全文获取类型
收费全文 | 327篇 |
免费 | 9篇 |
国内免费 | 3篇 |
专业分类
化学 | 265篇 |
数学 | 26篇 |
物理学 | 48篇 |
出版年
2023年 | 1篇 |
2022年 | 1篇 |
2021年 | 6篇 |
2020年 | 7篇 |
2019年 | 4篇 |
2018年 | 3篇 |
2017年 | 4篇 |
2016年 | 5篇 |
2015年 | 8篇 |
2014年 | 12篇 |
2013年 | 18篇 |
2012年 | 21篇 |
2011年 | 25篇 |
2010年 | 20篇 |
2009年 | 13篇 |
2008年 | 27篇 |
2007年 | 21篇 |
2006年 | 23篇 |
2005年 | 23篇 |
2004年 | 16篇 |
2003年 | 13篇 |
2002年 | 14篇 |
2001年 | 4篇 |
2000年 | 4篇 |
1999年 | 1篇 |
1998年 | 3篇 |
1997年 | 3篇 |
1996年 | 1篇 |
1995年 | 3篇 |
1994年 | 2篇 |
1993年 | 5篇 |
1992年 | 1篇 |
1991年 | 3篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1984年 | 3篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1977年 | 4篇 |
1975年 | 3篇 |
1965年 | 1篇 |
1954年 | 1篇 |
排序方式: 共有339条查询结果,搜索用时 328 毫秒
1.
2.
The self-organizing map (a neural network) was applied to the spectral pattern recognition of voice quality in 34 subjects: 15 patients operated on because of insufficient glottal closure and 19 subjects not treated for voice disorders. The voice samples, segments of sustained /a/, were perceptually rated by six experts. A self-organized acoustic feature map was first computed from tokens of /a/ and then used for the analysis of the samples. The locations of the samples on the map were determined and the distances from a normal reference were compared with the perceptual ratings. The map locations corresponded to the degree of audible disorder: the samples judged as normal were overlapping or close to the normal reference, whereas the samples judged as dysphonie were located further away from it. The comparison of pre- and postoperative samples of the patients showed that the perceived improvement of voice quality was also detected by the map. 相似文献
3.
The development of an amperometric biosensor for the determination of phenolic compounds is described, using quinoprotein glucose dehydrogenase. The enzyme is integrated into carbon paste and its ability to donate electrons to oxidized phenolic compounds during glucose oxidation is exploited. The sensor response is based on electrochemical oxidation of the phenolic compound followed by its enzymatic regeneration when the bulk solution contains glucose and the electrode is potentiostated at +500 mV (vs. Ag/AgCl/0.1 mol/L KCl). As the result of the catalytic analyte regeneration the electrodes offer very sensitive measurements of redox species like p-aminophenol and hydroquinone and catecholamines such as epinephrine, norepinephrine, and dopamine. The sensor performance is characterized for the different substrates. Highest sensitivity is achieved for p-aminophenol which could be determined at sub-nanomolar level. 相似文献
4.
Sandrine Bouquillon Ulla Létinois-Halbes Jacques Muzart 《Journal of organometallic chemistry》2003,687(2):377-383
The reaction between palladium acetate, (−)-ephedrine and potassium acetate led to bis-chelate complex Pd[OCH(Ph)NH(Me)]2 whose the trans-structure is obtained from calculations. The use of this complex to catalyze either the 1,4-hydrogenation of (E)-2-benzyliden-1-tetralone or Heck reaction of phenyl iodide with 3-methyl-3-buten-2-ol led to a low enantiomeric excess. 相似文献
5.
Sonesson AW Callisen TH Brismar H Elofsson UM 《Langmuir : the ACS journal of surfaces and colloids》2005,21(25):11949-11956
We have analyzed surface diffusion properties of a variant of Thermomyces lanuginosa lipase (TLL) on hydrophilic silica and silica methylated with dichlorodimethylsilane (DDS) or octadecyltrichlorosilane (OTS). For this study a novel method for analysis of diffusion on solid surfaces was developed. The method is based on fluorescence recovery after photobleaching using confocal microscopy. When a rectangular area of the sample was photobleached, fluorescence recovery could be analyzed as one-dimensional diffusion, resulting in simplified mathematical expressions for fitting the data. The method was initially tested by measuring bovine serum albumin diffusion on glass, which led to a diffusion coefficient in good correspondence to earlier reports. For the analysis of TLL diffusion, ellipsometry data of TLL adsorption were used to calibrate fluorescence intensity to surface density of lipase, enabling measurements of the diffusion coefficient at different surface densities. The average diffusion coefficient was calculated in two time intervals after adsorption. Mobile fraction and diffusion coefficient were lowest on the OTS surface, when extrapolated to infinite surface dilution. Moreover, the diffusion rate decreased with time on the hydrophobic surfaces. Our observations can be explained by the surface dependence on the distribution of orientations and conformations of adsorbed TLL, where the transition from the closed to the catalytically active open and more hydrophobic structure is important. 相似文献
6.
Nielsen UG Topsøe NY Brorson M Skibsted J Jakobsen HJ 《Journal of the American Chemical Society》2004,126(15):4926-4933
The first observations of the complete manifold of spinning sidebands (ssbs) including both the central and satellite transitions in (51)V MAS NMR spectra of surface vanadia nanoparticles on titania in DeNO(x) catalysts are presented. (51)V quadrupole coupling and chemical shift anisotropy parameters for the dominating vanadia structure are determined from (51)V MAS NMR spectra recorded at 9.4 and 14.1 T. Based on correlations previously established between (51)V NMR parameters and crystal structure data for inorganic vanadates, the NMR data are consistent with vanadium in a distorted octahedral oxygen coordination environment for the so-called strongly bonded vanadia species on the surface. The investigation includes two vanadia-titania model catalysts and six industrial-type DeNO(x) catalysts. 相似文献
7.
Chemical studies on antioxidant mechanisms and free radical scavenging properties of lignans 总被引:1,自引:0,他引:1
Eklund PC Långvik OK Wärnå JP Salmi TO Willför SM Sjöholm RE 《Organic & biomolecular chemistry》2005,3(18):3336-3347
The antioxidant activity, in terms of radical scavenging capacity, of altogether 15 different lignans was measured by monitoring the scavenging of the free radical 2,2-diphenyl-1-picrylhydrazyl (DPPH). The effect of differences in skeletal arrangement or the degree of oxidation of the lignans was investigated in a structure-activity relationship study. A large variety in the radical scavenging capacities of the different lignans was observed and related to some structural features. Lignans with catechol (3,4-dihydroxyphenyl) moieties exhibited the highest radical scavenging capacity, while the corresponding guaiacyl (3-methoxy-4-hydroxyphenyl) lignans showed a slightly weaker scavenging capacity. In addition, the butanediol structure was found to enhance the activity, whereas a higher degree of oxidation at the benzylic positions decreased the activity. Additionally, the readily available lignans (-)-secoisolariciresinol, a mixture of hydroxymatairesinol epimers and (-)-matairesinol were studied in more detail, including kinetic measurements and identification of oxidation products in the reactions with DPPH and ABAP (2,2-azobis(2-methylpropionamidine) dihydrochloride. The identification of reaction products, by GC-MS, HPLC-MS and NMR spectroscopy, showed that dimerisation of the two aromatic moieties was the major radical termination reaction. Also, the formation of adducts was a predominant reaction in the experiments with ABAP. The kinetic data obtained from the reactions between the lignans and DPPH indicated a complex reaction mechanism. 相似文献
8.
Antibacterial activity of methylated chitosan and chitooligomer derivatives: Synthesis and structure activity relationships 总被引:1,自引:0,他引:1
Ögmundur Vidar Rúnarsson Tapio Nevalainen Tomi Järvinen Jón M. Einarsson Margrét Valdimarsdóttir 《European Polymer Journal》2007,43(6):2660-2671
The purpose of this study was to synthesize series of methylated chitosaccharide derivatives, possessing various degree of methylation, and to determine their structure activity relationship (SAR) with regard to their antibacterial effect against Staphylococcus aureus. Chitosan polymer and chitooligomers were used as starting materials and were methylated by reaction with methyl iodide. Depending on the reaction conditions the degree of N-quaternization ranged from 0% to 74%, with varying degree of N,N-dimethylation, N-monomethylation and O-methylation. More selective N-quaternization could be obtained with protection group strategy. At pH 5.5 the chitosaccharide polymers and their methylated derivatives were active against S. aureus with minimal inhibitory concentration (MIC) ranging from 16 to 512 μg/mL. At pH 7.2 the non-quaternized derivatives were inactive but their highly N-quaternized derivatives showed MIC as low as 8 μg/mL. The chitooligomers, as well as their derivatives, were inactive at both pH’s. The SAR studies revealed that N-quaternization was mainly responsible for the antibacterial effects at pH 7.2, whereas it did not contribute to the antibacterial activity under acidic conditions. 相似文献
9.
Ulla Fiedler 《Analytica chimica acta》1977,89(1):101-109
A sodium ion-selective polymeric membrane electrode has been optimized, especially with reference to serum measurements. For a given combination of polymer and ligand, the choice of membrane solvent is critical. Potentiometric measurements and electrodialysis experiments have shown that the dielectric constant and solubility parameter of the solvent influence the electrode selectivities, stability, slope and limit of detection. For use in serum measurements, it is essential to use an appropriate analytical technique, such as Flow Injection Analysis, which permits exposures to serum for only short periods of time. 相似文献
10.
Kuuranne T Kotiaho T Pedersen-Bjergaard S Einar Rasmussen K Leinonen A Westwood S Kostiainen R 《Journal of mass spectrometry : JMS》2003,38(1):16-26
Anabolic androgenic steroids (AAS) are metabolized extensively in the human body, resulting mainly in the formation of glucuronide conjugates. Current detection methods for AAS are based on gas chromatographic/mass spectrometric (GC/MS) analysis of the hydrolyzed steroid aglycones. These analyses require laborious sample preparation steps and are therefore time consuming. Our interest was to develop a rapid and straightforward method for intact steroid glucuronides in biological samples, using liquid-phase microextraction (LPME) sample clean-up and concentration method combined with liquid chromatographic/tandem mass spectrometric (LC/MS/MS) analysis. The applicability of LPME was optimized for 13 steroid glucuronides, and compared with conventional liquid-liquid extraction (LLE) and solid-phase extraction (SPE) procedures. An LC/MS/MS method was developed for the quantitative detection of AAS glucuronides, using a deuterium-labeled steroid glucuronide as the internal standard. LPME, owing to its high specificity, was shown to be better suited than conventional LLE and SPE for the clean-up of urinary AAS glucuronides. The LPME/LC/MS/MS method was fast and reliable, offering acceptable reproducibility and linearity with detection limits in the range 2-20 ng ml(-1) for most of the selected AAS glucuronides. The method was successfully applied to in vitro metabolic studies, and also tested with an authentic forensic urine sample. For a urine matrix the method still has some unsolved problems with specificity, which should be overcome before the method can be reliably used for doping analysis, but still offering additional and complementary data for current GC/MS analyses. 相似文献