全文获取类型
收费全文 | 1846篇 |
免费 | 50篇 |
国内免费 | 8篇 |
专业分类
化学 | 1319篇 |
晶体学 | 14篇 |
力学 | 39篇 |
数学 | 265篇 |
物理学 | 267篇 |
出版年
2023年 | 12篇 |
2022年 | 39篇 |
2021年 | 40篇 |
2020年 | 46篇 |
2019年 | 31篇 |
2018年 | 42篇 |
2017年 | 29篇 |
2016年 | 73篇 |
2015年 | 42篇 |
2014年 | 56篇 |
2013年 | 113篇 |
2012年 | 99篇 |
2011年 | 115篇 |
2010年 | 73篇 |
2009年 | 61篇 |
2008年 | 103篇 |
2007年 | 82篇 |
2006年 | 71篇 |
2005年 | 63篇 |
2004年 | 59篇 |
2003年 | 60篇 |
2002年 | 56篇 |
2001年 | 28篇 |
2000年 | 27篇 |
1999年 | 17篇 |
1998年 | 12篇 |
1997年 | 21篇 |
1996年 | 23篇 |
1995年 | 11篇 |
1994年 | 11篇 |
1993年 | 15篇 |
1992年 | 10篇 |
1991年 | 13篇 |
1990年 | 7篇 |
1988年 | 9篇 |
1987年 | 8篇 |
1985年 | 10篇 |
1984年 | 11篇 |
1983年 | 9篇 |
1982年 | 7篇 |
1981年 | 16篇 |
1979年 | 8篇 |
1976年 | 7篇 |
1918年 | 8篇 |
1905年 | 6篇 |
1901年 | 11篇 |
1895年 | 6篇 |
1894年 | 6篇 |
1888年 | 6篇 |
1885年 | 9篇 |
排序方式: 共有1904条查询结果,搜索用时 15 毫秒
1.
After having introduced by ion implantation 57Fe to a local concentration of 7 at% into Co6Ag94, we observed it by conversion electron Mössbauer spectroscopy in the as-prepared state and after isochronal annealing. A superferromagnetic state is inferred, which is correlated with the ordering of the magnetic moments on the Fe clusters through chain-like or dendritic Co/Fe linear structures. The magnetic moment disordering temperature lies above 473 K. 相似文献
2.
3.
Nb6.74Ta5.26S4 has been prepared by high temperature techniques. The crystal structure has been determined from single crystal X-ray diffraction data (R/Rw = 0.0588/0.0655). The compound crystallizes in the orthorhombic space group Pnma with unit cell dimensions a = 959.11 (26) pm, b = 336.37 (10) pm, and c = 3282.51 (74) pm. The orthorhombic cell contains four formula units. Its structure is similar to that of Nb-rich sulfides, rather than to that of Ta-rich sulfides. The metal coordinations are capped distorted cubic prisms and pentagonal prisms while the coordinations of sulfur are capped trigonal prisms. 相似文献
4.
Dehydroluciferyl-coenzyme A (L-CoA) was chemically synthesized and characterized by MS, UV-vis spectrometry and RP-HPLC. The identity of the chemically synthesized compound with the one that was produced by firefly luciferase was confirmed. Moreover, the reversibility of the enzymatic conversion of dehydroluciferin ? dehydroluciferyl-adenylate ? L-CoA was also confirmed. The chemical synthesis of L-CoA, described here, may help the clarification of the activator effect of CoA on luciferase bioluminescent assays, in which the enzyme catalyzed formation of L-CoA and the consequent destruction of L-AMP is one of the possible explanations for that effect. 相似文献
5.
Elisabeth Egholm JacobsenErik van Hellemond Anders Riise MoenLucia Camino Vazquez Prado Thorleif Anthonsen 《Tetrahedron letters》2003,44(46):8453-8455
In esterifications of secondary alcohols catalyzed by immobilized lipase B from Candida antarctica (Novozym 435) the E-values decreased during the reaction. Hydrolysis of the corresponding butanoates showed the opposite effect. When an enantiopure (R)-alcohol, related but different, was added to the transesterification reaction, the E-value was significantly enhanced. 相似文献
6.
The structure of the hydrogenation product of barbatusin, a diterpenoid from Coleus barbatus Bentham has been revised on the basis of NMR and X-ray data. A geminal coupling of unusually high magnitude has been observed and analysed. 相似文献
7.
van Nostrum CF Benneker FB Brussaard H Kooijman H Veldman N Spek AL Schoonman J Feiters MC Nolte RJ 《Inorganic chemistry》1996,35(4):959-969
The synthesis of novel magnesium, copper, and metal-free porphyrazines, peripherally substituted with dithia-7-crown-2 (MPz(7)), dithia-15-crown-5 (MPz(15)), and dithia-18-crown-6 (MPz(18)) macrocycles is reported. These compounds are prepared starting from dicyanoethylene containing crown ethers 3, 2(1), and 2(2), respectively, which contain sulfur as well as oxygen heteroatoms. The "crowned" porphyrazines bind silver(I) and mercury(II) perchlorates. UV/vis spectroscopy and electron paramagnetic resonance measurements reveal that addition of the transition-metal ions leads to dimerization of the porphyrazine complexes. In the case of the dithia-18-crown-6-substituted porphyrazines, the dimers break up to form monomeric 6:1 guest-host complexes when more than 2 equiv of the metal ion is added. The single-crystal structures of the crown ether 2(2) and the porphyrazine MgPz(18) are presented. Compound C(14)H(20)N(2)O(4)S(2) (2(2)) crystallizes in the monoclinic space group P2(1)/c with a = 10.9310(13) ?, b = 19.383(3) ?, c = 8.6976(14) ?, beta = 108.898(11) degrees, V = 1743.5(5) ?(3), and Z = 4. The structure refinement converged to R = 0.0366 and R(w) = 0.0504. Compound C(56)H(82)MgN(8)O(17)S(8) (MgPz(18)) crystallizes in the triclinic space group P&onemacr; with a = 9.584(3) ?, b = 17.672(2) ?, c = 19.620(4) ?, alpha = 84.904(14) degrees, beta = 85.21(2) degrees, gamma = 89.29(2) degrees, V = 3298.4(13) ?(3), and Z = 2. The structure refinement converged to R1 = 0.0839 and wR2 = 0.2196. The electrical properties of H(2)Pz(18) have been studied by complex impedance spectroscopy. The bulk electrical conductivity of this compound is approximately 1 order of magnitude higher than that of the corresponding 18-crown-6 phthalocyanine. 相似文献
8.
García-Granados A López PE Melguizo E Moliz JN Parra A Simeó Y Dobado JA 《The Journal of organic chemistry》2003,68(12):4833-4844
Several triterpenic derivatives, with the A-ring functionalized, were semisynthesized from oleanolic and maslinic acids. The reactivities of sulfites, sulfate, and epoxides in these triterpene compounds were investigated under different reaction conditions. Moreover, contracted A-ring triterpenes (five-membered rings) were obtained, by different treatments of the sulfate 7. From the epoxide 8, deoxygenated and halohydrin derivatives were semisynthesized with several nucleophiles. Ozonolysis and Beckmann reactions were used to yield 4-aza compounds, from five-membered ring olanediene triterpenes. The X-ray structure of sulfate 7 is given and compared with density functional theory geometries. Theoretical (13)C and (1)H chemical shifts (gauge-invariant atomic orbital method at the B3LYP/6-31G*//B3LYP/6-31G* level) and (3)J(H,H) coupling constants were calculated for compounds 5-9 and 34-36, identifying the (R)- or (S)-sulfur and alpha- or beta-epoxide configurations together with 4-aza or 3-aza structures. 相似文献
9.
Rigol C Olea-Azar C Mendizábal F Otero L Gambino D González M Cerecetto H 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(13-14):2933-2938
Cyclic voltammetry and electron spin resonance (ESR) techniques were used in the investigation of several potential antiprotozoal thiosemicarbazones nitrofurane derivatives. A self-protonation process involving the protonation of the nitro group due to the presence of an acidic proton in the thiosemicarbazone moiety was observed in the first step of a CEE(rev) reduction mechanism of these derivatives. ESR spectra of the free radicals obtained by electrolytic reduction were characterized and analyzed. AM1 methodology was used to obtain the optimized geometries and UB3LYP calculations were performed to obtain the theoretical hyperfine coupling constants. The theoretical study exhibited an unusual assignment of the spin densities showing a free radical centered in the thiosemicarbazone moiety rather than the nitro which are in agreement with the experimental hyperfine pattern. 相似文献
10.
Stephan Weinbruch Michael Wentzel Manfred Kluckner Peter Hoffmann Hugo M. Ortner 《Mikrochimica acta》1997,125(1-4):137-141
In this paper procedures for the characterization of individual aerosol particles by element mapping in the electron microprobe are presented. The number, size and qualitative chemical composition of particles is derived from a combination of secondary or backscattered electron images and element distribution maps. Accuracy of the size distribution and reliability of the qualitative analysis procedure were checked with silicate samples. In order to obtain a semi-quantitative estimate of the chemical composition of individual particles the count rates taken from element distribution maps are corrected for matrix and geometric effects using particle ZAF procedures.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday 相似文献