全文获取类型
收费全文 | 1293篇 |
免费 | 35篇 |
国内免费 | 24篇 |
专业分类
化学 | 882篇 |
晶体学 | 15篇 |
力学 | 17篇 |
数学 | 289篇 |
物理学 | 149篇 |
出版年
2022年 | 4篇 |
2021年 | 29篇 |
2020年 | 12篇 |
2019年 | 18篇 |
2018年 | 26篇 |
2017年 | 20篇 |
2016年 | 38篇 |
2015年 | 31篇 |
2014年 | 45篇 |
2013年 | 106篇 |
2012年 | 71篇 |
2011年 | 76篇 |
2010年 | 49篇 |
2009年 | 37篇 |
2008年 | 61篇 |
2007年 | 85篇 |
2006年 | 73篇 |
2005年 | 60篇 |
2004年 | 68篇 |
2003年 | 45篇 |
2002年 | 51篇 |
2001年 | 33篇 |
2000年 | 22篇 |
1999年 | 16篇 |
1998年 | 18篇 |
1997年 | 14篇 |
1996年 | 15篇 |
1995年 | 20篇 |
1994年 | 11篇 |
1993年 | 19篇 |
1992年 | 17篇 |
1991年 | 10篇 |
1990年 | 13篇 |
1989年 | 10篇 |
1988年 | 5篇 |
1987年 | 9篇 |
1986年 | 4篇 |
1985年 | 14篇 |
1984年 | 15篇 |
1983年 | 8篇 |
1982年 | 12篇 |
1981年 | 17篇 |
1980年 | 5篇 |
1979年 | 3篇 |
1978年 | 8篇 |
1977年 | 5篇 |
1974年 | 3篇 |
1973年 | 6篇 |
1972年 | 5篇 |
1970年 | 2篇 |
排序方式: 共有1352条查询结果,搜索用时 15 毫秒
31.
Gas-liquid chromatography was applied in thermodynamic investigations of processes of complexation and enantioseparation by alpha- and [-cyclodextrins of chiral monoterpenoids. The distribution constants, stability constants and thermodynamic parameters enthalpy, entropy and free energy of the complexation processes were determined. It has been found that enantioseparation of monoterpenes by alpha- and beta-cyclodextrins is the result of formation of 1:2 stoichiometric complexes. When 1:1 stoichiometric complexes are formed, enantioselectivity is not observed. All investigated processes of complexation are enthalpy-driven regardless of the stoichiometry of the formed complexes. -deltaH, -TdeltaS and -deltaG of complexation process have higher values for bicyclic than for monocyclic monoterpenoids as well as for alpha-CD than for beta-CD. The first or second step of complexation may be responsible for enantioselectivity. 相似文献
32.
Janusz Jamrozik 《Monatshefte für Chemie / Chemical Monthly》1981,112(6-7):785-790
Condensation of 1,1,2,2,-tetrabromomethylcyclopropane with 1,8-dihydroxynaphthalene yielded the (7.7.1)-type propellane. The peri effect on the reaction and the product conformation is discussed. As a result condensation of 1,1-dibromomethylcyclopropane withperi-dihydroxynaphthalene gives the diether-type compound2 instead of the expected spirane2.
Jamrozik, J., Propellanes III. J. für prakt. Chemie, im Druck (1980). 相似文献
33.
Let G: (0, ∞) → (0, ∞) be logarithmically concave on a neighbourhood of ∞ and suppose limx→∞ G(x + δ)/G(x) = 1 for some δ > 0. Then, the functional equation $$g(x+1)=G(x)\cdot g(x),\ \ \ x\in (0,\infty),$$ admits, up to a multiplicative constant, at most one solution g: (0, ∞) → (0, ∞), geometrically convex on a neighbourhood of ∞. Sufficient conditions on G are given, for which also such a unique geometrically convex solution of (D) exists. This result improves the classical theorems of Bohr-Mollerup type and gives a new characterization of the gamma function and the q-gamma function for q ∈ (0, 1). 相似文献
34.
Janusz Grabowski 《Annals of Global Analysis and Geometry》1993,11(3):213-220
It is proved that for infinite dimensional Lie groups in the sense of the differential calculus of Frölicher and Kriegl the derivative of the exponential mappings is given by the formula d(exp)(X)Y=dexp(X)(e)
0
1
Adexp(–tX)
Y dt, where stands for the left translation ande is the neutral element.This work was supported by the Alexander von Humboldt-Stiftung. 相似文献
35.
A restricted access material (RAM), alkyl-diol-silica (ADS), was used to prepare a highly bio-compatible solid-phase microextraction (SPME) capillary for the automated and direct in-tube extraction of several benzodiazepines from human serum. The bifunctionality of the ADS extraction phase prevented fouling of the capillary by protein adsorption while simultaneously trapping the analytes in the hydrophobic porous interior. This the first report of a restricted access material utilized as an extraction phase for in-tube SPME. The approach simplified the required apparatus in comparison to existing RAM column switching procedures, and more importantly eliminated the excessive use of extraction solvents. The biocompatibility of the ADS material also overcame the existing problems with in-tube SPME that requires an ultrafiltration or other deproteinization step prior to handling biological samples, therefore further minimizing the sample preparation requirements. The calculated oxazepam, temazepam, nordazepam and diazepam detection limits were 26, 29, 22 and 24 ng/ml in serum, respectively. The method was linear over the range of 50-50 000 ng/ml with an average linear coefficient (R2) value of 0.9998. The injection repeatability and intra-assay precision of the method were evaluated with five injections of a 10-microg/ml serum sample (spiked with all compounds), resulting in an average RSD<7%. The ADS extraction column was robust, providing many direct injections of biological fluids for the extraction and subsequent determination of benzodiazepines. 相似文献
36.
It is shown that enantioselective solvent-generated liquid-liquid and liquid-solid Chromatographic systems with -cyclodextrin derivatives can be realized. The liquid-liquid systems are based on ternary solvent systems of limited miscibility, containing chiral additives; the chiral stationary phase is spontaneously generated on the porous microparticulate silica used as a solid support. In the solvent-generated adsorption systems a very small proportion of -cyclodextrin derivatives is added to the mobile phase. These components act as column activators, since they are strongly adsorbed on the RP solid support where they form new stereoselective adsorption sites. It is demonstrated that dynamically generated systems with -cyclodextrin derivatives as chiral agents are powerful and versatile tools for enantioseparation of different types of compounds. This technique creates not only a new type of selectivity but also leads to very stable and reproducible Chromatographic columns.Dedicated to Professor J. F. K. Huber on the occasion of his 65th birthday 相似文献
37.
In this paper we consider problems concerning the effectiveness of iterational calculations on vibrational analysis. Instead of the widespread least-squares method of force field refinement, another method is proposed based on the steepest-descent algorithm for calculation of the functional minimum of many variables. The new method does not require inverting of a large, poorly conditioned matrix or the introduction of experimental damping coefficients for improving the convergency of the calculations. Test calculations performed for several molecules exhibit a significant “elasticity” of the proposed algorithm allowing more precise reproduction of the molecular vibration frequencies than can be found in recently published works. 相似文献
38.
Prof. Dr. Stefan Smoliński Janusz Jamrozik Maria Jamrozik 《Monatshefte für Chemie / Chemical Monthly》1977,108(5):1145-1151
We have obtained four new bispirane systems in which both spiroatoms are vicinal atoms in cyclopropane or cyclobutane rings and in which the heterocyclic component has the basic structure of 1,4-dioxep-2-ene. We have shown that from two possibilities (bispiran, propellan) the general reaction leads only to a bispiran system. To the bispiran2 exhibiting the highest hyperchromism we ascribed the bispirocoplanar conformation (Fig. 1).
Mit 3 Abbildungen 相似文献
Mit 3 Abbildungen 相似文献
39.
Janusz B. Kyziol 《Journal of heterocyclic chemistry》1985,22(5):1301-1305
The synthesis of 3-nitrosocarbazole (I) by the Fischer-Hepp rearrangement of 9-nitrosocarbazole has been described. The resistance of I to oxidation provides evidence that it cannot be the intermediate in the conversion of 9-nitrosocarbazole to the C-nitro compounds. It has also been shown that I and its derivatives cannot be synthesized by the action nitrosyl chloride on carbazoles. Methylation of I yields 9-methyl-3-nitrosocarbazole, 9,9′-dimethyl-3-azocarbazole and 9,9′-dimethyl-3-azoxycarbazole as the main products. The mechanism of this disproportionation process has been proposed. The spectral data of I are given. 相似文献
40.
Gun'ko VM Mikhailova IV Zarko VI Gerashchenko II Guzenko NV Janusz W Leboda R Chibowski S 《Journal of colloid and interface science》2003,260(1):56-69
The interaction of fumed silica A-300 (S(BET) = 297 m2 g(-1)) with bovine serum albumin (prepared by different methods), ovalbumin, human hemoglobin, and gelatin as a function of pH, salinity, and concentrations of components in aqueous medium was studied by adsorption and photon correlation spectroscopy (PCS) methods. Comparison of equilibrium (incubation time t(i) approximately 1 h) adsorption of proteins on A-300, minute (t(i) approximately 1 min) flocculation rate, and the particle size distributions measured by the PCS method shows different rearrangement of particle swarms depending on pH, salinity, and concentration of proteins, especially at pH close to IEP of silica or proteins. The electrokinetic mobility of protein/silica swarms is greater than that of individual components at pH far from the IEP of proteins. Changes in the Gibbs free energy (DeltaG) on protein adsorption depend on pH (-DeltaG is minimal at pH 2, close to the IEP of silica, and maximal at pH between the IEP of protein and silica), concentration (-DeltaG is maximal at C(p) between 1 and 6 mg/ml), type of proteins, and their preparation technique. 相似文献