全文获取类型
收费全文 | 598篇 |
免费 | 22篇 |
专业分类
化学 | 388篇 |
晶体学 | 16篇 |
力学 | 16篇 |
数学 | 50篇 |
物理学 | 150篇 |
出版年
2023年 | 6篇 |
2022年 | 12篇 |
2021年 | 12篇 |
2020年 | 16篇 |
2019年 | 15篇 |
2018年 | 12篇 |
2017年 | 8篇 |
2016年 | 23篇 |
2015年 | 16篇 |
2014年 | 22篇 |
2013年 | 31篇 |
2012年 | 44篇 |
2011年 | 43篇 |
2010年 | 28篇 |
2009年 | 22篇 |
2008年 | 26篇 |
2007年 | 33篇 |
2006年 | 21篇 |
2005年 | 22篇 |
2004年 | 33篇 |
2003年 | 17篇 |
2002年 | 27篇 |
2001年 | 6篇 |
2000年 | 7篇 |
1999年 | 10篇 |
1998年 | 4篇 |
1997年 | 4篇 |
1996年 | 4篇 |
1995年 | 3篇 |
1994年 | 4篇 |
1993年 | 3篇 |
1991年 | 7篇 |
1990年 | 3篇 |
1989年 | 6篇 |
1988年 | 4篇 |
1987年 | 4篇 |
1986年 | 5篇 |
1985年 | 4篇 |
1984年 | 5篇 |
1982年 | 6篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1979年 | 3篇 |
1978年 | 4篇 |
1977年 | 3篇 |
1974年 | 4篇 |
1973年 | 4篇 |
1972年 | 6篇 |
1971年 | 2篇 |
1934年 | 1篇 |
排序方式: 共有620条查询结果,搜索用时 15 毫秒
61.
The reaction of gold(III) neutral complexes AuBr(CN)2(N–N) {N–N = 2,2′-bipyridine (bpy), 5,5′-dimethyl-2,2′-bipyridine (Me2bpy), 1,10-phenanthroline (phen)} with a stoichiometric amount of K[AuCl4] · 2H2O in nitromethane at room temperature led to the formation of 1:1 electrolytes which were characterized by NMR and IR spectroscopy,
conductivity measurements, elemental analyses and X-ray diffraction. Both the anions and the cations of these salts are singly
charged square-planar Au(III) complexes and the cations have general formula [AuCl2(N–N)]+. A hypothesis on the possible reaction mechanisms is presented to give an explanation for the formation of the reaction products. 相似文献
62.
Reid Tingley Valerio Bertolasi Keith Vaughan 《Journal of chemical crystallography》2006,36(12):831-839
A new series of bis-triazenes, the 1-aryl-2-[3-(3-[2-aryl-1-diazenyl]-1,3-diazepan-1-ylmethyl)-1,3-diazepan-1-yl]-1-diazenes has been synthesized from the reaction of diazonium salts with a mixture of 1,4-diaminobutane and formaldehyde. The structures of 1-(p-bromophenyl)-2-[3-{3-[2-(p-bromophenyl)-1-diazenyl]-1,3-diazepan-1-ylmethyl}-1,3-diazepan-1-yl]-1-diazene(1), 1-(p-cyanophenyl)-2-[3-{3-[2-(p-cyanophenyl)-1-diazenyl]-1,3-di azepan-1-ylmethyl}-1,3-diazepan-1-yl]-1-diazene(2), and 1-(p-methoxyphenyl)-2-[3-{3-[2-(p-methoxy-phenyl)-1-diazenyl]-1,3-diazepan-1-ylmethyl}-1,3-diazepan-1-yl]-1 diazene(3) have been unequivocally determined by X-ray crystallography. The new bis-triazenes are important since the structure contains the novel saturated heterocycle, 1,3-diazepane. The general conclusion of this study is that alkanediamines with 3 or 4 carbon atoms in the spacer link between the nitrogen atoms give rise to the linear bicyclic molecules of type 5, in contrast to the case of ethylenediamine (spacer link 2 carbon atoms), which affords molecules of type 6, which exemplify the general cage structure of type 4. The crystal structures of 1, 2 and 3 are compared with the previously reported structure of the hexahydropyrimidine analogue 8a(X=CN); compounds 2 and 8a(X=CN) are homologous with respect to the alkane spacer moiety. The structures of 2 and 8a(X=CN) are very different in one respect; in 2 the aryldiazenyl-1,3-diazepanyl groups are in the s-trans orientation around the central methylene group whereas in 8a(X=CN) the arrangement of the aryldiazenyl-hexahydropyrimidinyl groups is the s-cis orientation.Crystal data: 1 C23H30N8Br2, triclinic, space group P-1, a=8.3979(2), b=10.7828(3), c=14.4692(5) ?, α=83.670(1), β=78.662(1), γ=78.758(1)°, V=1256.48(6) ?3, for Z=2. 2 C25H30N10, monoclinic, space group P2
1
/n, a=13.4046(6), b=9.4482(4), c=10.6913(4)?, β=103.239(2)°, V=2490.5(2) ?3, for Z=4. 3 C25H36N8O2, triclinic, space group P-1, a=8.5223(3), b=10.6913(4), c=14.4034(7)?, α=85.657(2), β=78.731(2), γ=80.153(1)°, V=1266.88(9) ?3, for Z=2. 相似文献
63.
Philippe Schwaller Riccardo Petraglia Valerio Zullo Vishnu H. Nair Rico Andreas Haeuselmann Riccardo Pisoni Costas Bekas Anna Iuliano Teodoro Laino 《Chemical science》2020,11(12):3316
We present an extension of our Molecular Transformer model combined with a hyper-graph exploration strategy for automatic retrosynthesis route planning without human intervention. The single-step retrosynthetic model sets a new state of the art for predicting reactants as well as reagents, solvents and catalysts for each retrosynthetic step. We introduce four metrics (coverage, class diversity, round-trip accuracy and Jensen–Shannon divergence) to evaluate the single-step retrosynthetic models, using the forward prediction and a reaction classification model always based on the transformer architecture. The hypergraph is constructed on the fly, and the nodes are filtered and further expanded based on a Bayesian-like probability. We critically assessed the end-to-end framework with several retrosynthesis examples from literature and academic exams. Overall, the frameworks have an excellent performance with few weaknesses related to the training data. The use of the introduced metrics opens up the possibility to optimize entire retrosynthetic frameworks by focusing on the performance of the single-step model only.We present an extension of our Molecular Transformer model combined with a hyper-graph exploration strategy for automatic retrosynthesis route planning without human intervention. 相似文献
64.
Marek L. Główka Zbigniew J. Kamiński Gastone Gilli Valerio Bertolasi 《Journal of chemical crystallography》1986,16(4):569-576
C14H17NO4 crystallizes in the monoclinic space groupP21/n (Z=4) witha=10.208(2),b=10.888(2),c=11.909(2) Å, and=90.89(2)°. The structure was solved by direct methods and refined by full-matrix LSQ to anR factor of 0.036. The 4-oxo-1,3-dioxane ring is in a slightly distorted O(1)-sofa conformation flattened at the C(4) end with the 5-isopropyl substituent in a pseudoaxial position and planar lactone group. The molecules form dimers by means of intermolecular N-HO(4) hydrogen bonds of 3.091(2) Å. The1H NMR spectrum of the title compound shows unusual features. 相似文献
65.
Valerio Bozza 《General Relativity and Gravitation》2010,42(9):2269-2300
We review the theoretical aspects of gravitational lensing by black holes, and discuss the perspectives for realistic observations.
We will first treat lensing by spherically symmetric black holes, in which the formation of infinite sequences of higher order
images emerges in the clearest way. We will then consider the effects of the spin of the black hole, with the formation of
giant higher order caustics and multiple images. Finally, we will consider the perspectives for observations of black hole
lensing, from the detection of secondary images of stellar sources and spots on the accretion disk to the interpretation of
iron K-lines and direct imaging of the shadow of the black hole. 相似文献
66.
Scavia G Agostinelli E Laureti S Varvaro G Paci B Generosi A Albertini VR Kaciulis S Mezzi A 《The journal of physical chemistry. B》2006,110(11):5529-5536
A combined ultrahigh vacuum scanning tunneling microscopy (STM-UHV) and energy dispersive X-ray diffractometry/reflectometry (EDXD/EDXR) study of the evolution of face-centered cubic (fcc) Pt layer growth on MgO(100) by pulsed laser deposition as a function of the process parameters such as deposition temperature and deposition duration has been carried out. The aim of this study is to define the best experimental conditions to obtain a controlled film deposition selective on the Pt growth direction (either [111] or [002]). The evolution of the Pt surface morphology as a function of the deposition temperature (T(dep)) from 300 to 700 degrees C has been studied with STM and ED techniques. Results show that the Pt surface, characterized at T(dep) = 300 degrees C by a 3D island morphology, evolves at higher temperatures to a morphology in which the original islands coexist with a distribution of orthogonal 2D stripes. The two features can be associated with the [111] and [002] Pt growth directions of the fcc phase, respectively. For T(dep) = 700 degrees C, the island morphology of the (111) face completely disappears, while the merging process of the (002) stripes reaches completion. The evolution of the morphology at T(dep) = 600 degrees C as a function of the deposition time and thickness has then been studied with STM-UHV, revealing an initial growth of mosaic-like 3D islands. These independent islands, already interconnected, expand along two orthogonal directions and, for longer deposition times, lead to the texture of orthogonal stripes. The EDXR characterization providing the morphological parameters of the films, i.e., thickness and roughness, confirms the above observation and quantifies the effect of such morphological changes on the surface roughness of the Pt film, an important parameter for applications of Pt films as underlayer in magnetic recording media. 相似文献
67.
Electrospray ionization mass spectrometry (ESI-MS) is being increasingly employed in the study of metal-ligand equilibria in aqueous solution. In the present work, the ESI-MS spectral changes due to different settings of the following instrumental parameters are analyzed: the solution flow rate (F(S)), the nebulizer gas flow rate (F(G)), the sprayer potential (E), and the temperature of the entrance capillary (T). Twenty-eight spectra were obtained for each of six samples containing aluminum(III) and 2,3-dihydroxypyridine at various pH, in the absence or in the presence of a buffer and of sodium ions. Among the considered instrumental parameters, T produced the largest effects on the ionic intensities. F(S) and F(G) affected the ESI-MS spectra to a lower extent than T. In the investigated conditions E had the weakest effects on the spectra.The correlations observed between the ionic intensities and these instrumental parameters were interpreted considering the presence of three kinds of perturbations occurring in the ESI-MS ion source: formation of some dimers in the droplets, different transfer efficiencies from the droplets to the gas phase for different complexes (according to their surface activity), and subsequent partial thermal decomposition of the dimers and of one of the monomeric complexes in the gas phase. Our results show that the evaluation of the effects produced in the ESI-MS spectra by a change of instrumental parameters can allow to identify the perturbations occurring when metal-ligand solutions are studied by ESI-MS. 相似文献
68.
Here we report a new peptide modified mesoporous silica nanocontainer (PMSN) as a novel controlled release system. The peptides are part of a stimuli responsive nanovalve and ensure an efficient cellular uptake. 相似文献
69.
70.
Within a large class of exact solutions of the Einstein equations describing a black hole embedded in a Friedmann universe it is shown that, under certain assumptions, only those with comoving Hawking–Hayward quasi-local mass are generic, in the sense that they are late-time attractors. 相似文献