全文获取类型
收费全文 | 687篇 |
免费 | 50篇 |
国内免费 | 2篇 |
专业分类
化学 | 543篇 |
晶体学 | 6篇 |
力学 | 16篇 |
数学 | 40篇 |
物理学 | 134篇 |
出版年
2024年 | 3篇 |
2023年 | 7篇 |
2022年 | 14篇 |
2021年 | 22篇 |
2020年 | 28篇 |
2019年 | 28篇 |
2018年 | 26篇 |
2017年 | 24篇 |
2016年 | 43篇 |
2015年 | 24篇 |
2014年 | 21篇 |
2013年 | 40篇 |
2012年 | 56篇 |
2011年 | 48篇 |
2010年 | 43篇 |
2009年 | 27篇 |
2008年 | 43篇 |
2007年 | 37篇 |
2006年 | 28篇 |
2005年 | 30篇 |
2004年 | 15篇 |
2003年 | 18篇 |
2002年 | 20篇 |
2001年 | 3篇 |
2000年 | 11篇 |
1999年 | 4篇 |
1998年 | 4篇 |
1997年 | 5篇 |
1996年 | 5篇 |
1995年 | 1篇 |
1994年 | 4篇 |
1993年 | 7篇 |
1992年 | 5篇 |
1991年 | 12篇 |
1990年 | 2篇 |
1989年 | 4篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 5篇 |
1984年 | 2篇 |
1983年 | 6篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1979年 | 2篇 |
1978年 | 1篇 |
排序方式: 共有739条查询结果,搜索用时 15 毫秒
21.
Surface modified ormosil nanoparticles 总被引:1,自引:0,他引:1
Organically modified silanes (ORMOSIL) such as vinyl triethoxysilane readily aggregate in the aqueous cores of reverse micelles where the triethoxysilane moieties are hydrolyzed to form a hydrated silica network and the vinyl groups protruded out from the surface of the nanoparticles toward the hydrophobic side of the micellar interface. These particles are spherical and the size distribution of the particles is relatively narrow, with an average diameter of 87 nm. Surface vinyl silica nanoparticles so formed have been oxidized to surface carboxylic silica nanoparticles, followed by chemical conjugation with polyethyleneglycol amine (PEG amine) through the ethyl-3-(3-dimethylaminopropyl) (EDCI) carbodiimide reaction. The characteristic surface groups have been identified by Fourier transform infrared spectroscopy, while the size and the morphology of the particles have been studied by dynamic light scattering and transmission electron microscopy. It has been found that about 80-85% of the carboxylic groups are PEGylated during the EDCI reaction. 相似文献
22.
R.K. Jain N.S. Kambo Rakesh Goel 《Journal of Computational and Applied Mathematics》1983,9(4):361-367
Using Lobatto nodes, one-step methods of order six and eight have been obtained for the second-order differential equation y″ = f(x, y), y(x0) = y0, y′(x0) = y′0. The methods are shown to be P-stable. If , then at each integration step a system of dimension 3s, 4s, respectively, has to be solved. The numerical results, for two problems, obtained by using these methods are given in the end. 相似文献
23.
Prasain JK Patel R Kirk M Wilson L Botting N Darley-Usmar VM Barnes S 《Journal of mass spectrometry : JMS》2003,38(7):764-771
Electrospray ionization combined with tandem mass spectrometry was applied to a study of some representative chlorinated and nitrated isoflavones-potential metabolites of isoflavones in inflammatory cells. Upon collision-induced dissociation of deprotonated [M - H](-) ions of these compounds, a number of structurally characteristic product ions were produced. The product ion analysis of 3'- and 8-chlorodaidzein in the tandom mass spectra led to ready differentiation of these isomers. 3-Nitro derivatives of both genistein and daidzein have product ions due to the losses of HNO(2) and two OH groups. Chlorinated derivatives of isoflavones were detected in cell-based experiments and their structures were proposed by comparing the tandem mass spectra of their product ions with those of standards. This work provides a suitable analytical basis to aid the characterization of chlorinated and nitrated metabolites in studies in vivo and in vitro. 相似文献
24.
25.
The hetero Diels-Alder reaction of 1-amino-3-siloxy-1,3-butadiene (1a) with a range of unactivated aldehydes proceeds readily under remarkably mild conditions: at room temperature and in the absence of Lewis acid catalysts. The cycloadducts are formed in good yields and can be converted directly to the corresponding dihydro-4-pyrones using acetyl chloride. Ketones and imines are also reactive in hetero Diels-Alder reactions with this diene. 相似文献
26.
The solution structure of Cobeta-5'-deoxyadenosylimidazolylcobamide, Ado(Im)Cbl, the coenzyme B(12) analogue in which the axial 5,6-dimethylbenzimidazole (Bzm) ligand is replaced by imidazole, has been determined by NMR-restrained molecular modeling. A two-state model, in which a conformation with the adenosyl moiety over the southern quadrant of the corrin and a conformation with the adenosyl ligand over the eastern quadrant of the corrin are both populated at room temperature, was required by the nOe data. A rotation profile and molecular dynamics simulations suggest that the eastern conformation is the more stable, in contrast to AdoCbl itself in which the southern conformation is preferred. Consensus structures of the two conformers show that the axial Co-N bond is slightly shorter and the corrin ring is less folded in Ado(Im)Cbl than in AdoCbl. A study of the thermolysis of Ado(Im)Cbl in aqueous solution (50-125 degrees C) revealed competing homolytic and heterolytic pathways as for AdoCbl but with heterolysis being 9-fold faster and homolysis being 3-fold slower at 100 degrees C than for AdoCbl. Determination of the pK(a)'s for the Ado(Im)Cbl base-on/base-off reaction and for the detached imidazole ribonucleoside as a function of temperature permitted correction of the homolysis and heterolysis rate constants for the temperature-dependent presence of the base-off species of Ado(Im)Cbl. Activation analysis of the resulting rate constants for the base-on species show that the entropy of activation for Ado(Im)Cbl homolysis (13.7 +/- 0.9 cal mol(-1) K(-1)) is identical with that of AdoCbl (13.5 +/- 0.7 cal mol(-1) K(-1)) but that the enthalpy of activation (34.8 kcal mol(-1)) is 1.0 +/- 0.4 kcal mol(-1) larger. The opposite effect is seen for heterolysis, where the enthalpies of activation are identical but the entropy of activation is 5 +/- 1 cal mol(-1) K(-1) less negative for Ado(Im)Cbl. Extrapolation to 37 degrees C provides a rate constant for Ado(Im)Cbl homolysis of 2.1 x 10(-9) s(-1), 4.3-fold smaller than for AdoCbl. Combined with earlier results for the enzyme-induced homolysis of Ado(Im)Cbl by the ribonucleoside triphosphate reductase from Lactobacillus leichmannii, the catalytic efficiency of the enzyme for homolysis of Ado(Im)Cbl at 37 degrees C can be calculated to be 4.0 x 10(8), 3.8-fold, or 0.8 kcal mol(-1), smaller than for AdoCbl. Thus, the bulky Bzm ligand makes at best a <1 kcal mol(-1) contribution to the enzymatic activation of coenzyme B(12). 相似文献
27.
Rakesh?Kumar?MahajanEmail author Jyoti?Chawla Mandeep?Singh?BakshiEmail author 《Colloid and polymer science》2004,282(10):1165-1168
Cloud point (CP) measurements of Tween 20 and Tween 80 were carried out in the presence of various glycol oligomers and triblock polymers (TBP). The cloud points of both Tween 20 and 80 decrease in the presence of both types of additives. Among the glycol oligomeric additives, ethylene glycol monobutyl ether was found to reduce the CP maximum. An increase in the repeating units of polymeric glycol additives leads to a decrease in CP. Reduction in the CP in the presence of TBP depends upon the increase in hydrophobic/hydrophilic ratio among the polypropylene to polyethylene units. 相似文献
28.
A first principle study of hydrogen storage in titanium-doped small carbon clusters (C2nTin,n = 2–6)
Structural Chemistry - Hydrogen storage in Ti-doped small carbon clusters, C2nTin (n = 2–6), has been studied using density functional theory. Using the principle of maximum hardness (η)... 相似文献
29.
30.
Kapil Mohan Saini Rakesh K. Saunthwal Sushmita Akhilesh K. Verma 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(5):1017-1021
Transition-metal-free regioselective synthesis of functionalized amino-indenones by the reaction of ortho-alkynylaldehydes with a broad range of primary amines by intramolecular cyclization has been described. The designed reaction proceeds through KOH-mediated Prins-type cyclization and DMSO-promoted oxidation of the cyclopent-2-en-1-one system. The proposed mechanism and role of solvent were well supported by control experiments. For the first time, we have disclosed the reverse reactivity of (2-alkynyl)-arylaldimines in a super basic system. 相似文献