全文获取类型
收费全文 | 519篇 |
免费 | 23篇 |
国内免费 | 2篇 |
专业分类
化学 | 318篇 |
晶体学 | 4篇 |
力学 | 48篇 |
数学 | 110篇 |
物理学 | 64篇 |
出版年
2023年 | 5篇 |
2022年 | 10篇 |
2021年 | 21篇 |
2020年 | 3篇 |
2019年 | 8篇 |
2018年 | 12篇 |
2017年 | 9篇 |
2016年 | 29篇 |
2015年 | 25篇 |
2014年 | 19篇 |
2013年 | 31篇 |
2012年 | 26篇 |
2011年 | 40篇 |
2010年 | 29篇 |
2009年 | 30篇 |
2008年 | 26篇 |
2007年 | 41篇 |
2006年 | 29篇 |
2005年 | 31篇 |
2004年 | 21篇 |
2003年 | 15篇 |
2002年 | 18篇 |
2001年 | 4篇 |
1999年 | 6篇 |
1998年 | 2篇 |
1996年 | 6篇 |
1995年 | 2篇 |
1994年 | 2篇 |
1992年 | 4篇 |
1990年 | 2篇 |
1988年 | 2篇 |
1985年 | 2篇 |
1984年 | 4篇 |
1983年 | 4篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1978年 | 1篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1974年 | 1篇 |
1971年 | 1篇 |
1966年 | 1篇 |
1965年 | 1篇 |
1941年 | 1篇 |
1937年 | 1篇 |
1926年 | 1篇 |
1913年 | 1篇 |
1907年 | 1篇 |
1869年 | 1篇 |
排序方式: 共有544条查询结果,搜索用时 78 毫秒
51.
Gallo FR Multari G Federici E Palazzino G Giambenedetti M Petitto V Poli F Nicoletti M 《Natural product research》2011,25(13):1261-1270
Equisetum arvense L. is a herbaceous medicinal plant, commonly known as horsetail, whose extracts have been reported to possess diuretic and haemostatic properties. The aim of this study was to evaluate the use of fingerprint chromatographic methods on commercially available raw materials or preparations of E. arvense L. in order to ascertain their quality and identify possible adulterants using HPLC and HPTLC densitometry. Two chromatographic methods were used to determine the chemical fingerprints of E. arvense and other allied species. The first was based on HPTLC identification followed by densitometric measurement at 350?nm. The second was based on HPLC separation. The ease of sample preparation and the possibility of simultaneous analysis of several samples in a short time make HPTLC a method of choice for the comprehensive quality evaluation of herbal products. 相似文献
52.
53.
Gennari M Orio M Pécaut J Bothe E Neese F Collomb MN Duboc C 《Inorganic chemistry》2011,50(8):3707-3716
Sulfur-rich nickel metalloenzymes are capable of stabilizing Ni(I) and Ni(III) oxidation states in catalytically relevant species. In an effort to better understand the structural and electronic features that allow the stabilization of such species, we have investigated the electrochemical properties of two mononuclear N(2)S(2) Ni(II) complexes that differ in their sulfur environment. Complex 1 features aliphatic dithiolate coordination ([NiL], 1), and complex 2I is characterized by mixed thiolate/thioether coordination ([NiL(Me)]I, 2I). The latter results from the methylation of a single sulfur of 1. The X-ray structure of 2I reveals a distorted square planar geometry around the Ni(II) ion, similar to what was previously reported by us for 1. The electrochemical investigation of 1 and 2(+) shows that the addition of a methyl group shifts the potentials of both redox Ni(II)/Ni(I) and Ni(III)/Ni(II) redox couples by about 0.7 and 0.6 V to more positive values. Through bulk electrolyses, only the mononuclear dithiolate [Ni(I)L](-) (1(-)) and the mixed thiolate/thioether [Ni(III)L(Me)](2+) (2(2+)) complexes were generated, and their electronic properties were investigated by UV-vis and EPR spectroscopy. For 1(-) (Ni(I), d(9) configuration) the EPR data are consistent with a d(x(2))(-)(y(2)) based singly occupied molecular orbitals (SOMOs). However, DFT calculations suggest that there is also pronounced radical character. This is consistent with the small g-anisotropy observed in the EPR experiments. The spin population (Mulliken analysis) analysis of 1(-) reveals that the main contribution to the SOMO (64%) is due to the bipyridine unit. Time dependent density functional theory (TD-DFT) calculations attribute the most prominent features observed in the electronic absorption spectrum of 1(-) to metal to ligand charge transfer (MLCT) transitions. Concerning 2(2+), the EPR spectrum displays a rhombic signal with g(x) = 2.236, g(y) = 2.180, and g(z) = 2.039 in CH(3)CN. The g(iso) value is larger than 2.0, which is consistent with metal based oxidation. The unpaired electron (Ni(III), d(7) configuration) occupies a Ni-d(z(2)) based molecular orbital, consistent with DFT calculations. Nitrogen hyperfine structure is observed as a triplet in the g(z) component of the EPR spectrum with A(N) = 51 MHz. This result indicates the coordination of a CH(3)CN molecule in the axial position. DFT calculations confirm that the presence of a fifth ligand in the coordination sphere of the Ni ion is required for the metal-based oxidation process. Finally, we have shown that 1 exhibits catalytic reductive dehalogenation activity below potentials of -2.00 V versus Fc/Fc(+) in CH(2)Cl(2). 相似文献
54.
Locatelli M Epifano F Genovese S Carlucci G Koncić MZ Kosalec I Kremer D 《Natural product communications》2011,6(9):1275-1280
The anthraquinone profile, antioxidant and antimicrobial activities as well as the total phenol and total flavonoid contents were determined in methanol extracts of the barks of Rhamnus catharticus L. and R. orbiculatus Bornm. The most abundant anthraquinone derivatives in R. catharticus were physcion (67.8%) and emodin (26.2%), while R. orbiculatus contained mostly physcion (81.3%) and chrysophanol (14.6%). R. catharticus displayed better activity in the beta-carotene-linoleic acid assay, as well as chelating activity, whereas its activity in the reducing power assay was significantly lower than that of R. orbiculatus. Both methanol extracts showed antimicrobial activity against all microbial species tested (Staphylococcus aureus, Pseudomonas aeruginosa, Escherichia coli, Candida albicans, Aspergillus niger, Microsporum gypseum) with MIC values either equal to or lower than 2.50 mg/mL. R. catharticus and R. orbiculatus contained several anthranoid aglycones and their bark extracts demonstrated notable antioxidant and antimicrobial properties. The results obtained indicate the medicinal potential of these two species. 相似文献
55.
The U(1) gauge structure of torsion and dislocation in three dimensional Riemann-Cartan manifold have been studied. The local topological structure of dislocation have been presented by so-called topological method in which the quantum number is by Hopf indices and Brouwer degree. Furthermore, the relationship between the dislocation lines and Wilson lines of the U(1) gauge theory is discussed by using the Chern-Simons theory. 相似文献
56.
An innovative intense neutron generator of 14 MeV neutrons for the irradiation of future reactor materials is presented. Negative pions are produced inside a 5–10 T magnetic field by an intense deuteron beam interacting with a carbon target. The pions and the muons from pion decay in flight are collected in the backward direction and stopped in a deuterium-tritium-hydrogen target of high density. Using an 18 MW deuteron beam at 1.5 GeV (12 mA=7.5 × 1016d/s), circa 1016gt– /s can be generated, decaying to muons of which up to 1015 µ–/s stop in the D/T/H mixture. Assuming Xc=100 fusions per muon, the µCF source produces 14 MeV neutrons with a source strength of up to 1017 n/s, i.e. a neutron power of 200 kW. The environment of the second target, the neutron source itself, can be made to resemble part of the Tokamak ring to be simulated for irradiation test samples. 相似文献
57.
Marcello Mascini George G. Guilbault Ian R. Monk Colin Hill Michele Del Carlo Dario Compagnone 《Mikrochimica acta》2008,163(3-4):227-235
The aim of this work was to optimize, by means of molecular modeling software, biomimetic-based traps for pathogen detection suitable for analytical applications like screening or pre-analytical methods. The pathogen prototype system chosen was Listeria monocytogenes because of the large number of X ray and NMR structures available. 298 oligopeptides were computationally designed mimicking the binding pocket of the mammalian protein E-cadherin, the target of Listeria monocytogenes adhesion, internalin A. The contribution of individual peptides to bind was investigated using FRED, a protein-ligand docking program. Ten peptides were selected for experimental analysis taking as selection parameters the length, the position in the docking pocket and the score of simulated binding energy. A series of competition assays were carried out using high density colorimetric microarray using various bacteria species (Listeria monocytogenes, Listeria monocytogenes genetically modified without internalin A, Listeria innocua and Lactococcus lactis) in solution with computationally selected peptides. The data demonstrated that peptides could be able to distinguish Listeria monocytogenes with an EC50 up to 107cfu × mL?1. In particular the peptide with the best calculated binding score gave the highest statistically unambiguous response toward Listeria monocytogenes compared to other bacteria, demonstrating that rationally simulated approach can be useful as preliminary screening in the choice of biomimetic ligands. 相似文献
58.
Summary Some correlations are presented of experimental data, which mainly concern the transition from normal to anomalous flow at the inlet of Pitot tubes in dilute polymer solutions.Such transition is associated with the onset of pressure defect, and reveals some aspects of statistical regularity; when the polymer solution is fresh, it happens at a given value of the ratio of flow velocity to Pitot tube diameter v/d, and it seems not dependent or only slightly dependent on the diameter value alone. But the aging of the solution enhances the importance of the diameter value, and the transition value of v/d increases in a different way for different diameters, more quickly in the case of the bigger ones.This behaviour together with the observation that the viscosity does not affect significantly the phenomenon, brings the authors to confirm that such solutions cannot be considered as a viscoelastic continuum, but as a fluid with a structure due to large associations of water molecules and macromolecules, whose linear dimension is significant with respect to the probe diameter.
Sommario Vengono presentate alcune correlazioni fra i dati sperimentali che riguardano essenzialmente la transizione da flusso normale a flusso anomalo in prossimità ed all'interno della bocca dei tubi di Pitot immersi in soluzioni diluite di polimeri.La transizione è associata alla genesi del recupero incompleto di pressione e presenta caratteri di regolarità in senso statistico; con soluzioni fresche si ha transizione mediamente attorno ad un dato valore del rapporto v/d tra la velocità del flusso ed il diametro del Pitot, in modo indipendente o scarsamente dipendente dal valore del solo diametro.Ma, invecchiando la soluzione, anche il valore del diametro in sè rivela influenza, poiché il valore relativo alla transizione del rapporto v/d cresce più rapidamente per i diametri più grandi. Questo comportamento, assieme alla constatazione che la viscosità non ha influenza rilevante sul fenomeno, conduce a confermare che queste soluzioni non possono essere ritenute un continuo visco-elastico, ma piuttosto un fluido strutturato da larghe associazioni di molecole di acqua e macromolecole, con una dimensione lineare non insignificante in confronto al diametro del Pitot.相似文献
59.
Mono and disubstituted acetylenes react with aryl iodides containing a variety of functional groups in the presence of palladium catalyst, formic acid and a tertiary amine to give trisubstituted alkenes. 相似文献
60.