 184篇 |
2006年 | 177篇 |
2005年 | 216篇 |
2004年 | 163篇 |
2003年 | 137篇 |
2002年 | 140篇 |
2001年 | 111篇 |
2000年 | 137篇 |
1999年 | 47篇 |
1998年 | 38篇 |
1997年 | 34篇 |
1996年 | 55篇 |
1995年 | 29篇 |
1994年 | 48篇 |
1993年 | 36篇 |
1992年 | 50篇 |
1991年 | 44篇 |
1990年 | 39篇 |
1989年 | 39篇 |
1988年 | 52篇 |
1987年 | 41篇 |
1986年 | 60篇 |
1985年 | 54篇 |
1984年 | 56篇 |
1983年 | 30篇 |
1982年 | 33篇 |
1981年 | 34篇 |
1980年 | 29篇 |
1979年 | 31篇 |
1978年 | 28篇 |
1977年 | 26篇 |
1976年 | 21篇 |
1975年 | 32篇 |
1974年 | 28篇 |
1972年 | 21篇 |
排序方式: 共有3696条查询结果,搜索用时 0 毫秒
101.
Polyanionic glycopolymers were synthesized aiming at establishing a simple process for assembling glycosyl arrays. The synthetic glycopolymers carry the key carbohydrate epitopes of α-d-galactobioside (Gb2), β-lactoside, and α-d-mannopyranoside, each of which serves as a ligand of bacterial toxins and adhesion proteins. The Gb2 epitope, prepared from penta-O-acetyl-d-galactopyranose, was coupled with poly(ethylene-alt-maleic anhydride) in a polymer reaction to afford a Gb2-embedded glycopolymer having also carboxylate (COO−) polyanions at the side chain. The polyanionic glycopolymer was then applied to a preparation of sugar-coated gold electrodes, which involves an alternating layer-by-layer adsorption based on electrostatic interactions. The presence of the Gb2-coat on the surface was evidenced by Fourier transform infrared reflection absorption spectroscopy. The Gb2-coated glyco-chip was stable in 10 mM HEPES buffer containing 150 mM NaCl aq. Other glycopolymers carrying the β-lactoside and α-d-mannopyranoside epitopes were applied to the same assembling process. The derived glycosyl arrays will be useful for detecting Shiga toxins, other pathogenic toxins and viruses when applied as glyco-chips for surface plasmon resonance or quartz crystal microbalance technique. 相似文献
102.
Ikehata J Shinomiya K Kobayashi K Ohshima H Kitanaka S Ito Y 《Journal of chromatography. A》2004,1025(2):169-175
The effect of Coriolis force on the counter-current chromatographic separation was studied using centrifugal partition chromatography (CPC) with four different two-phase solvent systems including n-hexane-acetonitrile (ACN); tert-butyl methyl ether (MtBE)-aqueous 0.1% trifluoroacetic acid (TFA) (1:1); MtBE-ACN-aqueous 0.1% TFA (2:2:3); and 12.5% (w/w) polyethylene glycol (PEG) 1000-12.5% (w/w) dibasic potassium phosphate. Each separation was performed by eluting either the upper phase in the ascending mode or the lower phase in the descending mode, each in clockwise (CW) and counterclockwise column rotation. Better partition efficiencies were attained by the CW rotation in both mobile phases in all the two-phase solvent systems examined. The mathematical analysis also revealed the Coriolis force works favorably under the CW column rotation for both mobile phases. The overall results demonstrated that the Coriolis force produces substantial effects on CPC separation in both organic-aqueous and aqueous-aqueous two-phase systems. 相似文献
103.
[reaction: see text]. The zirconium-mediated intramolecular ester transfer reaction of N-alkenyl carbamate derivatives proceeded to give alpha-substituted gamma-aminobutyric acid (GABA) derivatives in good to excellent yields. Quenching experiments of the reaction mixture with iodine or O2 indicated the presence of a cyclopropane intermediate. The resulting iodide was converted to 2-substituted pyrrolidine-3-carboxylate and/or alpha-alkylidene-gamma-aminobutyric acid derivatives in a stereospecific manner. 相似文献
104.
The excitation wavelength dependences of the intensities of the Raman lines of pyrazine have been measured. The intensity enhancement of the non-totally symmetric Raman line at 925 cm?1 provided firm evidence of the vibronic coupling between the lowest 1B3u(n,π*) and second lowest 1B2u(π,π*) states. The excitation wavelength dependences of other non-totally symmetric Raman lines suggest also the various vibronic coupling schemes. 相似文献
105.
Three new metabolites, kunzeanones A (1), B (2), and C (3), along with three known compounds, cryptostrobin (4), (+)-spathulenol (5), and (−)-globulol (6), were isolated from the non-polar fraction of the dried leaves of Kunzea ambigua (Myrtaceae), which shows ichthyotoxicity toward a small fish, medaka. The structures of these new compounds were elucidated as condensates of alkylated phloroglucinol with methylflavanone and germacrane-type sesquiterpene, respectively, on the basis of spectral analyses including 1-D and 2-D NMR spectra. The stereochemistries of kunzeanones A and B were determined by X-ray crystallographic analysis. A sesquiterpene, (+)-spathulenol (5), among the isolates was characterized as the ichthyotoxic principle of the extract. 相似文献
106.
Akasaka T Maeda Y Wakahara T Mizushima T Ando W Walchli M Suzuki T Kobayashi K Nagase S Kako M Nakadaira Y Fujitsuka M Ito O Sasaki Y Yamamoto K Erata T 《Organic letters》2000,2(17):2671-2674
[reaction: see text]In the photochemical bis-germylation of C60 with 1,1,2,2-tetrakis(2,6-diethylphenyl)-1,2-digermirane (1), a cycloadduct (2) is obtained in high yield for the first time. Spectroscopic analysis and theoretical investigation confirm that 2 (which has C1 symmetry) results from 1,4-cycloaddition. Control experiments and laser flash photolysis experiments suggest that an exciplex intermediate is responsible for the formation of 2. The redox properties of 2 were examined by differential pulse voltammetry. 相似文献
107.
Ito M Clark CW Mortimore M Goh JB Martin SF 《Journal of the American Chemical Society》2001,123(33):8003-8010
A linear synthesis of the indole alkaloid (+/-)-akuammicine (2) was completed by a novel sequence of reactions requiring only 10 steps from commercially available starting materials. The approach features a tandem vinylogous Mannich addition and an intramolecular hetero Diels-Alder reaction to rapidly assemble the pentacyclic heteroyohimboid derivative 8 from the readily available hydrocarboline 6. Oxidation of the E ring of 8 gave the lactone 9 that was converted into deformylgeissoschizine (11). The subsequent elaboration of 11 into 2 was effected by a biomimetically patterned transformation that involved sequential oxidation and base-induced skeletal reorganization. A variation of these tactics was then applied to the synthesis of the C(18) hydroxylated akuammicine derivative 36. Because 36 had previously been converted into strychnine (1) in four steps, its preparation constitutes a concise, formal synthesis of this complex alkaloid. 相似文献
108.
A new synthetic method for the preparation of allyl amines has been developed. The key steps of this method are enantioselective addition of diethylzinc and [1,3]-chirality transfer through the [3.3] sigmatropic rearrangement of allyl cyanates. Stereocontrolled syntheses of lentiginosine (1) and polyoxamic acid derivative 2 from a common intermediate 7 derived from D-tartaric acid (8), have been accomplished. 相似文献
109.
Fatty acid methyl esters from various fats and oils were separated by comprehensive two-dimensional supercritical fluid chromatography with conventional packed columns and FID detection. The first dimension was a silica gel column and the second dimension was an ODS column. This combination was largely orthogonal for the separation of fatty acid methyl esters. The first dimension separations were primarily based on the number of double bonds while the second dimension separations were based on the chain length. The highly-ordered chromatograms and improved resolution allowed the easy detection and identification of minor components. Although the first dimension separations were performed under isobaric conditions where the peak width increased in proportion to the retention, the programming of the sampling duration allowed us to maintain the optimum re-injection frequency (3–4 times) per peak into the second dimension and so to minimize the total analysis time without deteriorating the resolution. 相似文献
110.
The coadsorption of carbon monoxide (CO) and water molecules on a Ru(0 0 1) surface has been studied by infrared spectroscopy, LEED and STM. At high CO coverage phases, a 2×2-(2CO+D2O) structure was observed on both UHV and electrode surfaces. Electrode potential dependent structures from CO and water adlayers on an electrode surface were reproduced on a UHV surface by controlling molecular orientations of the first layer and second over-layer water molecules. At lower CO coverages, a CO band center showed coverage dependent shift down to 1444 cm−1 due to an electron transfer from a lone pair of a water molecule to CO 2π*. 相似文献