全文获取类型
收费全文 | 672篇 |
免费 | 27篇 |
国内免费 | 4篇 |
专业分类
化学 | 425篇 |
晶体学 | 4篇 |
力学 | 16篇 |
数学 | 70篇 |
物理学 | 188篇 |
出版年
2023年 | 4篇 |
2022年 | 7篇 |
2021年 | 17篇 |
2020年 | 15篇 |
2019年 | 20篇 |
2018年 | 10篇 |
2017年 | 5篇 |
2016年 | 18篇 |
2015年 | 25篇 |
2014年 | 27篇 |
2013年 | 30篇 |
2012年 | 32篇 |
2011年 | 50篇 |
2010年 | 22篇 |
2009年 | 24篇 |
2008年 | 64篇 |
2007年 | 36篇 |
2006年 | 43篇 |
2005年 | 52篇 |
2004年 | 33篇 |
2003年 | 21篇 |
2002年 | 22篇 |
2001年 | 17篇 |
2000年 | 7篇 |
1999年 | 5篇 |
1998年 | 4篇 |
1997年 | 2篇 |
1996年 | 7篇 |
1994年 | 6篇 |
1993年 | 2篇 |
1991年 | 2篇 |
1989年 | 3篇 |
1988年 | 5篇 |
1987年 | 3篇 |
1986年 | 2篇 |
1985年 | 7篇 |
1984年 | 5篇 |
1982年 | 4篇 |
1981年 | 8篇 |
1979年 | 2篇 |
1978年 | 4篇 |
1977年 | 3篇 |
1976年 | 4篇 |
1975年 | 4篇 |
1973年 | 5篇 |
1972年 | 2篇 |
1971年 | 2篇 |
1958年 | 2篇 |
1935年 | 1篇 |
1914年 | 2篇 |
排序方式: 共有703条查询结果,搜索用时 968 毫秒
1.
Norbert Auner Larissa Zherlitsyna Michael Bolte 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(5):m199-m200
The title compound, [Cu8(C8H24O2Si)2(C3H7NO)8]·C4H4N2·C3H7NO, features a sandwich‐like cage enclosing a pyrazine molecule, both situated on a centre of inversion. In addition, the crystal structure contains one dimethylformamide molecule which is disordered over a centre of inversion. The copper layer, containing eight atoms, is located between two siloxanolate fragments. The whole structure of Cu atoms and siloxanolate rings is distorted by the pyrazine molecule, leading to an oval form. As a result, the angles between the Cu atoms differ at the copper layer. The difference in the angles could lead to some deviations in the Cu–Cu exchange interactions within the copper ring, which is of interest for molecular magnetism. 相似文献
2.
C. Caldera N. Caponio C. de Bernardi F. Delpiano G. Destefanis S. Morasca M. Puleo G. Schiavini F. Schiattone A. Stano E. Legros M. Billard 《Optical and Quantum Electronics》1994,26(5):S529-S545
Optical waveguide 3-dB couplers integrated on semicondutors have been studied, designed and fabricated, using both bulk and diluted multi-quantum-well InGaAsP/InP-based materials, grown by MOCVD. The device structure is based on the two-mode interference (TMI) principle and is fully compatible for integration with the optoelectronic and electronic components of a coherent receiver. Bulk material couplers provide an output balanced within 0.05 dB per nanometer and an excess loss of 1.4 dB, compared to a straight guide, while coupling loss to a tapered-lensed single mode fibre is 4 dB.Improved coupling efficiency to single-mode fibres is achieved by use of moderately diluted multi-quantum-well waveguides, which include InGaAsP wells and InP barriers: coupling loss to a tapered-lensed single-mode fibre as low as 0.5 dB and excess loss of 1.8 dB are featured. Couplers fabricated with this waveguide structure have a balance sensitivity of 0.03 to 0.04 dB per nanometer.A moderately diluted multi-quantum-well 3-dB coupler has been permanently pigtailed and butt-coupled to a dual balanced PIN photoreceiver. This hybrid assembly was tested in a coherent transmission system at 155 and 622 Mbits-1 showing sensitivities, for 10-9 BER, of about-38.0 dBm and-28.8 dBm, respectively. 相似文献
3.
The photoreactions of 4 and 2-pyridinecarbonitrile with cyclopentene carried out in acetone or in acetonitrile solutions lead, respectively, to 4-(2 cyclopentenyl)-pyridine and 2-(2 cyclopentenyl)pyridine . From 2-pyridinecarbonitrile a little amount of ketone is obtained. 相似文献
4.
Ronaldo Santos da Silva Maria Inês Basso Bernardi Antonio Carlos Hernandes 《Journal of Sol-Gel Science and Technology》2007,42(2):173-179
In this work, we have studied the influence of the pH on the synthesis and structural properties of the Ba0.77Ca0.23TiO3 nanopowders synthesized by a modified polymeric precursor method, in order to achieve non-agglomerated powders. Synthesis,
morphology, thermal reactions, crystallite and average particle size of the synthesized powders were investigated through
thermal analysis (DTA/TG), X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM) and Infrared spectroscopy.
In summary, Ba0.77Ca0.23TiO3 nanopowders were synthesized for the first time at a relative low temperature (500 °C). It was also found that the alkalinity
and acidity of the solution presented a great influence on the powder properties. The best results were obtained from solutions
with pH = 8.5 and 11 whose nanopowders presented weakly agglomerate, with homogeneous particle size and a narrow size distribution
(30–40 nm). This behavior could be explained based on the FT-IR results in which it was possible to see the increased of the
chelation in higher pHs. 相似文献
5.
Bernardi A Potenza D Capelli AM García-Herrero A Cañada FJ Jiménez-Barbero J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(20):4598-4612
As a step to delineate a strategy of ligand design for cholera toxin (CT), NMR studies were performed on several mimics of the GM1 ganglioside oligosaccharide. The conformation of these analogues was investigated first in solution and then upon binding to cholera toxin by transferred nuclear Overhauser effect (TR-NOE) measurements. It was demonstrated that CT selects a conformation similar to the global minima of the free saccharides from the ensemble of presented conformations. No evidence of major conformational distortions was obtained, but one or two of the available conformers of the hydroxyacid side chain appear to be selected in the bound state. The NMR data were interpreted with the aid of computer models, generated and analyzed by using a combination of different approaches (MacroModels' MC/EM and MC/SD, Autodock, and GRID). Analysis of the NMR data supported by computational studies allowed us to interpret the experimental observations and to derive workable models of the ligand:toxin complexes. These models suggest that the higher affinity of the (R)-lactic acid derivative 3 may stem from lipophilic interactions with a hydrophobic area in the toxin binding site located in the vicinity of the sialic acid side chain binding region of the CT:GM1 complex, and formed by the side chain of Ile-58 and Lys-34. Thus, the models obtained have allowed us to make useful design suggestions for the improvement of ligand affinity. 相似文献
6.
Ryabov AD Otto S Samuleev PV Polyakov VA Alexandrova L Kazankov GM Shova S Revenco M Lipkowski J Johansson MH 《Inorganic chemistry》2002,41(16):4286-4294
Structural and mechanistic aspects of orthoplatination of acetophenone and benzaldehyde oximes by the platinum(II) sulfoxide and sulfide complexes [PtCl(2)L(2)] (2, L = SOMe(2) (a), rac-SOMePh (b), R-SOMe(C(6)H(4)Me-4) (c), and SMe(2) (d)) to afford the corresponding platinacycles cis-(C,S)-[Pt(II)(C(6)H(3)-2-CR'=NOH-5-R)Cl(L)] (3, R, R' = H, Me) have been investigated. The reaction of acetophenone oxime with sulfoxide complex 2a in methanol solvent occurs noticeably faster than with sulfide complex 2d due to the fact that the sulfoxide is a much better platinum(II) leaving ligand than the sulfide. Evidence is presented that the orthoplatination is a multistep process. The formation of unreactive dichlorobis(N-oxime)platinum(II) cations accounts for the rate retardation by excess acetophenone oxime and suggests the importance of pseudocoordinatively unsaturated species for the C-H bond activation by Pt(II). A comparative X-ray structural study of dimethyl sulfoxide platinacycle 3b (R = R' = Me) and its sulfide analogue 3e (R = H, R' = Me), as well as of SOMePh complex 3c (R = H, R' = Me), indicated that they are structurally similar and a sulfur ligand is coordinated in the cis position with respect to the sigma-bound phenyl carbon. The differences concern the Pt-S bond distance, which is notably longer in the sulfide complex 3e (2.2677(11) A) as compared to that in sulfoxide complexes 3b (2.201(2)-2.215(2) A) and 3c (2.2196(12) A). Whereas the metal plane is practically a plane of symmetry in 3b due to the H-bonding between the sulfoxide oxygen and the proton at carbon ortho to the Pt-C bond, an S-bonded methyl of SOMePh and SMe(2) is basically in the platinum(II) plane in complexes 3c and 3e, respectively. There are intra- and intermolecular hydrogen bond networks in complex 3b. An interesting structural feature of complex 3c is that the two independent molecules in the asymmetric unit of the crystal reveal an extremely short Pt-Pt contact of 3.337 A. 相似文献
7.
Arosio D Fontanella M Baldini L Mauri L Bernardi A Casnati A Sansone F Ungaro R 《Journal of the American Chemical Society》2005,127(11):3660-3661
A high-affinity ligand of cholera toxin, the divalent glycocalix[4]arene 1, was obtained by exploiting a combination of structure-based design of glycomimetic monovalent ligands and affinity enhancements by multivalent presentation through a calix[4]arene scaffold. It exhibits a slightly higher affinity for the toxin than its natural ligand, the GM1 oligosaccharide. 相似文献
8.
9.
Various techniques, already suggested for improving the computational efficiency of the force relaxation method, have been applied here in conjunction with the variable metric algorithms suggested by Murtagh and Sargent and by Fletcher. Various tests have been performed to assess the computational efficiency of the resulting minimization procedures. In addition, procedures where the steps are defined in terms of a parabolic fitting of the forces in approximated normal coordinates have been tested. In all cases the forces are computed analytically. 相似文献
10.
Anna Bernardi Silvia Cardani Cesare Gennari Giovanni Poli Carlo Scolastico 《Tetrahedron letters》1985,26(52):6509-6512
MgBr2 mediated addition of Methyl α-methylthio propionate silylketene acetal to α and α,β-alkoxy aldehydes is highly 3,4 -selective (18:1). -α- methylene-β- hydroxy-?-alkoxy esters (6) and (8) are synthesized. 相似文献