全文获取类型
收费全文 | 730篇 |
免费 | 49篇 |
国内免费 | 13篇 |
专业分类
化学 | 478篇 |
晶体学 | 5篇 |
力学 | 20篇 |
数学 | 69篇 |
物理学 | 220篇 |
出版年
2024年 | 3篇 |
2023年 | 7篇 |
2022年 | 10篇 |
2021年 | 23篇 |
2020年 | 31篇 |
2019年 | 26篇 |
2018年 | 27篇 |
2017年 | 29篇 |
2016年 | 58篇 |
2015年 | 26篇 |
2014年 | 54篇 |
2013年 | 63篇 |
2012年 | 72篇 |
2011年 | 50篇 |
2010年 | 41篇 |
2009年 | 28篇 |
2008年 | 35篇 |
2007年 | 31篇 |
2006年 | 22篇 |
2005年 | 23篇 |
2004年 | 15篇 |
2003年 | 16篇 |
2002年 | 10篇 |
2001年 | 3篇 |
2000年 | 8篇 |
1999年 | 3篇 |
1998年 | 6篇 |
1997年 | 4篇 |
1996年 | 5篇 |
1995年 | 1篇 |
1994年 | 4篇 |
1993年 | 6篇 |
1992年 | 5篇 |
1991年 | 11篇 |
1990年 | 2篇 |
1989年 | 4篇 |
1988年 | 2篇 |
1987年 | 4篇 |
1986年 | 2篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 6篇 |
1982年 | 3篇 |
1981年 | 3篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1967年 | 1篇 |
1957年 | 1篇 |
排序方式: 共有792条查询结果,搜索用时 15 毫秒
51.
Pathak Madhvesh Bohra Rakesh Mehrotra Ram C. Lorenz Ingo-Peter Piotrowski Holger 《Transition Metal Chemistry》2003,28(2):187-192
Reactions of cis-dialkoxy-bis(acetylacetonato)titanium(IV), [(acac)2Ti(OR)2] (R = Et, Pr
i
) with alkoxyalkanols (ROCH2CH2OH) (R = Me, Et, n-Bu) in 1:1 and 1:2 molar ratios in refluxing benzene under anhydrous conditions yield [(acac)2Ti(OR)2–n
(OCH2CH2OR)
n
] (n = 1 or 2) complexes, which were purified by distillation under reduced pressure. On the basis of i.r. and n.m.r. (1H- and 13C-) spectral studies, a cis-octahedral environment around TiIV is proposed. On keeping the distilled dark brown-red viscous liquid [(acac)2Ti(OEt)(OCH2CH2OBu)] for 2 weeks, orange yellow crystals of [(acac)2TiO]2 were obtained. A single crystal X-ray diffraction study suggests the product is a new modification of [(acac)2TiO]2. 相似文献
52.
53.
Low‐temperature sol–gel transformation of methyl silicon precursors to silica‐based hybrid materials
Veena Dhayal Rakesh Bohra Meena Nagar Ajay Kaushik Sanjay Mathur Sven Barth 《应用有机金属化学》2008,22(11):629-636
Six new methyl silicon (IV) precursors of the type [MeSi{ON?C(R)Ar}3] [when R = Me, Ar = 2‐C5H4N ( 1 ), 2‐C4H3O ( 2 ) or 2‐C4H3S ( 3 ); and when R = H, Ar = 2‐C5H4N ( 4 ), 2‐C4H3O ( 5 ) or 2‐C4H3S ( 6 )] were prepared and structurally characterized by various spectroscopic techniques. Molecular weight measurements and FAB (Fast Atomic Bombardment) mass spectral studies indicated their monomeric nature. 1H and 13C{1H} NMR spectral studies suggested the oximate ligands to be monodentate in solution, which was confirmed by 29Si{1H} NMR signals in the region expected for tetra‐coordinated methylsilicon (IV) derivatives. Thermogravimetric analysis of 1 revealed the complex to be thermally labile, decomposing to a hybrid material of definite composition. Two representative compounds ( 2 and 4 ) were studied as single source molecular precursor for low‐temperature transformation to silica‐based hybrid materials using sol–gel technique. Formation of homogenous methyl‐bonded silica materials (MeSiO3/2) at low sintering temperature was observed. The thermogravimetric analysis of the methylsilica material indicated that silicon‐methyl bond is thermally stable up to a temperature of 400 °C. Reaction of 2 and Al(OPri)3 in equimolar ratio in anhydrous toluene yielded a brown‐colored viscous liquid of the composition [MeSi{ON?C(CH3)C4H3O}3.Al(OPri)3]. Spectroscopic techniques 1H, 13C{1H}, 27Al{1H} and 29Si{1H} NMR spectra of the viscous product indicated the presence of tetracoordination around both silicon and aluminum atoms. On hydrolysis it yielded methylated aluminosilicate material with high specific surface area (464 m2/g). Scanning electron micrography confirmed a regular porous structure with porosity in the nanometric range. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
54.
55.
Force-length relations at ambient temperature have been determined for a set of polyethylenes which represent a wide range in molecular weight and molecular constitution. Taking advantage of previous work from this laboratory, samples have been prepared in such a manner that the important independent structural variables can be identified and isolated and their influence on the different aspects of the deformation process assessed. Partial melting-recrystallization processes appear to play an important role. For the linear polymers there is a direct influence of molecular weight. The influence of molecular weight manifests itself in the structure of the interlamellar zone which has a major influence on the initial modulus as well as the ultimate properties. Copolymers and branched copolymers display quite different behavior. The most striking difference is the invariance of the ultimate properties with molecular weight, branching, and level of crystallinity. From the set of experimental results that are presented the molecular factors involved in the deformation process can be sorted out. It becomes quite evident that all of the basic structural regions, characteristic of semicrystalline polymers, contribute to the observations. Focus solely on the changes in the crystallite, in analogy to the deformation of small-molecule crystalline systems, is inadequate in the case of crystalline polymers. 相似文献
56.
Rakesh Kumar Singh P. Senthilkumaran Kehar Singh 《Optics and Lasers in Engineering》2009,47(7-8):831-841
Tight focusing of linearly and circularly polarized vortex beams is studied in the presence of third-order spherical aberration, using vectorial Debye–Wolf integral. Results for total intensity distribution are presented for both polarizations. In addition, results for x-, y-, and z-polarization components are presented for the circularly polarized beam. Generation of longitudinal optical vortex in the tightly focused left circularly polarized beam has also been demonstrated by plotting its phase distribution. Compensation for the effect of spherical aberration has been studied in the presence of defocusing. Effect of aberration on the dark core of a tightly focused azimuthally polarized beam is also investigated. 相似文献
57.
58.
Seafood, including fish, shrimp, clam, crab, mussel, oyster, lobster, squid, octopus, and cuttlefish samples, was used to compare the recovery of Salmonella serovars by different selective enrichment and isolation media. The samples were selectively enriched in Rappaport-Vassiliadis (RV) broth and tetrathionate broth (TT), followed by selective isolation on Hektoen enteric (HE) agar, xylose lysine desoxycholate (XLD) agar, bismuth sulfite (BS) agar, and Brilliant Green (BG) agar media. Of 443 seafood samples analyzed, 108 were found to be contaminated with Salmonella. The role of selective enrichment in Salmonella spp. recovery with RV medium was distinctly high (70%) compared to TT broth (30%). The selective enrichment in RV broth followed by selective isolation on XLD, HE, BS, and BG agar recovered Salmonella at levels of 56, 41, 28, and 16%, respectively. Similarly, after enrichment in TT broth, XLD and HE agars recovered 27 and 23% respectively. The recovery of Salmonella with enrichment in TT followed by isolation on BS and BG was abysmally low at 4.6 and 5%, respectively. There was no significant difference (P > 0.05) in the recovery of Salmonella using the combinations of XLD and HE media with selective enrichment in RV broth. However, performance difference (P < 0.05) was observed in the recovery when BS and BG with RV, and XLD, HE, BS, and BG agars with TT broth were used. The present study showed that the combination of RV with XLD was the most efficient media for isolation of Salmonella from seafood when compared to other isolation media combinations. 相似文献
59.
Biechele TL Camp ND Fass DM Kulikauskas RM Robin NC White BD Taraska CM Moore EC Muster J Karmacharya R Haggarty SJ Chien AJ Moon RT 《Chemistry & biology》2010,17(11):1177-1182
To identify new protein and pharmacological regulators of Wnt/β-catenin signaling, we used a cell-based reporter assay to screen a collection of 1857 human-experienced compounds for their ability to enhance activation of the β-catenin reporter by a low concentration of WNT3A. This identified 44 unique compounds, including the FDA-approved drug riluzole, which is presently in clinical trials for treating melanoma. We found that treating melanoma cells with riluzole in?vitro enhances the ability of WNT3A to regulate gene expression, to promote pigmentation, and to decrease cell proliferation. Furthermore riluzole, like WNT3A, decreases metastases in a mouse melanoma model. Interestingly, siRNAs targeting the metabotropic glutamate receptor, GRM1, a reported indirect target of riluzole, enhance β-catenin signaling. The unexpected regulation of β-catenin signaling by both riluzole and GRM1 has implications for the future uses of this drug. 相似文献
60.
Clifford MN Wu W Kirkpatrick J Jaiswal R Kuhnert N 《Rapid communications in mass spectrometry : RCM》2010,24(21):3109-3120
The chlorogenic acids of Gardeniae Fructus used traditionally as a Chinese herbal medicine (zhizi) have been investigated qualitatively by liquid chromatography/multi-stage mass spectrometry (LC/MS(4)). Twenty-nine chlorogenic acids were detected and twenty-five characterised to regioisomer level on the basis of their fragmentation, twenty-four for the first time from this source. Assignment to the level of individual regioisomers was possible for three caffeoylquinic acids, three dicaffeoylquinic acids, three sinapoylquinic acids, four caffeoyl-sinapoylquinic acids, two feruloyl-sinapoylquinic acids, one p-coumaroyl-sinapoylquinic acid, three (3-hydroxy, 3-methyl)glutaroylquinic acids, two (3-hydroxy, 3-methyl)glutaroyl-feruloylquinic acids, one (3-hydroxy, 3-methyl)glutaroyl-dicaffeoylquinic acid, and one (3-hydroxy, 3-methyl)glutaroyl-caffeoyl-feruloylquinic acid. Six (3-hydroxy, 3-methyl)glutaroyl-caffeoylquinic acids were detected and two were tentatively assigned as 3-caffeoyl-4-(3-hydroxy, 3-methyl)glutaroylquinic acid and 3-caffeoyl-5-(3-hydroxy, 3-methyl)glutaroylquinic acid. The (3-hydroxy, 3-methyl)glutaroyl residue modifies the mass spectral fragmentation behavior and elution sequence compared with the chlorogenic acids that contain only a cinnamic acid residue(s). Fourteen of these twenty-nine chlorogenic acids have not previously been reported from any source. 相似文献