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排序方式: 共有111条查询结果,搜索用时 15 毫秒
1.
There are consistently estimable parameters of interest whose semiparametric Fisher information vanishes at some points of the model in question. Here we investigate how bad this is for estimation. 相似文献
2.
We consider the point-line geometries that arise as a shadow space in a spherical building with a diagram of type An, Bn, Cn, Dn or En, and determine in which cases the geometry is spanned by the set of points on an apartment. It turns out that this happens precisely in the cases corresponding to a minimal weight. 相似文献
3.
Wuister SF de Mello Donegá C Meijerink A 《Journal of the American Chemical Society》2004,126(33):10397-10402
Luminescence temperature antiquenching (LTAQ) is observed for water-soluble CdTe quantum dots (QDs) capped with aminoethanethiol (AET). The efficient exciton emission (quantum efficiency of approximately 40% at 300 K) is quenched almost completely as the QD solutions are cooled to below 230 K and is fully recovered around 270 K upon warming up to room temperature (LTAQ). Temperature-dependent lifetime measurements show that the quenching rate is high, resulting in an on/off behavior. No LTAQ is observed for CdTe QDs capped with aminoundecanethiol (AUT). The LTAQ is explained by the influence of solvent freezing on the surface of the QD core. Freezing of the solvation water molecules surrounding the QD will induce strain in the capping shell, due to the interaction between water and the charged heads of the capping molecules. Short carbon chains (AET) will propagate the strain to the QD surface, creating surface quenching states, whereas long and flexible chains (AUT) will dissipate the strain, thus avoiding surface distortion. Freezing-point depression by the addition of methanol results in a lowering of the transition temperature. Additional support is provided by the size dependence of the LTAQ: smaller particles, with higher local ionic strength due to a higher density of charged NH(3)(+) surface groups, experience a lower transition temperature due to stronger local freezing-point depression. 相似文献
4.
M I Selala J J Janssens V Coucke S Andries P J Schepens 《Journal of chromatography. A》1989,489(1):51-56
During the past two decades, the use of retention times in gas chromatography has been augmented by mass spectrometric data. By providing both the retention indices and spectrometric data, this technique has greatly improved gas chromatographic identification analysis. However, although gas chromatography-mass spectrometry has become pre-eminent, several drawbacks still remain. The mass spectral library often gives erroneous identifications when concentrations near the detection limit are analysed, when gas chromatographically interfering substances are present, or when structural isomers or compounds exhibiting identical retention behaviour are analysed. Linked with gas chromatography-mass spectrometry, Fourier transform infrared spectroscopy can be a powerful complementary technique in peak identification analysis. Some spectral data to illustrate this point are presented. 相似文献
5.
Jurva U Wikström HV Bruins AP 《Rapid communications in mass spectrometry : RCM》2002,16(20):1934-1940
Oxygen radicals are generated in vivo by various processes, often as toxic intermediates in different metabolic transformations, and have been shown to play an important role for a large number of diseases. In this article we introduce an electrochemical flow-through system that allows generation of hydroxyl radicals for reaction with xenobiotics and subsequent detection of the oxidation products on-line with high-performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS). The system is based on the Fenton reaction and is predominantly aimed at the generation of hydroxyl radicals; however, by minor variations to the system, a broad range of other radicals can be produced. Optimization of the system was performed with the radical scavenger 5,5-dimethyl-1-pyrroline-N-oxide (DMPO). Under the same physical conditions, one injection through the electrochemical cell gave a higher yield of the oxidation product N-hydroxy-5,5-dimethylpyrrolidin-2-one than what was attained after 60 min with a chemical Fenton system catalyzed by ascorbic acid. Since the iron is added as Fe(3+), the initial mixture is 'inactive' until it reaches the electrochemical cell. This makes it very suitable for on-line analysis of the generated compounds, since the whole reaction mixture, including substrate, can be kept in a vial in an autosampler. The system described provides a useful tool for investigation of new radical scavengers and antioxidants. Since the hydroxyl radical adds readily to unsaturated pi-systems, the technique is also suitable for on-line generation and characterization of potential drug metabolites resulting from hydroxylation of double bonds and aromatic systems. 相似文献
6.
Asmin Andries Alan Feyaerts Djalila Mekahli Ann Van Schepdael 《Electrophoresis》2022,43(9-10):1010-1018
The development of a simple HILIC-LC-MS/MS method to quantify the plasma levels of allantoin, inosine, hypoxanthine, and adenosine, using stripped plasma for the bioanalytical method validation, was the purpose of this study. Chromatographic separation conducted using an XBridge BEH Amide column (2.1 × 150 mm, 3.5 μm) was achieved under gradient elution with two mobile phases: 0.1% formic acid–ACN (5:95) and 0.1% formic acid–ACN (50:50). Multiple reaction monitoring MS detection was performed using a triple quadrupole. The method validation experiments were performed according to the European Medicines Agency and the U.S. Food and Drug Administration guidelines. The lower LOQ was 50 nM, 5 nM, 20 nM, and 2 nM for allantoin, inosine, hypoxanthine, and adenosine, respectively. The recovery was repeatable and stable. The intraday precision ranged from 1.6% to 6.5%, while the interday precision ranged from 3.4% to 58.7%. Therefore, it is necessary to make a matrix-matched calibration curve each day to overcome this issue. Since the quality control samples’ stability did not always comply with the guidelines, the samples need to be analyzed soon after collection. 相似文献
7.
Orlinskii SB Schmidt J Baranov PG Hofmann DM de Mello Donegá C Meijerink A 《Physical review letters》2004,92(4):047603
Electron paramagnetic resonance and electron nuclear double resonance (ENDOR) experiments on ZnO nanoparticles reveal the presence of shallow donors related to interstitial Li and Na atoms. The shallow character of the wave function is evidenced by the multitude of 67Zn ENDOR lines and further by the hyperfine interactions with the 7Li and 23Na nuclei that are much smaller than for atomic lithium and sodium. In the case of the Li-doped nanoparticles, an increase of the hyperfine interaction with the 7Li nucleus and with the 1H nuclei in the Zn(OH)(2) capping layer is observed when reducing the size of the nanoparticles. This effect is caused by the confinement of the shallow-donor 1s-type wave function that has a Bohr radius of about 1.5 nm, i.e., comparable to the dimension of the nanoparticles. 相似文献
8.
Abstract: The synthesis of a fluorescent naphthalenic derivative, as a potential ligand of melatonin receptors is described through a multisteps procedure from 1-(2-acetylaminoethyl)-7-methoxynaphthalene. 相似文献
9.
Ayed Salman Andries P. Engelbrecht Mahamed G.H. Omran 《European Journal of Operational Research》2007
Differential evolution (DE) is generally considered as a reliable, accurate, robust and fast optimization technique. DE has been successfully applied to solve a wide range of numerical optimization problems. However, the user is required to set the values of the control parameters of DE for each problem. Such parameter tuning is a time consuming task. In this paper, a self-adaptive DE (SDE) algorithm which eliminates the need for manual tuning of control parameters is empirically analyzed. The performance of SDE is investigated and compared with other well-known approaches. The experiments conducted show that SDE generally outperform other DE algorithms in all the benchmark functions. Moreover, the performance of SDE using the ring neighborhood topology is investigated. 相似文献
10.
In this survey recent results about q-analogues of some classical theorems in extremal set theory are collected. They are related to determining the chromatic number of the q-analogues of Kneser graphs. For the proof one needs results on the number of 0-secant subspaces of point sets, so in the second part of the paper recent results on the structure of point sets having few 0-secant subspaces are discussed. Our attention is focussed on the planar case, where various stability results are given. 相似文献