全文获取类型
收费全文 | 857篇 |
免费 | 20篇 |
国内免费 | 1篇 |
专业分类
化学 | 724篇 |
晶体学 | 1篇 |
力学 | 2篇 |
数学 | 70篇 |
物理学 | 81篇 |
出版年
2021年 | 5篇 |
2020年 | 5篇 |
2019年 | 5篇 |
2018年 | 5篇 |
2017年 | 6篇 |
2016年 | 9篇 |
2015年 | 13篇 |
2014年 | 8篇 |
2013年 | 34篇 |
2012年 | 24篇 |
2011年 | 29篇 |
2010年 | 21篇 |
2009年 | 22篇 |
2008年 | 46篇 |
2007年 | 34篇 |
2006年 | 30篇 |
2005年 | 32篇 |
2004年 | 26篇 |
2003年 | 27篇 |
2002年 | 23篇 |
2001年 | 8篇 |
2000年 | 7篇 |
1999年 | 20篇 |
1998年 | 11篇 |
1997年 | 3篇 |
1996年 | 6篇 |
1995年 | 11篇 |
1994年 | 14篇 |
1993年 | 10篇 |
1992年 | 3篇 |
1991年 | 7篇 |
1990年 | 9篇 |
1989年 | 6篇 |
1987年 | 4篇 |
1986年 | 3篇 |
1985年 | 4篇 |
1982年 | 5篇 |
1980年 | 5篇 |
1979年 | 4篇 |
1978年 | 3篇 |
1977年 | 3篇 |
1975年 | 5篇 |
1967年 | 4篇 |
1966年 | 3篇 |
1965年 | 10篇 |
1963年 | 43篇 |
1962年 | 87篇 |
1961年 | 69篇 |
1960年 | 57篇 |
1959年 | 30篇 |
排序方式: 共有878条查询结果,搜索用时 15 毫秒
31.
The trinuclear Cu(II) complex [(talen)Cu(II)(3)] (1) using the new triplesalen ligand H(6)talen has been synthesized and structurally characterized. The three Cu(II) ions are bridged in a m-phenylene linkage by the phloroglucinol backbone of the ligand. This m-phenylene bridging mode results in ferromagnetic couplings with an S(t) = (3)/(2) spin ground state, which has been analyzed by means of EPR spectroscopy and DFT calculations. The EPR spectrum exhibits an unprecedented pattern of 10 hyperfine lines due to the coupling of three Cu(II) ions (I = (3)/(2)). Resonances around g = 4 in both perpendicular and parallel mode EPR spectra demonstrate a zero-field splitting of D approximately 74 x 10(-4) cm(-1) arising from anisotropic/antisymmetric exchange interactions. The DFT calculations show an alteration in the sign of the spin densities of the central benzene ring corroborating the spin-polarization mechanism as origin for the ferromagnetic coupling. 相似文献
32.
Daniel Ayuk Mbi Egbe Eckhard Birckner Elisabeth Klemm 《Journal of polymer science. Part A, Polymer chemistry》2002,40(15):2670-2679
Luminophoric dialdehyde 1,4‐bis[4‐formylphenylethynyl‐(2,5‐dioctadecyloxyphenyl)‐buta‐1,3‐diyne] ( 4 ) enables the synthesis of diyne‐containing hybrid polyphenyleneethynylene/poly(p‐phenylenevinylene) polymer poly[1,4‐phenylene‐ethynylene‐1,4‐(2,5‐dioctadecyloxy)phenylene‐butadi‐1,3‐ynylene‐1,4‐(2,5‐dioctadecyloxy)phenylene‐ethynylene‐1,4‐phenylene‐ethene‐1,2‐diyl‐1,4‐(2,5‐dioctadecyloxy)phenylene‐ethene‐1,2‐diyl] ( 7 ) with a well‐defined general structure (? Ph? C?C? Ar? C?C? C?C? Ar? C?C? Ph? CH?CH? Ar? CH?CH? )n, which was confirmed by NMR and infrared spectroscopy. The highly luminescent material is thermostable, soluble in usual organic solvents through the grafting of octadecyloxy side groups, and can be processed into transparent films. With the aim to investigate the effect of ? C?C? C?C? in the photophysical behavior of 7 , a comparison of the photophysics of monomers 3 [1,4‐bis(4‐formylphenylethynyl)‐2,5‐dioctadecyloxybenzene] and 4 and subsequently of their respective polymers 6 and 7 has been carried out. Similar photophysical behaviors for 6 (poly[1,4‐phenylenethynylene‐1,4‐(2,5‐dioctadecyloxyphenylene)ethene‐1,2‐diyl]) and 7 were observed in dilute CHCl3 solution as a result of an identical chromophore system responsible for the absorption (λa = 448 nm) and emission (λf = 490 nm) in both compounds. The increased planarization and enhanced rigidity of the conjugated backbone in the solid state at room temperature as well as in frozen dilute tetrahydrofuran solution at 77 K cause the bathochromic shift of the absorption and emission spectra. The large octadecyloxy side chains obviously limit strong π‐π interchain interactions in the solid films, which explains the high fluorescence quantum yields of 35 and 52% obtained for 6 and 7 , respectively. The energetically arduous migration of the π electron through the diyne units not only requires a higher threshold voltage for the detection of photoconductivity in 7 but could possibly limit radiationless deactivation channels of the exciton, which explains the approximate 20% fluorescence quantum yields difference between 6 and 7 in the solid state. The electron‐withdrawing effect of the triple bonds confer both 6 and 7 with a good electron‐accepting property (Eox = 1.39 V vs Ag/AgCl) if used in light‐emitting diode devices. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2670–2679, 2002 相似文献
33.
Bill E Bothe E Chaudhuri P Chlopek K Herebian D Kokatam S Ray K Weyhermüller T Neese F Wieghardt K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,11(1):204-224
The bidentate ligands N-phenyl-o-phenylenediamine, H(2)((2)L(N)IP), or its analogue 2-(2-trifluoromethyl)anilino-4,6-di-tert-butylphenol, ((4)L(N)IP), react with [Co(II)(CH(3)CO(2))(2)]4H(2)O and triethylamine in acetonitrile in the presence of air yielding the square-planar, four-coordinate species [Co((2)L(N))(2)] (1) and [Co((4)L(O))(2)] (4) with an S=1/2 ground state. The corresponding nickel complexes [Ni((4)L(O))(2)] (8) and its cobaltocene reduced form [Co(III)(Cp)(2)][Ni((4)L(O))(2)] (9) have also been synthesized. The five-coordinate species [Co((2)L(N))(2)(tBu-py)] (2) (S=1/2) and its one-electron oxidized forms [Co((2)L(N))(2)(tBu-py)](O(2)CCH(3)) (2 a) or [Co((2)L(N))(2)I] (3) with diamagnetic ground states (S=0) have been prepared, as has the species [Co((4)L(O))(2)(CH(2)CN)] (7). The one-electron reduced form of 4, namely [Co(Cp)(2)][Co((4)L(O))(2)] (5) has been generated through the reduction of 4 with [Co(Cp)(2)]. Complexes 1, 2, 2 a, 3, 4, 5, 7, 8, and 9 have been characterized by X-ray crystallography (100 K). The ligands are non-innocent and may exist as catecholate-like dianions ((2)L(N)IP)(2-), ((4)L(N)IP)(2-) or pi-radical semiquinonate monoanions ((2)L(N)ISQ)(*) (-), ((4)L(N)ISQ)(*) (-) or as neutral benzoquinones ((2) L(N)IBQ)(0), ((4) L(N)IBQ)(0); the spectroscopic oxidation states of the central metal ions vary accordingly. Electronic absorption, magnetic circular dichroism, and EPR spectroscopy, as well as variable temperature magnetic susceptibility measurements have been used to experimentally determine the electronic structures of these complexes. Density functional theoretical (DFT) and correlated ab initio calculation have been performed on the neutral and monoanionic species [Co((1)L(N))(2)](0,-) in order to understand the structural and spectroscopic properties of complexes. It is shown that the corresponding nickel complexes 8 and 9 contain a low-spin nickel(II) ion regardless of the oxidation level of the ligand, whereas for the corresponding cobalt complexes the situation is more complicated. Spectroscopic oxidation states describing a d(6) (Co(III)) or d(7) (Co(II)) electron configuration cannot be unambiguously assigned. 相似文献
34.
Özlem Usluer Christian Kästner Mamatimin Abbas Christoph Ulbricht Vera Cimrova Andreas Wild Eckhard Birckner Nalan Tekin Niyazi Serdar Sariciftci Harald Hoppe Silke Rathgeber Daniel A. M. Egbe 《Journal of polymer science. Part A, Polymer chemistry》2012,50(16):3425-3436
This article reports on the synthesis, characterization, and properties of various anthracene‐containing poly (p‐phenylene‐ethynylene)‐alt‐poly(p‐phenylene‐vinylene) (PPE‐PPV) polymers (AnE‐PVs) bearing statistical distributions of various side chains. Primarily, the ratio of linear octyloxy and branched 2‐ethylhexyloxy side chains at the poly(p‐phenylene vinylene) (PPV) parts was varied, leading to the polymers stat, stat1, and stat2. Furthermore, polymers also containing asymmetric substituted PPV and poly(p‐phenylene ethynylene) units (bearing methoxy and 2‐ethylhexyloxy side chains) were prepared yielding stat3, stat4, and stat5. These materials exhibit a broad variation in their photovoltaic properties. It is once more shown that side chains and their distribution can crucially affect the photovoltaic device performance. The introduction of units with asymmetric substitution into these systems seems to be harmful for their utilization in photovoltaic applications. Organic field‐effect transistors were fabricated to investigate hole mobilities in these new materials. Large variance was observed, falling in the range of almost two orders of magnitude, indicating rather different π–π stacking behavior of the polymer backbones owing to side‐chain modifications. Moreover, a selection of the new polymeric systems was investigated regarding their potential for light‐emitting diode (LED) applications. Polymer LEDs using the polymers AnE‐PVstat, ‐stat3, ‐stat4, and ‐stat5, as the active layer showed turn‐on voltage of ~2 V and exhibited red light emission. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
35.
Applications of Clifford’s Geometric Algebra 总被引:1,自引:0,他引:1
We survey the development of Clifford’s geometric algebra and some of its engineering applications during the last 15 years. Several recently developed applications and their merits are discussed in some detail. We thus hope to clearly demonstrate the benefit of developing problem solutions in a unified framework for algebra and geometry with the widest possible scope: from quantum computing and electromagnetism to satellite navigation, from neural computing to camera geometry, image processing, robotics and beyond. 相似文献
36.
Pieter Bouckenooge Oliver Bauer Kathrin Eckhard Herman Terryn 《Surface and interface analysis : SIA》2020,52(4):174-184
In this paper, the behaviour of the industrial applied Ti/Zr conversion coating (CC) pretreatment on rolled automotive aluminium samples (AA5182) is analysed. Due to its nanometre lateral and depth resolution, Auger electron spectroscopy (AES) is used to analyse the CC distribution at surface cathodic intermetallic particles. As a result of its high surface sensitivity, the AES technique is very susceptible to differences in the top contamination layer thickness. It is demonstrated that AES point measurements performed on aluminium model samples coated with 1.5 and 3 nm of Ti (oxide) layer cannot differentiate the two-layer thicknesses if a difference in the top contamination thickness is not taken into account. A data analysis methodology is introduced, based on the ratio of normalized peak areas (enrichment ratios), to eliminate the effect of the contamination layer thickness. The experimental validation of the methodology is performed on the model samples, demonstrating errors of 2% on the enrichment ratios on similar samples with different contamination layer thicknesses, while the conventional spectra quantification results in errors of 49%. The methodology is also theoretically substantiated within certain constraints. By the use of the AES methodology, an enriched Ti and Zr deposition is confirmed at the cathodic intermetallic particles at the surface of the industrial no-rinse CC sprayed automotive aluminium sheet samples. 相似文献
37.
Eckhard Weissflog Max Schmidt 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3):383-384
Abstract The reaction of bromine with trimeric thioacetic aldehyde leads to the formation of the title compound which may be used as starting material for the synthesis of new methyl-substituted cyclic and linear thioalkanes. 相似文献
38.
39.
40.
Eckhard Steffen 《Journal of Graph Theory》2015,78(3):195-206
Let G be a bridgeless cubic graph. Consider a list of k 1‐factors of G. Let be the set of edges contained in precisely i members of the k 1‐factors. Let be the smallest over all lists of k 1‐factors of G. Any list of three 1‐factors induces a core of a cubic graph. We use results on the structure of cores to prove sufficient conditions for Berge‐covers and for the existence of three 1‐factors with empty intersection. Furthermore, if , then is an upper bound for the girth of G. We also prove some new upper bounds for the length of shortest cycle covers of bridgeless cubic graphs. Cubic graphs with have a 4‐cycle cover of length and a 5‐cycle double cover. These graphs also satisfy two conjectures of Zhang 18 . We also give a negative answer to a problem stated in 18 . 相似文献