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101.
Eric Hughes Eric B. Brouwer Robin K. Harris 《Journal of magnetic resonance (San Diego, Calif. : 1997)》1999,138(2):256
For compounds giving “crowded” 1-dimensional magic-angle-spinning spectra, information about the local atomic environment in the form of the chemical shift anisotropy (CSA) is sacrificed for high resolution of the less informative isotropic chemical shift. Magic-angle-turning (MAT) NMR pulse sequences preserve the CSA information by correlating it to the isotropic chemical shift in a 2-dimensional experiment. For low natural abundance nuclei such as 13C and 15N and under 1H heteronuclear dipolar decoupling conditions, the dominant NMR interaction is the chemical shift. For abundant nuclei such as 1H, 19F, and 31P, the homonuclear dipolar interaction becomes a significant contribution to the observed linewidth in both F1 and F2 dimensions. We incorporate MREV8 homonuclear multiple-pulse decoupling sequences into the MAT experiment to give a multiple-pulse MAT (MP-MAT) experiment in which the homonuclear dipolar interaction is suppressed while maintaining the chemical shift information. Extensive use of computer simulation using GAMMA has guided the pulse sequence development. In particular, we show how the MREV8 pulses can be incorporated into a quadrature-detected sequence such as MAT. The MP-MAT technique is demonstrated for a model two-site system containing a mixture of silver trifluoroacetate and calcium difluoride. The resolution in the isotropic evolution dimension is improved by faster sample spinning, shorter MREV8 cycle times in the evolution dimension, and modifications of the MAT component of the pulse sequence. 相似文献
102.
Brouwer N Liu Q Harrington D Kohen J Vemulpad S Jamie J Randall M Randall D 《Molecules (Basel, Switzerland)》2005,10(10):1252-1262
The Australian Aboriginal people have used plants as medicine and food for thousands of years, however, this traditional knowledge is documented only to a limited extent, and is in danger of being lost. The Indigenous Bioresources Research Group (IBRG) aims to help Australian Aboriginal communities to preserve their customary medicinal knowledge, and to provide information that can be used for their cultural or educational purposes, as well as for scientific advancement. This work is undertaken in close collaboration with Australian Aboriginal communities in New South Wales. The project is multidisciplinary, combining an ethnobotanical and an ethnopharmacological approach, which includes biological and chemical investigations, as well as developing best practices for protecting traditional knowledge. This paper describes the general strategy of the project as well as methods used in the ethnopharmacological study. Ethnobotanical databases are set up for each participating community. Plant material is collected, extracted, and active compounds are isolated using a bioassay-guided fractionation approach. All extracts and compounds are tested for biological activity in antimicrobial assays (disc diffusion, resazurin, fluorescein diacetate), neurological assays or anti-inflammatory assays, depending on their traditional use. 相似文献
103.
We show for binary Armstrong codes Arm(2, k, n) that asymptotically n/k ≤ 1.224, while such a code is shown to exist whenever n/k ≤ 1.12. We also construct an Arm(2, n ? 2, n) and Arm(2, n ? 3, n) for all admissible n. 相似文献
104.
A. M. Brouwer R. D. Mout P. H. Maassen van den Brink H. J. van Ramesdonk J. W. Verhoeven
J. M. Warman
S. A. Jonker 《Chemical physics letters》1991,180(6):556-562Three bridged electron donor—acceptor systems are investigated containing a 4-cyano-1-ethenylnaphthalene electron-acceptor and piperidine (compound 1), phenylpiperazine (2) and 4-methoxyphenylpiperazine (3) electron-donating groups. In the intramolecular charge-transfer states of 1 and 2, the extent of charge separation is similar, but in compound 3 the positive charge is shifted towards the more powerful arylamine donor site, which results in a significantly greater dipole moment. Optical absorption spectra of model radical cations demonstrate that the predominant charge localization on the trialkyl nitrogen in 2 and on the aryl nitrogen in 3 are a consequence of the bistable nature of the piperazine donors. 相似文献
105.
An attempt was made to correlate retention behavior on a high-performance liquid chromatographic (HPLC) system employing an immobilized alpha 1-acid glycoprotein (AAG) column with AAG binding behavior for various compounds. Protein binding was assessed by propranolol displacement studies in an equilibrium dialysis system using isolated AAG. HPLC retention behavior poorly correlated with propranolol displacement from AAG. This system is not suitable for use as a screening tool for AAG affinity. 相似文献
106.
E. R. Brouwer E. A. Struys J. J. Vreuls U. A. T. Brinkman 《Fresenius' Journal of Analytical Chemistry》1994,350(7-9):487-495
A liquid chromatographic method using gradient elution and diode array UV detection for the trace level determination of seven synthetic pyrethroids is described. The procedure involves automated on-line preconcentration on precolumns containing octadecylbonded silica using a Prospekt. Although the analytes display a mixed hydrophobic/hydrophilic behaviour, both breakthrough on the precolumn and adsorption to inner walls and surfaces can be prevented by adding Brij-35, a neutral surfactant, to the aqueous sample. The procedure has been tested for the analysis of surface water; detection limits typically are at the sub-g/l level and repeatability is excellent. The automated system is robust and there are no maintenance problems.Dedicated to Professor Dr. Dieter Klockow on the occasion of his 60th birthday 相似文献
107.
In N-(2,5-di-tert-butylphenyl)-9-pyrrolidinoperylene-3,4-dicarboximide (5PI) the absorption and emission spectra display large solvatochromic shifts, but, remarkably, the Stokes shift is practically independent of solvent polarity. This unique behavior is caused by the extraordinarily large ground-state dipole moment of 5PI, which further increases upon increasing the solvent polarity, whereas the excited-state dipole moment is less solvent dependent. In the corresponding piperidine compound, 6PI, this effect is much less important owing to the weaker coupling between the amino group and the aromatic imide moiety, and in the corresponding naphthalimide, 5NI, it is absent. The latter shows the conventional solvatochromic behavior of a push-pull substituted conjugated system, that is, minor shifts in absorption and a larger change in the emission energy with solvent polarity. 相似文献
108.
Fyfe CA Brouwer DH Lewis AR Villaescusa LA Morris RE 《Journal of the American Chemical Society》2002,124(26):7770-7778
The local structure of the [SiO(4/2)F]- unit in fluoride-containing as-synthesized STF zeolite has been experimentally determined by a combination of solid-state NMR and microcrystal X-ray diffraction to be very close to trigonal bipyramidal. Because the fluoride ions are disordered over two sites, the resulting local structure of the [SiO(4/2)F]- unit from a conventional XRD refinement is an average between tetrahedral SiO(4/2) and five-coordinate [[SiO(4/2)F]-, giving an apparent F-Si distance longer than expected. The correct F-Si distance was determined by slow spinning MAS and fast spinning (19)F/(29)Si CP and REDOR solid-state NMR experiments and found to be between 1.72 and 1.79 A. In light of this, the X-ray structure was re-refined, including the disorder at Si3. The resulting local structure of the [SiO(4/2)F]- unit was very close to trigonal bipyramidal with a F-Si distance of 1.744 (6) A, in agreement with the NMR results and the prediction of Density Functional Theory calculations. In addition, further evidence for the existence of a covalent F-Si bond is provided by a (19)F-->(29)Si refocused INEPT experiment. The resonance for the five-coordinate species at -147.5 ppm in the (29)Si spectrum is a doublet due to the (19)F/(29)Si J-coupling of 165 Hz. The peaks in this doublet have remarkably different effective chemical shift anisotropies due to the interplay of the CSA, dipolar coupling, and J-coupling tensors. The distortions from tetrahedral geometry of the neighboring silicon atoms to the five-coordinate Si3 atom are manifested in increased delta(aniso) values. This information, along with F-Si distances measured by (19)F-->(29)Si CP experiments, makes it possible to assign half of the (29)Si resonances to unique tetrahedral sites. As well as determining the local geometry of the [SiO(4/2)F]- unit, the work presented here demonstrates the complementarity of the solid-state NMR and X-ray diffraction techniques and the advantages of using them together. 相似文献
109.
Brouwer DH Darton RJ Morris RE Levitt MH 《Journal of the American Chemical Society》2005,127(29):10365-10370
Since zeolites are notoriously difficult to prepare as large single crystals, structure determination usually relies on powder X-ray diffraction (XRD). However, structure solution (i.e., deriving an initial structural model) directly from powder XRD data is often very difficult due to the diffraction phase problem and the high degree of overlap between the individual reflections, particularly for materials with the structural complexity of most zeolites. Here, we report a method for structure determination of zeolite crystal structures that combines powder XRD and nuclear magnetic resonance (NMR) spectroscopy in which the crucial step of structure solution is achieved using solid-state (29)Si double-quantum dipolar recoupling NMR, which probes the distance-dependent dipolar interactions between naturally abundant (29)Si nuclei in the zeolite framework. For two purely siliceous zeolite blind test samples, we demonstrate that the NMR data can be combined with the unit cell parameters and space group to solve structural models that refine successfully against the powder XRD data. 相似文献
110.