全文获取类型
收费全文 | 1519篇 |
免费 | 81篇 |
国内免费 | 9篇 |
专业分类
化学 | 1182篇 |
晶体学 | 20篇 |
力学 | 6篇 |
数学 | 175篇 |
物理学 | 226篇 |
出版年
2023年 | 8篇 |
2022年 | 15篇 |
2021年 | 25篇 |
2020年 | 23篇 |
2019年 | 30篇 |
2018年 | 22篇 |
2017年 | 12篇 |
2016年 | 45篇 |
2015年 | 47篇 |
2014年 | 49篇 |
2013年 | 79篇 |
2012年 | 89篇 |
2011年 | 101篇 |
2010年 | 73篇 |
2009年 | 54篇 |
2008年 | 76篇 |
2007年 | 68篇 |
2006年 | 48篇 |
2005年 | 63篇 |
2004年 | 64篇 |
2003年 | 43篇 |
2002年 | 53篇 |
2001年 | 26篇 |
2000年 | 21篇 |
1999年 | 21篇 |
1998年 | 27篇 |
1997年 | 27篇 |
1996年 | 25篇 |
1995年 | 19篇 |
1994年 | 14篇 |
1993年 | 13篇 |
1992年 | 18篇 |
1991年 | 12篇 |
1990年 | 15篇 |
1989年 | 8篇 |
1988年 | 9篇 |
1987年 | 13篇 |
1986年 | 13篇 |
1985年 | 13篇 |
1984年 | 12篇 |
1983年 | 6篇 |
1982年 | 13篇 |
1981年 | 13篇 |
1980年 | 20篇 |
1979年 | 14篇 |
1978年 | 12篇 |
1977年 | 13篇 |
1975年 | 10篇 |
1973年 | 10篇 |
1969年 | 8篇 |
排序方式: 共有1609条查询结果,搜索用时 15 毫秒
1.
2.
3.
Polymer lightguides of PMMA doped with the azo dyes methyl-red and N, N-dihexyl-4-amino-4'-nitro-azobenzene (DHANA) are investigated with respect to their opto-optical properties. The trans-cis photoisomerisation of the dyes leads to reversible polarization-dependent optically induced refractive index changes. The index changes are anisotropic. Birefringence is measured using index matched lightguides. The changes with respect to each polarization are determined by leaky mode spectroscopy and by using a half-integrated interferometer. These changes are intensity dependent and, with a suitable geometry, bistability at low intensities (3 mW/mm3) can be obtained. 相似文献
4.
Susanne K. Wiedmer Toni Andersson Marika Sündermann Marja‐Liisa Riekkola Heikki Tenhu 《Journal of Polymer Science.Polymer Physics》2007,45(19):2655-2663
Cationic polyelectrolytes were synthesized and used as semipermanent coating materials for capillaries in electrophoresis. The polyelectrolytes used were a homopolymer of poly(methacryl oxyethyl trimethylammonium chloride) (PMOTAC) and its poly(ethylene glycol) (PEG)‐grafted analogue. Two PMOTAC polyelectrolytes, with molar masses of 85,000 and 300,000 g/mol, and PEG‐grafted PMOTAC with a molar mass of 280,000 g/mol were synthesized and then characterized by size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR) spectroscopy. Attachment of the polyelectrolytes to the wall of the fused silica capillary for electrophoresis caused the electroosmotic flow (EOF) to reverse. The polyelectrolyte coatings were tested over the pH range 2–11 at different buffer ionic strengths, and the most stable and strongest anodic EOFs were obtained at acidic pH values with low ionic strength buffers. Between runs the capillary is merely rinsed for 2 or 3 min with the background electrolyte solution. With the PMOTAC coatings at pH values ≤5, the RSDs of the EOFs were less than 2.9% after 60 injections. The effects of the molar mass of the polycation and of PEGylation of PMOTAC on the interactions between the polycations and basic proteins were studied at acidic pH values. The differences in the effective electrophoretic mobilities, resolution values, and plate numbers of the proteins with the different coatings were due to the EOF, as demonstrated through calculations of reduced mobilities, relative resolution values, and relative plate numbers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2655–2663, 2007 相似文献
5.
In the system (poly-(N-vinyl carbazole) (PVK): trinitrofluorenone (TNF) a photoconductive complex is formed. Thin metal films are sputtered on BK7 glass substrates, forming two electrodes with 1 mm separation. The photoconductive complex is deposited from a solution in chlorobenzene/tetrahydrofurane on the glass substrate between the electrodes, forming a photoconductive detector. Photoconductivity of these planar detectors is studied using He-Ne laser light (=633 nm) as a function of electric field and for different TNF concentrations. An increase of photosensitivity is found for high TNF concentrations.Time resolution of the photoconductive PVK:TNF detector is investigated using a ruby pulse laser (=694 nm). The possible use of such detectors in combination with other polymer lightguides is demonstrated. Compared to most polymer waveguide materials PVK exhibits a rather high refractive index ofn=1.7. Thus the coupling of light into the photoconductive film is achieved directly. The planar structure allows further integration of polymeric components for optoelectronics. 相似文献
6.
Rudolf O. Duthaler Peter Herold Susanne Wyler-Helfer Martin Riediker 《Helvetica chimica acta》1990,73(3):659-673
Chloro(cyclopentadienyl)bis(1,2:5,6-di-O-isopropylidene-α-D -glucofuranos-3-O-yl)titanium ( 1 ) is used for the transmetallation of Li-enolates obtained from propionyl derivatives. While such Ti-enolates of ketones and hydrazones appear to be unreactive, the (E)enolate 13 of 2,6-dimethylphenyl propionate ( 11 ) adds to the re-side of aldehydes, affording various syn-aldols 14 with high dia- and enantioselectivity (92–97% ds, 91–97% ee, cf. Scheme 2 and Table 1). Racemic syn-aldols (±)- 14 are obtained analogously from the achiral bis(2-propyloxy)-Ti-enolate 15 (Scheme 2 and Table 2). In contrast to the unstable Li-enolate 10 , the Ti-enolates 13 and 15 isomerize at ?30°, presumably to the thermodynamically more stable (Z)-enolates (Scheme 4), While the diastereoselectivity of the achiral enolate 15 is lost upon this equilibration, the chiral (Z)-enolate 27 quite unexpectedly affords anti-aldols 12 of high optical purity (94–98% ec) and, in most cases, with acceptable-to-good diastereoselectivity (82–90% ds). Notable exceptions are branched unsaturated and aromatic aldehydes which form a greater proportion of synepimers of moderate optical purity (Scheme 5 and Table 3). Consistent with these findings, re-facial-and ami -selective aldol-addition is also exhibited by the (Z)-configurated Ti-enolate 22 of N-propionyl-oxazolidi-none 19 (Scheme 3). 相似文献
7.
Leva S Lichte A Burmeister J Muhn P Jahnke B Fesser D Erfurth J Burgstaller P Klussmann S 《Chemistry & biology》2002,9(3):351-359
Mirror-image oligonucleotide ligands (Spiegelmers) that bind to the pharmacologically relevant target gonadotropin-releasing hormone I (GnRH) with high affinity and high specificity have been identified using the Spiegelmer technology. GnRH is a decapeptide that plays an important role in mammalian reproduction and sexual maturation and is associated with several benign and malignant diseases. First, aptamers that bind to D-GnRH with dissociation constants of 50-100 nM were isolated out of RNA and DNA libraries. The respective enantiomers of the DNA and RNA aptamers were synthesized, and their binding to L-GnRH was shown. These Spiegelmers bind to L-GnRH with similar affinity to that of the corresponding aptamers that bind to D-GnRH. We further demonstrated dose-dependent inhibition of GnRH-induced Ca(2+) release in Chinese hamster ovary cells that were stably transfected with the human GnRH receptor. 相似文献
8.
Burkhard Schmidt Ingo Franke Franz-Josef Witteler Michael Binder 《Helvetica chimica acta》1983,66(8):2564-2571
The novel cannabinoids (6aR, 10aR)-N-ethyl-Δ8-tetrahydrocannabinol-18-amide (15) and (6aR, 10aR, 17 RS)-N-ethyl-17-methyl-Δ8- tetrahydrocannabinol-18-amide (16) , designed as cannabinoid affinity ligands, were synthesized from the corresponding acids 11 and 12 via the N-hydroxysuccinimide esters. Amide 16 was tested in the rat and was generalized to Δ9-tetrahydrocannabinol, being 5 times less potent than the training drug. An improved synthesis of (6aR, 10aR)-17,18-didehydro-Δ8-tetrahydrocannabinol (23) is reported. As model reaction for the preparation of a tritiated Δ8-tetrahydrocannabinol, compound 23 was selectively deuterated at C(17) and C(18) in benzene/Et3N using [(C6H5)3P]3RuCl2 as catalyst. 相似文献
9.
One-bond 13C, 13C-spin-coupling constants have been measured, with natural isotope abundance, in η4-diene, η3-allyl and η2-ene transition-metal carbonyl complexes. Typical values of 1J(C,C) are given for Fe-, Ru- and Os-complexes with the three types of olefinic ligands. The effects of substituents and the structural significance of the C,C-coupling constants are discussed. 相似文献
10.
The syntheses of p-substituted 2-methyl-4-phenylbuten(1)-carboxylic acid derivatives are described, using Blanc's chloromethylation reaction, the Friedel-Crafts alkylation of unsaturated ketones or the Meerwein arylation; the formed intermediates react in subsequent steps to the title compounds. 相似文献