全文获取类型
收费全文 | 1824篇 |
免费 | 103篇 |
国内免费 | 2篇 |
专业分类
化学 | 1387篇 |
晶体学 | 4篇 |
力学 | 36篇 |
综合类 | 1篇 |
数学 | 241篇 |
物理学 | 260篇 |
出版年
2023年 | 28篇 |
2022年 | 28篇 |
2021年 | 33篇 |
2020年 | 53篇 |
2019年 | 35篇 |
2018年 | 26篇 |
2017年 | 23篇 |
2016年 | 89篇 |
2015年 | 79篇 |
2014年 | 80篇 |
2013年 | 91篇 |
2012年 | 110篇 |
2011年 | 115篇 |
2010年 | 83篇 |
2009年 | 69篇 |
2008年 | 108篇 |
2007年 | 115篇 |
2006年 | 105篇 |
2005年 | 100篇 |
2004年 | 84篇 |
2003年 | 68篇 |
2002年 | 38篇 |
2001年 | 28篇 |
2000年 | 26篇 |
1999年 | 24篇 |
1998年 | 12篇 |
1997年 | 11篇 |
1996年 | 9篇 |
1995年 | 6篇 |
1994年 | 12篇 |
1993年 | 8篇 |
1992年 | 15篇 |
1991年 | 13篇 |
1990年 | 6篇 |
1989年 | 5篇 |
1988年 | 8篇 |
1986年 | 8篇 |
1985年 | 10篇 |
1984年 | 13篇 |
1983年 | 10篇 |
1982年 | 13篇 |
1981年 | 8篇 |
1980年 | 11篇 |
1979年 | 8篇 |
1978年 | 8篇 |
1977年 | 12篇 |
1976年 | 13篇 |
1975年 | 9篇 |
1974年 | 6篇 |
1965年 | 4篇 |
排序方式: 共有1929条查询结果,搜索用时 0 毫秒
11.
12.
13.
Joachim Angelkort Sander van Smaalen Prof. Dr. Sven Oliver Hauber Mark Niemeyer 《无机化学与普通化学杂志》2007,633(7):1031-1035
Single crystal X‐ray diffraction of Eu(SC36H49)2 has revealed a first order phase transition at a temperature of 119 K, that involves a reduction of the specific volume by 1 %. The transition corresponds to a doubling of the unit cell, as it is the result from reorientations of isopropyl groups that appear at peripheral sites of the organic ligands. It is argued that a denser packing is achieved at the expense of a less favourable conformation of one of the two crystallographically‐independent complexes in the low‐temperature phase. The Bond‐Valence method is used to show that interactions of equal strengths are present between europium and both sulphur atoms and both coordinating phenyl rings. 相似文献
14.
Jan E. Almlöf P. Ulf Isacsson P. Johan Mjöberg Wiktor M. Ralowski 《Chemical physics letters》1974,26(2):215-217
Minimal basis set ab initio SCF LCAO MO calculations with gaussian-type have been performed for different conformations of the styrene molecule. The computations show the molecule to be planar and the rotational barrier of the vinyl group is estimated to 3.9 kcal/mole. 相似文献
15.
An easy synthesis of 2-aryl-3,3-dichloroazetidines, a rather unexplored class of azaheterocycles, is described. The title compounds were easily obtained by reduction of the corresponding 4-aryl-3,3-dichloro-2-azetidinones with monochloroalane, which in turn were synthesized by a ketene-imine [2 + 2] cycloaddition. The reactivity of 3,3-dichloroazetidines with bases was investigated, yielding 2-[dimethoxy(aryl)methyl]aziridines by ring contraction when treated with sodium methoxide. Furthermore, reacting the 3,3-dichloroazetidines with sodium hydride in DMSO, followed by aqueous workup, afforded 1-alkyl-2-aroylaziridines, by hydrolysis of the intermediate 2-azetines and ring closure of the transient 3-amino-2-chloro-1-phenyl-1-propanone derivatives. Monitoring this reaction in an NMR tube, using sodium hydride in DMSO-d(6), allowed the characterization of the intermediate strained heterocyclic enamines, i.e., 2-azetines, by (1)H and (13)C NMR. 相似文献
16.
The reactivity of a Cr‐Te multilayer film consisting of 326 Cr/Te double‐layers with about 88(3) at% Te was investigated with in‐situ X‐ray diffraction. The occurrence of a superstructure reflection caused by the multilayer system is observed. During the annealing procedure between 80 and 90 °C the layer‐by‐layer arrangement is destroyed and elemental Te crystallizes. After 6 h isothermal annealing at 140 °C CrTe3 starts to crystallize. The amount and the crystal size of CrTe3 increase with raising temperature and Te is consumed during the growth process. At 220 °C the formation of crystalline Cr2Te3 is observed and between 220 and 260 °C CrTe3 is completely decomposed into Cr2Te3. The two Cr tellurides grow as highly textured materials. The size of CrTe3 crystals is significantly larger than that of Cr2Te3. For a co‐deposited Cr‐Te film with composition 77(3) at% Te the tri‐telluride and elemental Te crystallize simultaneously. The texture of CrTe3 is less pronounced and different reflections of the tri‐telluride occur besides the (h00)‐reflections. Up to 160 °C a pronounced increase of the crystallite size is observed and the crystals are significantly larger than those obtained with the multifilm sample. At 130 °C the crystallization kinetics seem to be controlled by nucleation. 相似文献
17.
Sven J. Cyvin Jon Brunvoll Björg N. Cyvin John L. Bergan E. Brendsdal 《Structural chemistry》1991,2(6):555-566
Hollow hexagons form a subclass of primitive coronoid systems. The macrocyclic aromatic hydrocarbon kekulene corresponds to a hollow hexagon. The hollow hexagons for given numbers of hexagonal units (h) were enumerated by computer aid, but also an analytical solution for the numbers of hollow hexagons was achieved. For the Kekulé structure counts (k) of a hollow hexagon a general formula is reported. Also the maximum and minimumK numbers are considered.This article is Part VI of the series Enumeration and Classification of Coronoid Hydrocarbons. For Part V, see ref. [36]. 相似文献
18.
The molecular properties of hemicelluloses located in the surface and inner layers of fibers present in hardwood and softwood pulps, together with the effects of different bleaching processes on these properties, have been investigated in this study. In order to separate the hemicelluloses located in these two layers, fibers were subjected to mechanical peeling and then separated by filtration into surface (filtrate) and inner layer materials. The materials thus obtained were characterized with respect to their polysaccharide compositions and uronic acid contents. The molar mass parameters of the hemicelluloses (extracted by alkali) were determined by employing size-exclusion chromatography in combination with off-line MALDI mass spectrometry. For all of the pulps examined, the relative content of xylan was found to be greater in the surface layer of the fiber than in the corresponding inner layer. The xylan polymers of the surface layer exhibited higher molar masses and lower frequencies of uronic acid side groups than did the xylans in the inner fiber layer. In connection with ozone treatment, hexenuronic acid residues in the surface layer xylan were removed to a greater extent than in the case of the inner layers, indicating a gradient for the reaction with ozone across the fiber wall. The xylan polymer remaining on the surface of the softwood pulps after completion of the chlorine dioxide bleaching process was predominantly uncharged. 相似文献
19.
Dominick Maes Silvia Debenedetti Sven Mangelinckx Norbert De Kimpe 《Tetrahedron》2005,61(9):2505-2511
The synthesis of three highly oxygenated naturally occurring coumarins, 8-methoxy-6,7-methylenedioxycoumarin, 5-methoxy-6,7-methylenedioxycoumarin and 5,8-dimethoxy-6,7-methylenedioxycoumarin is described for the first time, together with a new method for the preparation of ayapin (6,7-methylenedioxycoumarin). Comparison of the spectroscopic data of the synthetic tetraoxygenated coumarin 5,8-dimethoxy-6,7-methylenedioxycoumarin with literature reports resulted in the structural revision of several natural coumarins. Two coumarins, both identified as 5,8-dimethoxy-6,7-methylenedioxycoumarin must have other structures, while the structure of another coumarin, described as the isomeric 7,8-dimethoxy-5,6-methylenedioxycoumarin has to be revised to 5,8-dimethoxy-6,7-methylenedioxycoumarin. 相似文献
20.
The structural stability of hen egg white lysozyme in solution and adsorbed to small colloidal silica particles at various surface concentrations was investigated using hydrogen-deuterium (H/D) exchange in combination with mass spectrometry (HDX-MS) and differential scanning calorimetry (DSC). The combination of HDX-MS and DSC allows a full thermodynamic analysis of the lysozyme structure as both the enthalpy and the Gibbs free energy can be derived from the various measurements. Moreover, both HDX-MS and DSC provide information on the relative structural heterogeneity of lysozyme in the adsorbed state compared to that in solution. Results demonstrated that at high surface coverage, the structural stability of lysozyme was only marginally affected by adsorption to silica particles whereas the unfolding enthalpy decreased by more than 10%, meaning that the entropy of lysozyme increased with a similar value upon adsorption. Furthermore, the structural heterogeneity increased considerably. At lower surface concentrations, the structural heterogeneity increased further whereas the enthalpy of unfolding decreased. Further analyses of the HDX-MS experiments clearly indicated that folding/unfolding of lysozyme occurs through a two-domain process. These two domains had a similar amount of structural elements and a difference in stabilization energy of 8 kJ/mol, regardless if lysozyme was in solution or adsorbed to silica. 相似文献