全文获取类型
收费全文 | 464篇 |
免费 | 12篇 |
专业分类
化学 | 335篇 |
晶体学 | 7篇 |
力学 | 2篇 |
数学 | 8篇 |
物理学 | 124篇 |
出版年
2021年 | 6篇 |
2017年 | 4篇 |
2016年 | 8篇 |
2015年 | 8篇 |
2014年 | 6篇 |
2013年 | 9篇 |
2012年 | 16篇 |
2011年 | 24篇 |
2010年 | 10篇 |
2009年 | 8篇 |
2008年 | 15篇 |
2007年 | 18篇 |
2006年 | 18篇 |
2005年 | 21篇 |
2004年 | 31篇 |
2003年 | 21篇 |
2002年 | 22篇 |
2001年 | 14篇 |
2000年 | 10篇 |
1999年 | 10篇 |
1998年 | 7篇 |
1997年 | 4篇 |
1996年 | 5篇 |
1995年 | 7篇 |
1994年 | 6篇 |
1993年 | 6篇 |
1992年 | 4篇 |
1990年 | 4篇 |
1988年 | 3篇 |
1984年 | 3篇 |
1982年 | 4篇 |
1981年 | 5篇 |
1979年 | 5篇 |
1978年 | 8篇 |
1977年 | 5篇 |
1975年 | 4篇 |
1973年 | 5篇 |
1969年 | 4篇 |
1941年 | 4篇 |
1940年 | 3篇 |
1935年 | 7篇 |
1934年 | 5篇 |
1933年 | 4篇 |
1930年 | 3篇 |
1926年 | 6篇 |
1925年 | 6篇 |
1904年 | 3篇 |
1899年 | 4篇 |
1898年 | 3篇 |
1885年 | 5篇 |
排序方式: 共有476条查询结果,搜索用时 15 毫秒
161.
We show that for a wide class of Euclidean scalar field equations, there exist non-trivial solutions, and the non-trivial solution of lowest action is spherically symmetric. This fills a gap in a recent analysis of vacuum decay by one of us.Work supported in part by the US National Science Foundation under grant Nr. PHY75-20427 相似文献
162.
163.
The error propagation is given for routine analysis by in situ evaluation in TLC using the methods with internal or external standard. The internal standard method will need four different measurements of peak height or area, while the external standard method uses only two measurements. Therefore in the latter case the error of the spotting volume will cause errors in the determined concentration. By error propagation it can be shown, that the internal standard method gives better results, if the error in measuring peak height or area is less than the error of the spotting volume. 相似文献
164.
165.
Ohne Zusammenfassung 相似文献
166.
Rayat S Majumdar P Tipton P Glaser R 《Journal of the American Chemical Society》2004,126(32):9960-9969
The nitrosative deaminations (37 degrees C, NaNO2, NaAc buffer, pH 3.7) of guanosine 1r in (18O)water (97.6%) and of [6-18O]-1r in normal water were studied. [6-(18)O]-1r was prepared from 2-amino-6-chloropurine riboside using adenosine deaminase. The reaction products xanthosine 3r and oxanosine 4r were separated by HPLC and characterized by LC/MS analysis and 13C NMR spectroscopy. The 18O-isotopic shifts on the 13C NMR signals were measured and allowed the identification of all isotopomers formed. The results show that oxanosine is formed via 5-cyanoimino-4-oxomethylene-4,5-dihydroimidazole, 5, and its 1,4-addition product 5-cyanoamino-4-imidazolecarboxylic acid, 6. This hydration of 5 to 6 leads to aromatization and greatly dominates over water addition to the cyanoimino group of 5 to form 5-guanidinyliden-4-oxomethylene-4,5-dihydroimidazole, 7. 5-Guanidinyl-4-imidazolecarboxylic acid, 8, the product of water addition to 6, is not involved. 相似文献
167.
Complex formation of monomeric thallium(III) species with 2,2'-bipyridine (bipy) in dimethyl sulfoxide (dmso) and acetonitrile solutions was studied by means of multinuclear ((1)H, (13)C, and (205)Tl) NMR spectroscopy. For the first time, NMR signals of the individual species [Tl(bipy)(m)(solv)](3+) (m = 1-3) were observed despite intensive ligand and solvent exchange processes. The tris(bipy) complex was crystallized as [Tl(bipy)(3)(dmso)](ClO(4))(3)(dmso)(2) (1), and its crystal structure determined. In this compound, thallium is seven-coordinated; it is bonded to six nitrogen atoms of the three bipy molecules and to an oxygen atom of dmso. Metal-metal bonded binuclear complexes [(NC)(5)Pt-Tl(CN)(n)(solv)](n)(-) (n = 0-3) have been modified by attaching bipy molecules to the thallium atom. A reaction between [(NC)(5)Pt-Tl(dmso)(4)](s) and 2,2'-bipyridine in dimethyl sulfoxide solution results in the formation of a new complex, [(NC)(5)Pt-Tl(bipy)(solv)]. The presence of a direct Pt-Tl bond in the complex is convincingly confirmed by a very strong one-bond (195)Pt-(205)Tl spin-spin coupling ((1)J((195)Pt-(205)Tl) = 64.9 kHz) detected in both (195)Pt and (205)Tl NMR spectra. In solutions containing free cyanide, coordination of CN(-) to the thallium atom occurs, and the complex [(NC)(5)Pt-Tl(bipy)(CN)(solv)](-) ((1)J((195)Pt-(205)Tl) = 50.1 kHz) is formed as well. Two metal-metal bonded compounds containing bipy as a ligand were crystallized and their structures determined by X-ray diffractometry: [(NC)(5)Pt-Tl(bipy)(dmso)(3)] (2) and [(NC)(5)Pt-Tl(bipy)(2)] (3). The Pt-Tl bonding distances in the compounds, 2.6187(7) and 2.6117(5) A, respectively, are among the shortest reported separations between these two metals. The corresponding force constants in the molecules, 1.38 and 1.68 N/cm, respectively, were calculated using Raman stretching frequencies of the Pt-Tl vibrations and are characteristic for a single metal-metal bond. Electronic absorption spectra were recorded for the [(NC)(5)Pt-Tl(bipy)(m)(solv)] compounds, and the optical transition was attributed to the metal-metal bond assigned. 相似文献
168.
169.
Kehlet CT Sivertsen AC Bjerring M Reiss TO Khaneja N Glaser SJ Nielsen NC 《Journal of the American Chemical Society》2004,126(33):10202-10203
We present the first solid-state NMR experiments developed using optimal control theory. Taking heteronuclear dipolar recoupling in magic-angle-spinning NMR as an example, it proves possible to significantly improve the efficiency of the experiments while introducing robustness toward instrumental imperfections such as radio frequency inhomogeneity. The improvements are demonstrated by numerical simulations as well as practical experiments on a 13Calpha,15N-labeled powder of glycine. The experiments demonstrate a gain of 53% in the efficiency for 15N to 13Calpha coherence transfer relative to the typically double-cross-polarization experiments. 相似文献
170.
13C NMR study of halogen bonding of haloarenes: measurements of solvent effects and theoretical analysis 总被引:1,自引:0,他引:1
Glaser R Chen N Wu H Knotts N Kaupp M 《Journal of the American Chemical Society》2004,126(13):4412-4419
Solvent effects on the NMR spectra of symmetrical (X = F (1), X = Cl (2), X = Br (3), X = I (4), X = NO2 (5), X = CN (6)) and unsymmetrical (X = I, Y = MeO (7), Y = PhO (8)) para-disubstituted acetophenone azines X-C6H4-CMe=N-N=CMe-C6H4-Y and of models X-C6H4-CMe=N-Z (X = I, Z = H (9), Z = NH2 (10)), 4-iodoacetophenone (11), and iodobenzene (12) were measured in CDCl(3), DMSO, THF, pyridine, and benzene to address one intramolecular and one intermolecular issue. Solvent effects on the (13)C NMR spectra are generally small, and this finding firmly establishes that the azine bridge indeed functions as a "conjugation stopper," an important design concept in our polar materials research. Since intermolecular halogen bonding of haloarenes do occur in polar organic crystalline materials, the NMR solution data pose the question as to whether the absence of solvent shifts indicates the absence of strong halogen bonding in solution. This question was studied by the theoretical analysis of the DMSO complexes of iodoarenes 4, 9-12, and of iodoacetylene. DFT and MP2 computations show iodine bonding, and characteristic structural and electronic features are described. The nonrelativistic complexation shifts and the change in the spin-orbit induced heavy atom effect of iodine compensate each other, and iodine bonding thus has no apparent effect on Ci in the iodoarenes. For iodides, complexation by DMSO occurs and may or may not manifest itself in the NMR spectra. The absence of complexation shifts in the NMR spectra of halides does not exclude the occurrence of halogen bonding in solution. 相似文献