全文获取类型
收费全文 | 29298篇 |
免费 | 3046篇 |
国内免费 | 2053篇 |
专业分类
化学 | 19522篇 |
晶体学 | 234篇 |
力学 | 137篇 |
综合类 | 50篇 |
数学 | 81篇 |
物理学 | 12232篇 |
综合类 | 2141篇 |
出版年
2024年 | 58篇 |
2023年 | 228篇 |
2022年 | 757篇 |
2021年 | 775篇 |
2020年 | 889篇 |
2019年 | 875篇 |
2018年 | 743篇 |
2017年 | 857篇 |
2016年 | 1351篇 |
2015年 | 1348篇 |
2014年 | 1420篇 |
2013年 | 2370篇 |
2012年 | 1772篇 |
2011年 | 1930篇 |
2010年 | 1584篇 |
2009年 | 2001篇 |
2008年 | 1875篇 |
2007年 | 2023篇 |
2006年 | 1852篇 |
2005年 | 1473篇 |
2004年 | 1282篇 |
2003年 | 1101篇 |
2002年 | 853篇 |
2001年 | 707篇 |
2000年 | 606篇 |
1999年 | 592篇 |
1998年 | 477篇 |
1997年 | 447篇 |
1996年 | 372篇 |
1995年 | 319篇 |
1994年 | 231篇 |
1993年 | 217篇 |
1992年 | 193篇 |
1991年 | 148篇 |
1990年 | 110篇 |
1989年 | 94篇 |
1988年 | 142篇 |
1987年 | 65篇 |
1986年 | 45篇 |
1985年 | 35篇 |
1984年 | 33篇 |
1983年 | 8篇 |
1982年 | 27篇 |
1981年 | 29篇 |
1980年 | 22篇 |
1978年 | 9篇 |
1976年 | 7篇 |
1973年 | 10篇 |
1972年 | 7篇 |
1971年 | 7篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
71.
Esko Taskinen 《Structural chemistry》2002,13(1):61-71
Selected group frequencies of the IR spectra of a number of 2-substituted 4-methylene-1,3-dioxolanes (a) and their endocyclic isomers, 2-substituted 4-methyl-1,3-dioxoles (b), have been studied to establish their usefulness as a measure of the strength of p– conjugation in the O—C=C moieties of the title compounds. In the exo compounds (a), the C=C stretching frequencies C=C and the in-phase, out-of-plane bending (wagging) frequencies CH2
w of the =CH2 group were found to be linearly related, besides to each other, also to the electron-donating character of the substituents and the 13C NMR chemical shift of the C atom of the exocyclic CH2 group. This suggests that the two IR group frequencies of the exo isomers are linearly related to the strength of p– conjugation in the O—C=C moiety. The C=C stretching absorption of the exo compounds in the 1600–1700 cm–1 region appeared as a doublet, shown to arise from Fermi resonance of the C=C fundamental with the CH2
w overtone. The C=C frequencies of the endo compounds support some previous findings of an unexpected strength of p– conjugation in the 2-alkoxy derivatives. Finally, DFT calculations at the B3LYP/6-31G* level of theory are shown to give accurate predictions of the effect of 2-substituents on the group frequencies. 相似文献
72.
Walrand J Lengelé M Blanquet G 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(14):3299-3303
Using diode-laser spectroscopy, the intensities of 58 lines of the v(1) + v(1/2) - v(1/2) band and 36 lines of the 2v(1) - v(1) band of OCS have been measured. The corresponding band strengths S(0)(v) and the vibrational transition dipoles micro(v) have been derived through least squares fitting of these individual intensities. The band strengths values have been determined with a precision better than 2.5%. 相似文献
73.
I. I. Chuev S. M. Aldoshin E. G. Atovmyan D. B. Frolov A. N. Utenyshev 《Russian Chemical Bulletin》1996,45(4):851-855
N-Thenylidene- andN-(o-nitrobenzylidene)hydrazides of isonicotinic acid have been studied by X-ray structural analysis and IR spectroscopy. In the crystalline state, these molecules are linked through intermolecular N—H ... Npy hydrogen bonds. Carbonyl groups are not involved in intermolecular hydrogen bonds. However, it was found that the C=O group participates in an attractive interaction with the sulfur atom of the thiophene group. The energy of this interaction is comparable with the energies of intermolecular C=O ... H—N hydrogen bonds in amides.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 896–900, April, 1996. 相似文献
74.
Jorge Pavez Maritza Páez Armelle Ringuedé Fethi Bedioui José H. Zagal 《Journal of Solid State Electrochemistry》2005,9(1):21-29
We studied the electrocatalytic activity of cobalt tetra-aminophthalocyanine (CoTAPc) for the reduction of molecular oxygen (O2) on adsorbed monomeric and on electropolymerized films of different thicknesses on glassy carbon (GC) electrode. The polymeric films, denoted poly-CoTAPc, were first characterized by electrochemical impedance spectroscopy and it appears that the types of phenomena revealed to be occurring depend less on the film thickness in basic than in acid media. For O2 reduction, the results showed that poly-CoTAPc is more active than the monomeric CoTAPc adsorbed on GC. Indeed, rotating ring-disk electrode data showed that polymeric CoTAPc promotes the four-electron reduction of O2 to water in parallel to a two-electron reduction to give peroxide. On monomeric and thin films of poly-CoTAPc, a two-electron reduction mechanism predominates. In basic media the activity increases very slightly with thickness, whereas in acid media this increase is more pronounced. This parallels the observed behavior revealed by electrochemical impedance spectroscopy. 相似文献
75.
Carl Nordling 《Angewandte Chemie (International ed. in English)》1972,11(2):83-92
A substance on which X-rays fall emits photoelectrons and Auger electrons. The energy spectra of the electrons emitted provide information about the electronic structure in the specimen, ranging from the innermost atomic levels and their dependence on the chemical environment to the molecular orbitals of the valence electrons and the band structure in solids. Electron spectra of this nature can now be recorded with high-resolution instruments; their analysis offers new aspects for investigation of chemical composition. The method of electron spectroscopy developed for this purpose, which has now been developed to a high degree of perfection, will be referred to in the following discussion as ESCA (Electron Spectroscopy for Chemical Analysis). 相似文献
76.
A new complex of europium(II) with ethylenediaminetetraacetic acid was obtained by electrochemical reduction. The compound is composed of polymeric chains, guanidinium cations and water molecules. The Eu2+ cation is eight‐coordinate (two nitrogen atoms and six carboxylate oxygen atoms), and contrary to europium(III) complexes with edta, does not contain water molecules in the first coordination sphere. Relationships between the coordination mode and IR as well as UV–Vis spectra are discussed. 相似文献
77.
Solid solutions NaCl—CdCl2 were studied in an interval of CdCl2 concentrations of 0.05—3 mol.% by Raman spectroscopy. The molecular form Na2CdCl4 decomposes: Na2CdCl4 2Na+ + Cd2+ + 2Cl2
– + 2e–; 2Na + 2e– 2Na0. Free sodium atoms form color centers of crystal (F centers) in the region of jumpwise changing the partition coefficient of CdCl2 in NaCl (K jump). 相似文献
78.
C. Maes J. Devaux R. Legras I. W. Parsons 《Journal of polymer science. Part A, Polymer chemistry》1995,33(12):1943-1955
A monofunctional maleimide-ended model compound was synthesized and purified. The thermal curing of this compound was followed by size exclusion chromatography and the molecular masses of the oligomers formed during the curing reaction were determined by mass spectroscopy. It was found that high molecular mass species were not thermally stable. At high temperature and after enough time, a strong decrease in the polydispersity of the oligomers and a significantly preferential formation of trimer were observed. From 13C-NMR characterization, a five membered ring structure was found for the trimer, which explains the thermal stability of this species. © 1995 John Wiley & Sons, Inc. 相似文献
79.
Preparation and characterization of the first derivatives of the fused macropolyhedral anion [B22H22]2− are reported. The species [B22H21OH]2− (1) and [B22H21OEt]2− (2) are obtained from workup of the products of the reaction between HgBr2 and [NBzlEt3]2[B22H22]; a cluster involving the conjoining of a closo-B12 icosahedron with a nido-B10 cluster. Washing the products with ethanol followed by thin-layer chromatography allows the isolation of 1 and 2, reproducibly, in yields of 27 and 20%, respectively. The species were characterized by NMR spectroscopy, elemental analysis and X-ray diffraction studies. The crystal structure determinations of the two species identify novel features. Apparently the influence of the O atoms in the ions [B22H21OH]2− and [B22H21OEt]2− results in the lengthening of what was a gunwale B---B connection adjacent to the junction of the two cages such that the distances are 2.180 and 2.230 Å, respectively. These latter are longer than the corresponding distance in the parent species [B22H22]2−, which is 2.09 Å; quite long for a normal B---B distance. Thus it is assumed that these B atoms, in 1 and 2, one of which bears the substituent, are not bonded to each other. 相似文献
80.
利用阻抗谱测定氧化锆试样的电导率 总被引:1,自引:0,他引:1
利用阻抗谱测定了2.18%MgO稳定的ZrO2试样在空气中的电导率随温度的变化曲线。结果表明,在1165~1 730 K温度变化范围内,电导率在6.0×10-4~3.3×10-2S.cm-1范围内变化;电导率随温度变化曲线可分为4段,其中,在1 423~1 523 K范围内发生单斜相向四方相的转变,1 673 K以上存在四方相向立方相的转变,导致电导率的跳跃升高。 相似文献