全文获取类型
收费全文 | 370篇 |
免费 | 33篇 |
国内免费 | 1篇 |
专业分类
化学 | 313篇 |
晶体学 | 5篇 |
力学 | 2篇 |
数学 | 28篇 |
物理学 | 56篇 |
出版年
2023年 | 3篇 |
2021年 | 6篇 |
2020年 | 9篇 |
2019年 | 7篇 |
2018年 | 8篇 |
2016年 | 16篇 |
2015年 | 19篇 |
2014年 | 17篇 |
2013年 | 12篇 |
2012年 | 25篇 |
2011年 | 30篇 |
2010年 | 14篇 |
2009年 | 8篇 |
2008年 | 30篇 |
2007年 | 21篇 |
2006年 | 20篇 |
2005年 | 17篇 |
2004年 | 20篇 |
2003年 | 11篇 |
2002年 | 18篇 |
2001年 | 8篇 |
2000年 | 10篇 |
1999年 | 2篇 |
1998年 | 3篇 |
1997年 | 3篇 |
1996年 | 2篇 |
1995年 | 3篇 |
1993年 | 2篇 |
1991年 | 4篇 |
1990年 | 5篇 |
1989年 | 2篇 |
1988年 | 9篇 |
1987年 | 4篇 |
1985年 | 2篇 |
1984年 | 3篇 |
1983年 | 1篇 |
1982年 | 3篇 |
1981年 | 5篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1978年 | 3篇 |
1977年 | 1篇 |
1975年 | 1篇 |
1974年 | 3篇 |
1973年 | 2篇 |
1972年 | 2篇 |
1971年 | 2篇 |
1969年 | 1篇 |
1968年 | 1篇 |
1965年 | 1篇 |
排序方式: 共有404条查询结果,搜索用时 15 毫秒
31.
[structure: see text] Sterically hindered tetraaminomethylated resorcarenes form inclusion complexes in CDCl(3) with acetonitrile and acetaldehyde, which are kinetically stable on the NMR time scale at 233 K. 相似文献
32.
In the literature one basic work can be found that describes an attempt to verify the applicability of the orthotropic plate wave theory to paper. In the present study we have repeated the key experiment and also modified the original experimental set-up to be able to make new complementary measurements. The performed verification attempt is based on a key experiment in which an ultrasonic resonance method is used. When it is applied to paper, a second resonance can be observed in addition to the one that originates from the asymmetric A0 mode. The result of the verification experiment is conclusive only if the source of this second resonance is the symmetric S0 mode. Our results show that the second resonance is not generated by the S0 mode. Instead, they indicate that the source is a longitudinal wave propagating in the thickness direction of the paper. We therefore conclude that the applicability of the orthotropic plate wave theory to paper cannot be verified by performing the key experiment that is described in the literature. 相似文献
33.
34.
Günter Haufe Thomas C. RosenOliver G.J. Meyer R. FröhlichKari Rissanen 《Journal of fluorine chemistry》2002,114(2):189-198
Monofluorinated cyclopropanecarboxylates are available in racemic or optically active form by transition metal-catalyzed reactions of vinylfluorides with diazoacetates. From α-fluorostyrene and tert-butyl diazoacetate in the presence of 2 mol% of an enantiopure bis(oxazoline) copper complex, a 81:19 mixture of tert-butyl trans- and cis-2-fluoro-2-phenylcyclopropanecarboxylates was obtained with high enantiomeric excess (ee) of 93 or 89%, respectively. The corresponding racemic ethylesters were used as starting materials for the synthesis of carboxamides, of the cis- and trans-isomers of analogues of tranylcypromine, an anti-depressive drug and several of its homologous fluorinated cyclopropylmethyl and cyclopropylethyl amines. Corresponding enantiopure cyclopropylmethanols and several of their derivatives were synthesized also. Solid state structures of a selection of these compounds were examined by X-ray crystallography. Particularly, the cis-configurated fluorinated phenylcyclopropane derivatives showed extremely close intermolecular CH?FC contacts. The shortest of such distances (2.17 Å) was found in the N-(4-bromophenyl)carbamate of (1S,2R)-(2-fluoro-2-phenylcyclopropyl)methanol. 相似文献
35.
Michael Müller Prof. Dr. Markus Albrecht Verena Gossen Tanja Peters Andreas Hoffmann Prof. Dr. Gerhard Raabe Dr. Arto Valkonen Prof. Kari Rissanen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(41):12446-12453
The directionality of interaction of electron‐deficient π systems with spherical anions (e.g,. halides) can be controlled by secondary effects like NH or CH hydrogen bonding. In this study a series of pentafluorophenyl‐substituted salts with polyhalide anions is investigated. The compounds are obtained by aerobic oxidation of the corresponding halide upon crystallization. Solid‐state structures reveal that in bromide 2 , directing NH–anion interactions position the bromide ion in an η1‐type fashion over but not in the center of the aromatic ring. The same directing forces are effective in corresponding tribromide salt 3 . In the crystal, the bromide ion is paneled by four electron‐deficient aromatic ring systems. In addition, compounds 4 and 6 , which have triiodide and the rare tetraiodide dianion as anions, are described. Computational studies reveal that the latter is highly unstable. In the present case it is stabilized by the crystal lattice, for example, by interaction with electron‐deficient π systems. 相似文献
36.
Cametti M Ilander L Valkonen A Nieger M Nissinen M Nauha E Rissanen K 《Inorganic chemistry》2010,49(24):11473-11484
Ditopic salophen-UO(2) receptors 1-4 and 7 co-crystallize with tetramethylammonium (TMA) chloride and fluoride salts producing good quality crystals amenable for X-ray diffraction characterization. The arrangement of the receptor and salt units in the crystal lattice is such that tetrameric ball-shaped assemblies are formed, where an inner cluster of four TMA cations are surrounded by an outer shell of four UO(2)-bound anions. These elaborate architectures, which occur in all cases, regardless of a certain degree of structural modification on the receptors, lead to lattices that belong to non-centrosymmetric (NCS) space groups. Interestingly, the tetragonal symmetry of the tetrameric ball-shaped assemblies is either retained (I4?) or lost (R3c and I4?3d) at the lattice level, without compromising the NCS nature of the crystal lattices. The principal X-ray investigation on TMAX (X = Cl/F) co-crystals, that is, 1-(TMA)Cl, 2-(TMA)Cl, 3-(TMA)Cl, 4-(TMA)Cl, 7-(TMA)Cl, and 7-(TMA)F, is accompanied by NMR and electrospray ionization (ESI) mass spectrometry studies to gather additional insight on the modality of formation of the solid state structures observed. The important role of cation-π interactions in the receptor-salt recognition process is renewed and strengthened by comparison with NMR titration data with a novel reference compound, the salophen-UO(2) complex 8. Given the importance of NCS and polar crystalline solids in the development of functional materials, this study shows that this property can be introduced into elaborate host-guest systems, as those which assemble in the architectures described here, thus expanding its field of applicability. 相似文献
37.
Tero Tuuttila Manu Lahtinen Juhani Huuskonen Kari Rissanen 《Thermochimica Acta》2010,497(1-2):109-116
The thermal properties of twelve Janus-type dendrimers up to the second generation were evaluated by termogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Compounds consist of the dendritic bisMPA based polyester moieties, and either 3,4-bis-dodecyloxybenzoic acid, 3,5-bis-dodecyloxybenzoic acid or 3,4,5-tris-dodecyloxybenzoic acid moieties, attached to opposite sides of the pentaerythritol core. The thermal stability of the compounds was evaluated by TGA, displaying onset decomposition temperatures (Td) at around 250 °C. DSC measurements upon heating and cooling confirmed that OH terminated Janus dendrimers featuring large polarity difference in opposite sides display liquid crystalline phases with exception of 3,5-type G1 dendrimer; while acetonide terminated dendrimers displayed merely melting transitions. Dendrimers having terminal alkyl chains at positions 3,4 or 3,4,5 in aromatic moieties exhibited enantiotropic mesophases. However, the thermal behavior of the dendrimers with 3,5-substitution pattern was different: the 3,5-type G1 dendrimer exhibit a lack of mesomorphic transition, and in the case of the 3,5-type G2 dendrimer, the mesophase was absent in the first heating scan but was observed during the subsequent cooling and heating scans at the rate of 10 °C/min. 相似文献
38.
V.S. Kolhinen T. EronenD. Gorelov J. HakalaA. Jokinen A. KankainenJ. Rissanen J. SuhonenJ. Äystö 《Physics letters. [Part B]》2011
The double-electron-capture Q value for the 136Ce decay to 136Ba has been determined at JYFLTRAP. The measured value 2378.53(27) keV excludes the energy degeneracy with the 0+ excited state of the decay daughter 136Ba at 2315.32(7) keV in a resonant 0νECEC decay by 11.67 keV. The new Q value differs from the old adopted value 2419(13) keV (Atomic Mass Evaluation 2003) by 40 keV and is 50 times more precise. Our calculations show that the precise Q value renders the resonant 0νECEC decay of 136Ce undetectable by the future underground detectors. We measured also the double-β decay Q value of 136Xe to be 2457.86(48) keV which agrees well with the value 2457.83(37) keV measured at the Florida State University. 相似文献
39.
40.