全文获取类型
收费全文 | 917篇 |
免费 | 25篇 |
国内免费 | 2篇 |
专业分类
化学 | 536篇 |
晶体学 | 3篇 |
力学 | 28篇 |
数学 | 123篇 |
物理学 | 254篇 |
出版年
2023年 | 4篇 |
2022年 | 9篇 |
2021年 | 18篇 |
2020年 | 14篇 |
2019年 | 8篇 |
2018年 | 9篇 |
2017年 | 10篇 |
2016年 | 24篇 |
2015年 | 19篇 |
2014年 | 29篇 |
2013年 | 57篇 |
2012年 | 52篇 |
2011年 | 73篇 |
2010年 | 43篇 |
2009年 | 31篇 |
2008年 | 56篇 |
2007年 | 60篇 |
2006年 | 50篇 |
2005年 | 64篇 |
2004年 | 38篇 |
2003年 | 31篇 |
2002年 | 26篇 |
2001年 | 11篇 |
2000年 | 15篇 |
1999年 | 8篇 |
1998年 | 7篇 |
1997年 | 8篇 |
1996年 | 13篇 |
1995年 | 3篇 |
1994年 | 14篇 |
1993年 | 6篇 |
1992年 | 11篇 |
1991年 | 9篇 |
1990年 | 7篇 |
1989年 | 9篇 |
1988年 | 9篇 |
1987年 | 10篇 |
1986年 | 5篇 |
1985年 | 13篇 |
1984年 | 6篇 |
1983年 | 5篇 |
1982年 | 5篇 |
1981年 | 4篇 |
1979年 | 4篇 |
1978年 | 7篇 |
1977年 | 8篇 |
1976年 | 3篇 |
1974年 | 3篇 |
1973年 | 2篇 |
1972年 | 2篇 |
排序方式: 共有944条查询结果,搜索用时 78 毫秒
51.
The effects of quasi-periodicity on the splitting of invariant manifolds are examined. We have found that some harmonics that could be expected to be dominant in some ranges of the perturbation parameter actually are nondominant. It is proved that, under reasonable conditions, this is due to the arithmetic properties of the frequencies. 相似文献
52.
53.
Daiana T. Mancini Eugenio F. Souza Melissa S. Caetano Teodorico C. Ramalho 《Magnetic resonance in chemistry : MRC》2014,52(4):129-137
The phenylbenzothiazole compounds show antitumor properties and are highly selective. In this paper, the 99Tc chemical shifts based on the (99mTc)(CO)3(NNO) complex conjugated to the antitumor agent 2‐(4′‐aminophenyl)benzothiazole are reported. Thermal and solvent effects were studied computationally by quantum‐chemical methods, using the density functional theory (DFT) (DFT level BPW91/aug‐cc‐pVTZ for the Tc and BPW91/IGLO‐II for the other atoms) to compute the NMR parameters for the complex. We have calculated the 99Tc NMR chemical shifts of the complex in gas phase and solution using different solvation models (polarizable continuum model and explicit solvation). To evaluate the thermal effect, molecular dynamics simulations were carried, using the atom‐centered density matrix propagation method at the DFT level (BP86/LanL2dz). The results highlight that the 99Tc NMR spectroscopy can be a promising technique for structural investigation of biomolecules, at the molecular level, in different environments. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
54.
The Adimurthi–Druet [1] inequality is an improvement of the standard Moser–Trudinger inequality by adding a -type perturbation, quantified by , where is the first Dirichlet eigenvalue of Δ on a smooth bounded domain. It is known [3], [10], [14], [19] that this inequality admits extremal functions, when the perturbation parameter α is small. By contrast, we prove here that the Adimurthi–Druet inequality does not admit any extremal, when the perturbation parameter α approaches . Our result is based on sharp expansions of the Dirichlet energy for blowing sequences of solutions of the corresponding Euler–Lagrange equation, which take into account the fact that the problem becomes singular as . 相似文献
55.
Jorge Castellanos-Soriano Allen T. Ekubo Mark R. J. Elsegood Nuria Lastra-Calvo Aman Mantry Arturo Martinez-Insua-Rodriguez 《Phosphorus, sulfur, and silicon and the related elements》2017,192(5):570-575
New tetraalkylaminophosphonium chlorides were readily prepared by four-fold condensation of commercially available [P(CH2OH)4]Cl with a range of fifteen aryl based primary amines, in EtOH, at ambient temperature. All compounds have been characterized by FT–IR spectroscopy and elemental analysis. Solution 31P{1H} NMR studies of these chloride salts reveal their instability with respect to various PIII/PV species. The structures of three examples have been determined by single crystal X-ray diffraction and confirm the pseudotetrahedral arrangement around the PV center. Extensive N–H···Cl hydrogen bonding is observed. 相似文献
56.
M. Angeles Castro José M. Miguel del Corral M. Lucena Rodríguez Arturo San Feliciano 《Tetrahedron letters》2012,53(5):519-521
Cyclisation of terpenylnaphthohydroquinone derivatives or terpenylquinone cycloadducts, obtained from methyl myrcecommunate, was performed in the presence of HI, I2 or BF3·OEt2 and provides efficient synthetic strategies for the preparation of pentacyclic terpenylquinones. 相似文献
57.
Arturo Arduini Alessandro Casnati Massimo Fabbi Patrizia Minari Andrea Pochini Anna Rita Sicuri 《Supramolecular chemistry》2013,25(3-4):235-246
Abstract The development of new synthetic methods for the monoalkylation of calix[4]arenes at the lower rim allows the synthesis of a new class of trihydroxamate siderophores. Three chelating hydroxamic acid units are introduced through a sequence of reactions which blocks the macrocycle in the cone conformation. The new ligands obtained form neutral 1:1 complexes (FeL) with iron (III), which are stable in EtOH/H2O 9:1 at pH 2–7. Calix[4]arene bis-crown ethers are prepared by exploiting the selective 1,2-(proximal) functionalization of calix[4]arenes at the lower rim. These ligands are, however, less effective in complexing alkali metal cations compared with the 1,3-calix[4]arene crown-ethers which, in their partial cone structure, offer a better shielding for the complexed cations. Rigid upper rim-bridged calix[4]arenes potentially useful for the inclusion of neutral molecules are prepared by exploiting the selective 1,3-diformylation of calix[4]arene at the upper rim. Finally a new chloromethylation method for calix[4]arenes blocked in the cone conformation is described together with the synthesis of new cavitands. 相似文献
58.
Dr. Annalisa Mancini Dr. M. Carla Aragoni Dr. Neil Bricklebank Dr. Carlo Castellano Prof. Francesco Demartin Prof. Francesco Isaia Prof. Vito Lippolis Dr. Anna Pintus Dr. Massimiliano Arca 《化学:亚洲杂志》2013,8(3):639-647
The reactions of 4,5,6,7‐tetrathiocino‐[1,2‐b:3,4‐b′]‐1,3,8,10‐tetrasubstituted‐diimidazolyl‐2,9‐dithiones (R2,R′2‐todit; 1 : R=R′=Et; 2 : R=R′=Ph; 3 : R=Et, R′=Ph) with Br2 exclusively afforded 1:1 and 1:2 “T‐shaped” adducts, as established by FT‐Raman spectroscopy and single‐crystal X‐ray diffraction in the case of complex 1? 2 Br2. On the other hand, the reactions of compounds 1 – 3 with molecular I2 provided charge‐transfer (CT) “spoke” adducts, among which the solvated species 3? 2 I2 ? (1?x)I2 ? x CH2Cl2 (x=0.94) and ( 3 )2 ? 7 I2 ? x CH2Cl2, (x=0.66) were structurally characterized. The nature of all of the reaction products was elucidated based on elemental analysis and FT‐Raman spectroscopy and supported by theoretical calculations at the DFT level. 相似文献
59.
Schubert M Balcazar M Lopez A Peña P Flores JH Knöller K 《Isotopes in environmental and health studies》2007,43(3):215-226
The non-aqueous phase-liquid (NAPL)-contaminated aquifer at a major refinery site in Mexico was investigated. Owing to the depth of the contaminated aquifer section (NAPL source zone) of over 100 m below the surface, the actual aquifer material was not accessible for sampling. Information on the residual NAPL contamination of the aquifer could only be obtained indirectly by analysing groundwater samples from a few wells available at the site. To tackle the problem, an approach alternative to conventional groundwater analysis for dissolved NAPL was chosen. For evaluating the recent contamination and estimating its probable future development, the radioisotope radon-222 and the stable isotopes 13C, 34S and 18O were used as naturally occurring contamination tracers and process indicators. Radon was used as partitioning tracer for the approximate localization and semi-quantitative assessment of the NAPL source zone. The stable isotopes were used as indicators for naturally occurring biodegradation processes, which might potentially be implemented into future remediation schemes. 相似文献
60.
Dr. Philip Junker Alicia Rey Planells Prof. Dr. Arturo Espinosa Ferao Prof. Dr. Rainer Streubel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(36):9350-9359
Several phosphaquinodimethanes and their M(CO)5 complexes (M=Cr, Mo, W) and model derivatives have been theoretically investigated regarding the quest of non-innocence. Computed structural and electronic properties of the P-Me/NH2 substituted phosphaquinodimethanes and tungsten complexes revealed an interesting non-innocent ligand behaviour for the radical anion complexes with distonic ion character and a strong rearomatization of the middle phenyl ring. The latter was further probed taking also geometric aromaticity (HOMA) and quinoid distortion parameters (HOMQc) into account, as well as NICS(1). Furthermore, the effect of the P-substitution was investigated for real (or plausible) complexes and their free ligands focusing on the resulting aromaticity at the middle phenyl ring and vertical one-electron redox processes. The best picture of ligand engagement in redox changes was provided by representing NICS(1) values versus HOMA and the new geometric distortion parameter HOMQc8. 相似文献