全文获取类型
收费全文 | 860篇 |
免费 | 1篇 |
国内免费 | 4篇 |
专业分类
化学 | 630篇 |
晶体学 | 7篇 |
力学 | 29篇 |
数学 | 91篇 |
物理学 | 108篇 |
出版年
2023年 | 7篇 |
2022年 | 5篇 |
2021年 | 7篇 |
2020年 | 7篇 |
2019年 | 4篇 |
2016年 | 4篇 |
2015年 | 7篇 |
2014年 | 6篇 |
2013年 | 31篇 |
2012年 | 38篇 |
2011年 | 56篇 |
2010年 | 23篇 |
2009年 | 16篇 |
2008年 | 47篇 |
2007年 | 63篇 |
2006年 | 51篇 |
2005年 | 50篇 |
2004年 | 63篇 |
2003年 | 44篇 |
2002年 | 36篇 |
2001年 | 8篇 |
2000年 | 5篇 |
1999年 | 11篇 |
1998年 | 8篇 |
1997年 | 12篇 |
1996年 | 12篇 |
1995年 | 11篇 |
1994年 | 11篇 |
1993年 | 10篇 |
1992年 | 7篇 |
1991年 | 6篇 |
1990年 | 16篇 |
1989年 | 10篇 |
1988年 | 4篇 |
1987年 | 4篇 |
1986年 | 5篇 |
1985年 | 8篇 |
1984年 | 21篇 |
1983年 | 10篇 |
1982年 | 17篇 |
1981年 | 5篇 |
1980年 | 12篇 |
1979年 | 10篇 |
1978年 | 18篇 |
1977年 | 13篇 |
1976年 | 13篇 |
1975年 | 8篇 |
1974年 | 8篇 |
1973年 | 5篇 |
1968年 | 3篇 |
排序方式: 共有865条查询结果,搜索用时 15 毫秒
21.
The study of the mass analysed ion kinetic energy spectra of deuterated derivatives of aniline, aminopyridines and 2-chloro-5-aminopyridine shows that prior to HCN loss, hydrogen scrambling does not occur for aminopyridines and is limited but noticeable for aniline. In the case of this last compound the extent of scrambling varies markedly for small variations in the energy of the ions studied, these variations being within the energy window corresponding to metastable ions. Furthermore, an examination of the mass analysed ion kinetic energy spectra of monodeuterated derivatives of aminopyridines leads to the rejection of the generally accepted mechanism for HCN loss from the molecular ions of these compounds. 相似文献
22.
Chardon-Noblat S Horner O Chabut B Avenier F Debaecker N Jones P Pécaut J Dubois L Jeandey C Oddou JL Deronzier A Latour JM 《Inorganic chemistry》2004,43(5):1638-1648
Reaction of the unsymmetrical phenol ligand 2-((bis(2-pyridylmethyl)amino)methyl)-6-(((2-pyridylmethyl)benzylamino)methyl)-4-methylphenol (HL-Bn) or its 2,6-dichlorobenzyl analogue (HL-BnCl(2)) with Fe(H(2)O)(6)(ClO(4))(2) in the presence of disodium m-phenylenedipropionate (Na(2)(mpdp)) followed by exposure to atmosphere affords the diiron(II,III) complexes [Fe(2)(L-Bn)(mpdp)(H(2)O)](ClO(4))(2) and [Fe(2)(L-BnCl(2))(mpdp)(CH(3)OH)](ClO(4))(2), respectively. The latter complex has been characterized by X-ray crystallography. It crystallizes in the monoclinic system, space group P2(1)/n, with a = 13.3095(14) A, b = 20.1073(19) A, c = 19.4997(19) A, alpha = 90 degrees, beta = 94.471(2) degrees, gamma = 90 degrees, V = 5202.6(9) A(3), and Z = 4. The structure of the compound is very similar to that of [Fe(2)(L-Bn)(mpdp)(H(2)O)](BPh(4))(2) determined earlier, except for the replacement of a water by a methanol on the ferrous site. Magnetic measurements of [Fe(2)(L-Bn)(mpdp)(H(2)O)](BPh(4))(2) reveal that the two high-spin Fe ions are moderately antiferromagnetically coupled (J = -3.2(2) cm(-)(1)). Upon dissolution in acetonitrile the terminal ligand on the ferrous site is replaced by a solvent molecule. The acetonitrile-water exchange has been investigated by various spectroscopic techniques (UV-visible, NMR, M?ssbauer) and electrochemistry. The substitution of acetonitrile by water is clearly evidenced by M?ssbauer spectroscopy by a reduction of the quadrupole splitting value from 3.14 to 2.41 mm/s. In addition, it causes a 210 mV downshift of the oxidation potential of the ferrous site and a similar reduction of the stability domain of the mixed-valence state. Exhaustive electrolysis of a solution of [Fe(2)(L-Bn)(mpdp)(H(2)O)](2+) shows that the aqua diferric species is not stable and undergoes a chemical reaction which can be partly reversed by reduction to the mixed-valent state. This and other electrochemical observations suggest that upon oxidation of the diiron center to the diferric state the aqua ligand is deprotonated to a hydroxo. This hypothesis is supported by M?ssbauer spectroscopy. Indeed, this species possesses a large quadrupole splitting value (DeltaE(Q) >or= 1.0 mm.s(-)(1)) similar to that of analogous complexes with a terminal phenolate ligand. This study illustrates the drastic effects of aqua ligand exchange and deprotonation on the electronic structure and redox potentials of diiron centers. 相似文献
23.
Michel F Thomas F Hamman S Saint-Aman E Bucher C Pierre JL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(17):4115-4125
Galactose oxidase (GO) is an enzyme that catalyzes two-electron oxidations. Its active site contains a copper atom coordinated to a tyrosyl radical, the biogenesis of which requires copper and dioxygen. We have recently studied the properties of electrochemically generated mononuclear Cu(II)-phenoxyl radical systems as model compounds of GO. We present here the solution chemistry of these ligands under various copper and dioxygen statuses: N(3)O ligands first chelate Cu(II), leading, in the presence of base, to [Cu(II)(ligand)(CH(3)CN)](+) complexes (ortho-tert-butylated ligands) or [(Cu(II))(2)(ligand)(2)](2+) complexes (ortho-methoxylated ligands). Excess copper(II) then oxidizes the complex to the corresponding mononuclear Cu(II)-phenoxyl radical species. N(2)O(2) tripodal ligands, in the presence of copper(II), afford directly a copper(II)-phenoxyl radical species. Addition of more than two molar equivalents of copper(II) affords a Cu(II)-bis(phenoxyl) diradical species. The donor set of the ligand directs the reaction towards comproportionation for ligands possessing an N(3)O donor set, while disproportionation is observed for ligands possessing an N(2)O(2) donor set. These results are discussed in the light of recent results concerning the self-processing of GO. A path involving copper(II) disproportionation is proposed for oxidation of the cross-linked tyrosinate of GO, supporting the fact that both copper(I) and copper(II) activate the enzyme. 相似文献
24.
Amination of 4-nitrophenol, umbelliferone and 4-methylumbelliferone gave the corresponding oxyamines 1-3. These oxyamines react with aldehydes and ketones to form oximes. In the case of aliphatic aldehydes and electron-poor aromatic aldehydes, the oximes undergo base-catalyzed fragmentation in aqueous buffer in the presence of bovine serum albumin to give the parent phenols, which is the acyclic analog of Kemp's elimination reaction of 5-nitrobenzisoxazole 28. The process can be used as a spectrophotometric assay for formaldehyde under aqueous neutral conditions. 相似文献
25.
26.
Jean-Louis Kraus 《合成通讯》2013,43(7):827-832
The specific synthesis of a new glyphosate tetrazole analogue with pesticidal properties is reported. 相似文献
27.
Valerie Lefevre Jean-Louis Ripoll 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):371-372
The retro-ene reaction of allylthio- and propargylthiosilanes led, under flash vacuum thermolysis (FVT) conditions, to unhindered silanethiones, characterized by their derivatives, and also directly by coupling of the FVT with gas-phase spectrometries. Monomeric silicon oxysulfide has been generated similarly. The unsubstituted silanethione was not obtained, but dehydrogenated into silicon monosulfide during FVT. 相似文献
28.
This work presents an automatic system, based on an electronic tongue, for resolution of mixtures of three pesticides. Inhibition detections were performed during the steady state of biosensors response. Three biosensors were built using two enzymes, electric eel (EE), genetically-modified Drosophila melanogaster (B131), and electric eel co-immobilized with drosophila melanogaster (BH). Calibrations curves for paraoxon, dichorlvos, and carbofuran were performed in the ranges 0.4–50.4 µM, 0.01–1.01 µM, 0.01–0.41 µM with LOD of 3.91 × 10?8, 6.30 × 10?11, and 5.84 × 10?10, respectively. An artificial neural network (ANN) was used to model the combined response of three pesticides. A set of 19 mixtures were prepared in order to train the artificial neural network, the modeling was validated with a set of 6 spiked samples of river water. The error and recovery yields were found in consistent with expected values. 相似文献
29.
Marta Rámirez Johnny Bullón José Andérez Isabel Mira Jean-Louis Salager 《Journal of Dispersion Science and Technology》2013,34(1-3):309-321
The research work on why and how distribution bimodality tends to reduce the viscosity of a particulate suspension is reviewed. The transfer of the corresponding concepts to emulsions requires some statistical tools, and becomes particularly easy with probability scale plotting which is reviewed. Viscosity reduction can be attained for different kinds of fine and coarse emulsion associations. The results are shown to depend on the characteristics of the base emulsions as well as on the way they are mixed. 相似文献
30.
Gérôme F Février S Pryamikov AD Auguste JL Jamier R Blondy JM Likhachev ME Bubnov MM Semjonov SL Dianov EM 《Optics letters》2007,32(10):1208-1210
An all-silica photonic bandgap fiber composed of a low-index core surrounded by alternating high- and low-index rings allows us to achieve a large mode area (500 microm(2)) and large chromatic dispersion. Sharp resonances from the even Bragg mode to odd ring modes theoretically lead to 20,000 ps/(nm km) chromatic dispersion when large bends are applied. By nature, sharp resonances are sensitive to inhomogeneities along the fiber length. Under experimental conditions, the resonances are broadened and the dispersion coefficient is decreased to 1000 ps/(nm km). However, to the best of our knowledge, this is the largest dispersion coefficient reported using a large mode area fiber. 相似文献