全文获取类型
收费全文 | 29321篇 |
免费 | 112篇 |
国内免费 | 270篇 |
专业分类
化学 | 10917篇 |
晶体学 | 260篇 |
力学 | 1408篇 |
综合类 | 12篇 |
数学 | 8998篇 |
物理学 | 8108篇 |
出版年
2022年 | 33篇 |
2021年 | 64篇 |
2020年 | 35篇 |
2019年 | 29篇 |
2018年 | 1198篇 |
2017年 | 1452篇 |
2016年 | 725篇 |
2015年 | 569篇 |
2014年 | 482篇 |
2013年 | 701篇 |
2012年 | 3172篇 |
2011年 | 2333篇 |
2010年 | 1812篇 |
2009年 | 1559篇 |
2008年 | 576篇 |
2007年 | 621篇 |
2006年 | 623篇 |
2005年 | 4447篇 |
2004年 | 3927篇 |
2003年 | 2321篇 |
2002年 | 502篇 |
2001年 | 286篇 |
2000年 | 89篇 |
1999年 | 180篇 |
1998年 | 108篇 |
1997年 | 68篇 |
1996年 | 62篇 |
1995年 | 48篇 |
1994年 | 55篇 |
1992年 | 179篇 |
1991年 | 153篇 |
1990年 | 137篇 |
1989年 | 109篇 |
1988年 | 100篇 |
1987年 | 62篇 |
1986年 | 43篇 |
1985年 | 42篇 |
1984年 | 29篇 |
1983年 | 29篇 |
1979年 | 29篇 |
1976年 | 82篇 |
1975年 | 38篇 |
1974年 | 41篇 |
1973年 | 48篇 |
1972年 | 39篇 |
1970年 | 35篇 |
1969年 | 37篇 |
1968年 | 37篇 |
1967年 | 31篇 |
1966年 | 37篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
121.
Conversion reactions of n-butenes over zeolites and amorphous catalysts have been investigated to deduce the factor that determines the selectivity
for the skeletal isomerization producing isobutene. The effects of pore structure and acid site concentration on the selectivity
for the skeletal isomerization are discussed on various catalysts. The pore structures of FER and CLI zeolites induce the
distant locations of butene molecules, accelerating monomolecular skeletal isomerization. On the other hand, acid site concentration
determines the preferred reaction path of n-butenes on amorphous catalysts. Oligomerization followed by cracking that produces various hydrocarbons is suppressed on
the catalyst with low acid site concentration, resulting in high selectivity for isobutene. The feasibility of monomolecular
skeletal isomerization on zeolites and amorphous catalysts is confirmed by its reversibility with high selectivity. 相似文献
122.
Sébastien Fiorucci Jer?me Golebiowski Daniel Cabrol-Bass Serge Antonczak 《Chemphyschem》2004,5(11):1726-1733
Flavonoids are naturally occurring phenol derivatives present in substantial amounts in a large variety of plants, fruits and vegetables daily eaten by humans. Most of these compounds exhibit several interesting biological activities, such as antiradical and antioxidant actions. Indeed, by complexation with specific enzymes, flavonoids are notably liable to metabolize molecular dioxygen. On the basis of experimental results describing oxygenolysis of the flavonoid quercetin, activated by the enzyme quercetin 2,3-dioxygenase (2,3-QD),ur attention has focused on the role of metal center in the activation of the substrate quercetin. Thus, in the present study, by means of DFT calculations at the B3LYP/ 6-31(+)G* level on model molecular systems, we describe different mechanisms for dioxygen metabolization by quercetin. Stationary points are described, and energetic and structural analyses along the reaction paths are reported. Our calculations show that the copper cation must act as an oxidant towards the substrate and that the reaction proceeds through a 1,3-cycloaddition. 相似文献
123.
Trace analysis of rapamycin in human blood by micellar electrokinetic chromatography 总被引:1,自引:0,他引:1
A capillary electrophoretic method with UV detection at 278 nm has been developed for analysis of the immunosuppressant rapamycin (sirolimus) in human blood at low microgram per liter levels. Separation has been achieved in an acidic carrier electrolyte containing sodium dodecylsulfate and 30% (v/v) acetonitrile. For sample clean-up and preconcentration, an off-line solid-phase extraction step using a silica-based reversed-phase material and an on-capillary focussing technique were employed. The latter allows the injection of increased sample volumes without excessive band broadening. Although this new method is less sensitive than existing liquid chromatographic procedures combined with mass spectrometry, it is fully suited to routine analysis of rapamycin in blood from patients treated with this drug. Last but not least the low costs make it an attractive alternative to established methods. 相似文献
124.
125.
The discovery of selective cyclooxygenase-2 (COX-2) inhibitors represents a major achievement of the efforts over the past few decades to develop therapeutic treatments for inflammation. To gain insights into designing new COX-2-selective inhibitors, we address the energetic and structural basis for the selective inhibition of COX isozymes by means of a combined computational protocol involving docking experiment, force field design for the heme prothetic group, and free energy perturbation (FEP) simulation. We consider both COX-2- and COX-1-selective inhibitors taking the V523I mutant of COX-2 to be a relevant structural model for COX-1 as confirmed by a variety of experimental and theoretical evidences. For all COX-2-selective inhibitors under consideration, we find that free energies of binding become less favorable as the receptor changes from COX-2 to COX-1, due to the weakening and/or loss of hydrogen bond and hydrophobic interactions that stabilize the inhibitors in the COX-2 active site. On the other hand, COX-1-selective oxicam inhibitors gain extra stabilization energy with the change of residue 523 from valine to isoleucine because of the formations of new hydrogen bonds in the enzyme-inhibitor complexes. The utility of the combined computational approach, as a valuable tool for in silico screening of COX-2-selective inhibitors, is further exemplified by identifying the physicochemical origins of the enantiospecific selective inhibition of COX-2 by -substituted indomethacin ethanolamide inhibitors. 相似文献
126.
127.
Xianfeng?You Feng?Chen Jinlong?ZhangEmail author 《Journal of Sol-Gel Science and Technology》2005,34(2):181-187
TiO2 powders were prepared by sol–gel template method and calcined under different conditions. XRD, BET and TEM were used to characterize the TiO2 powders obtained. The photocatalytic activity of TiO2 was investigated by the degradation of methyl orange. It was found that TiO2 powder has the highest photocatalytic activity at a calcination temperature of 673 K. The effects of physical properties such as surface area, crystallinity and crystal phase on the photocatalytic activity of TiO2 were discussed. 相似文献
128.
129.
Rongbiao?WangEmail author Herbert?Schmiedel Bernd-Reiner?Paulke 《Colloid and polymer science》2004,283(1):91-97
Isothermal titration calorimetry (ITC) measurements of the mixture of the cationic surfactant cetyl trimethyl ammonium bromide (CTAB) with negatively charged, hairy copolymer latices (poly-(2,3-epoxypropylmethacrylate-co-methacrylic acid) in different ratio) at high water excess indicate a monomer adsorption mechanism of CTAB by the polymer particles. The number of adsorbed CTAB molecules at saturation corresponds approximately to the number of negative elementary charges bound at the surface of the latices. The mixing enthalpy is the sum of demicellization and sorption enthalpies. At 25 °C for CTAB the demicellization enthalpy amounts to 10 kJ/mol, whereas the adsorption enthalpy varies from –7 kJ/mol (surface charge density of the latices
=–0.37 C/m2) to +3 kJ/mol (=–0.085 C/m2). The hydrodynamic radius
RH of the latex particles upon titration of cationic detergent and salt (NaBr) decreases by about 2 nm until the onset of aggregation near the isoelectric point. Titration of nonionic or anionic detergents has much less influence on the hydrodynamic radius and produces no measurable adsorption heat. The results are consistent within a model of latex particles with extended negatively charged polymer chains interacting predominantly via Coulombic forces with detergents. 相似文献
130.
Veronica?StigssonEmail author G?ran?Kloow Ulf?Germg?rd Niclas?Andersson 《Cellulose (London, England)》2005,12(4):395-401
Controlling the reduction in molecular weight of the cellulose chains is essential in the production of carboxymethyl cellulose
(CMC). Such a reduction can be achieved by the addition of cobalt during the process of cobalt(II) ions, which act as a catalyst
for oxidative cleavage, and the influence thereof has been studied under a variety of conditions. This study has resulted
in a model that summarises the effects of the added amount of cobalt, the time for the cobalt reaction, the temperature in
the mercerisation stage of the CMC-manufacturing process and finally the effect of the temperature in the etherification stage.
It is shown that it is important for cobalt to be present during the mercerisation stage in order to achieve the desired viscosity. 相似文献