全文获取类型
收费全文 | 577篇 |
免费 | 27篇 |
国内免费 | 1篇 |
专业分类
化学 | 445篇 |
晶体学 | 2篇 |
力学 | 8篇 |
数学 | 54篇 |
物理学 | 96篇 |
出版年
2023年 | 4篇 |
2022年 | 2篇 |
2021年 | 3篇 |
2020年 | 11篇 |
2019年 | 5篇 |
2018年 | 14篇 |
2017年 | 9篇 |
2016年 | 28篇 |
2015年 | 23篇 |
2014年 | 32篇 |
2013年 | 47篇 |
2012年 | 39篇 |
2011年 | 33篇 |
2010年 | 29篇 |
2009年 | 13篇 |
2008年 | 36篇 |
2007年 | 37篇 |
2006年 | 36篇 |
2005年 | 22篇 |
2004年 | 20篇 |
2003年 | 19篇 |
2002年 | 16篇 |
2001年 | 5篇 |
2000年 | 7篇 |
1999年 | 6篇 |
1998年 | 4篇 |
1996年 | 3篇 |
1995年 | 3篇 |
1994年 | 2篇 |
1993年 | 7篇 |
1992年 | 6篇 |
1991年 | 4篇 |
1990年 | 2篇 |
1989年 | 2篇 |
1985年 | 4篇 |
1984年 | 3篇 |
1982年 | 4篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1978年 | 5篇 |
1977年 | 2篇 |
1975年 | 2篇 |
1970年 | 2篇 |
1959年 | 8篇 |
1958年 | 7篇 |
1957年 | 3篇 |
1956年 | 3篇 |
1954年 | 10篇 |
1933年 | 2篇 |
1907年 | 1篇 |
排序方式: 共有605条查询结果,搜索用时 62 毫秒
21.
Summary The addition of dienes to the system [(Cp2TiCl)2] LiAlH4toluene changes the system so that the complex [Cp2TiAlH4] is quantitatively formed instead of a titanocene hydride — aluminium hydride cluster. The complex [Cp2TiAlH4] is further converted into 3-allyltitanocene derivatives ([Cp2TiA]) if the diene structure is suitable for formation of stable [Cp2TiA] compounds and if the equilibrium [Cp2TiAlH4]+diene[Cp2TiA]+A1H3 is shifted towards the formation of [Cp2TiA] by the excess of diene. All the compounds [Cp2TiA] exhibit high-resolution e.s.r. spectra at g=1.993, showing interaction of the unpaired electron with the cyclopentadienyl and 3-allyl protons. The e.s.r. spectra clearly reveal the presence of alkyl substituents atsyn-1,3-positions of 3-allyl ligand, and show a triplet of multiplets for (3-allyl)titanocene, doublets of multiplets for (1-alkyl-3-allyl)titanocenes and single multiplets for (1,3-dialkyl-3-allyl)-titanocenes. thermal isomerization of (1,3-dimethyl-3-allyl)-titanocene and (1-methyl-3-ethyl-3-allyl)titanocene, hitherto considered as the stable Cp2TiA compounds, into (1-alkyl-3-allyl)titanocenes was confirmed by e.s.r. and electronic absorption spectroscopy as well as by chemical means. 相似文献
22.
Tomáš Hartman Vladimír Herzig Miloš Buděšínský Jindřich Jindřich Radek Cibulka Tomáš Kraus 《Tetrahedron: Asymmetry》2012,23(22-23):1571-1583
A series of flavin–cyclodextrin conjugates has been prepared and tested in the enantioselective oxidations of prochiral aromatic and aliphatic sulfides with hydrogen peroxide. The newly prepared conjugates contain isoalloxazinium or alloxazinium moieties attached to the primary rim of α- and β-cyclodextrins at the C-6 positions. In addition, flavinium units were attached to the secondary rim of the β-cyclodextrin macrocycle. The relationship between the structural features and the catalytic performance of the conjugates, including those recently reported by us, was analyzed. The rate and enantioselectivity of the sulfoxidations catalyzed by flavin–cyclodextrin conjugates are influenced mainly by the size of the cyclodextrin cavity, the type of flavin unit (alloxazine or isoalloxazine), and by the relative orientation of the flavin and cyclodextrin moieties. 相似文献
23.
Věra Hamplová Alexej Bubnov Corresponding author Miroslav Kašpar Vladimíra Novotná Yveta Lhotáková Milada Glogarová 《Liquid crystals》2013,40(12):1463-1469
New chiral liquid crystalline materials containing a keto group and two lactate units attached to the mesogenic core have been synthesized and studied. All the new compounds show the paraelectric SmA, ferroelectric SmC* and antiferroelectric SmC*A phases each over rather broad temperature ranges. The properties of the phases were characterized by DSC, electro-optical and dielectric studies. The spontaneous polarization, tilt angle, helical pitch, and switching times were determined for the polar phases. 相似文献
24.
An efficient two-step synthetic route for preparation of the important Pigment Yellow 181 intermediate 4-amino-N-(4-carbamoylphenyl)benzamide is described. The synthetic pathway reflects requirements that are important for industrial applications. Optimisation of the reaction steps was performed to improve yields and procedures. The overall yield was higher than 78 %. 相似文献
25.
This study examines the alkylation of diphenylamine (DPA) with nonene (NON) in a liquid phase catalyzed by acid-treated clay-based catalysts from commercial suppliers (Fulcat 22B, Nobelin MM, and Jeltar 300). Alkylations were conducted to achieve the highest possible selectivity of diisononyldiphenylamine (DNDPA), low selectivity of monoisononyldiphenylamine, and a maximum triisononyldiphenylamine yield of 4%. This study also examines the reaction conditions to selectively form dialkylated diphenylamine from DPA and NON in a batch reactor. Repeated use of the catalyst during the alkylation of DPA with NON was also investigated. Catalyst deactivation takes place during the alkylation of each batch and intensifies with repeated catalyst use, resulting in low DNDPA selectivity. The regenerated catalyst was sufficiently active only until the regeneration of the first and second batches. After the third batch, the catalyst’s selectivity for DNDPA was very low, and its reuse in the alkylation of DPA with NON was not efficient. Therefore, to achieve the maximum length of catalyst activity, the fresh catalyst was gradually added to the used catalyst from a previous batch, thus maintaining a high activity of eight batches. The reduction in catalyst activity was probably caused by the irreversible adsorption of substances on the surface, a loss of microporous structure, and a loss of surface acidity. DPA or alkylated products are adsorbed on the surface oxygen of the catalyst through nitrogen and form nitro formations. The fresh and regenerated catalysts were characterized by their surface area, surface acidity, pore size distribution, and pore volume. 相似文献
26.
27.
New bent-core liquid crystalline dimers with W-shaped molecular geometry have been prepared and studied. We have modified the dimer shape by variation of the connecting part between two bent-core units and changing the terminal chains (perfluoroalkyl, siloxanealkyl). Additionally, we have altered the inner bend angle value (120°, 60° and 148°) by utilization of different aromatic units. Mesomorphic properties of new dimers were established based on the texture observation in the polarizing microscope and DSC measurements. Moreover, x-ray structural analysis has been performed for selected dimers to confirm phase identification. For most of the studied dimers, nematic or columnar phases have been detected, for several compounds appearing in a nematic-columnar phase sequence on cooling from the isotropic phase. The studied dimers showed richer polymorphism than their monomeric counterparts. 相似文献
28.
We show that the classical Cauchy problem for the incompressible 3d Navier-Stokes equations with (?1)-homogeneous initial data has a global scale-invariant solution which is smooth for positive times. Our main technical tools are local-in-space regularity estimates near the initial time, which are of independent interest. 相似文献
29.
30.
Karel Kolomazník Ji?í Pecha Veronika Friebrová Dagmar Janá?ová Vladimír Va?ek 《Heat and Mass Transfer》2012,48(9):1505-1512
Biostimulators are substances able to enhance the immune system of cultivated crops and support plant metabolism. Their utilization helps to reduce the amount of chemicals used in agriculture. To perform the desired effect, a biostimulator must be able to penetrate into the plant tissue. The time of penetration however, is limited, since the biostimulator must remain in a liquid state. This is of great importance—especially in field conditions, where the treated plants are exposed to different weather condition and other extrinsic factors. A mathematical model based on diffusion mechanisms has been elaborated to describe the biostimulator transport process from penetration of the leaves into the plant’s inner tissues. By means of the effective diffusion coefficient of the prepared specific protein hydrolyzate, this model can be used to estimate the time necessary for the uptake of the minimal active amount of the biostimulator. 相似文献