全文获取类型
收费全文 | 341篇 |
免费 | 30篇 |
专业分类
化学 | 306篇 |
晶体学 | 3篇 |
力学 | 5篇 |
数学 | 7篇 |
物理学 | 50篇 |
出版年
2023年 | 3篇 |
2022年 | 5篇 |
2021年 | 6篇 |
2020年 | 6篇 |
2019年 | 8篇 |
2018年 | 9篇 |
2017年 | 4篇 |
2016年 | 10篇 |
2015年 | 14篇 |
2014年 | 15篇 |
2013年 | 16篇 |
2012年 | 31篇 |
2011年 | 33篇 |
2010年 | 23篇 |
2009年 | 17篇 |
2008年 | 27篇 |
2007年 | 20篇 |
2006年 | 24篇 |
2005年 | 21篇 |
2004年 | 18篇 |
2003年 | 17篇 |
2002年 | 12篇 |
2001年 | 1篇 |
2000年 | 2篇 |
1999年 | 2篇 |
1998年 | 1篇 |
1997年 | 4篇 |
1996年 | 4篇 |
1995年 | 1篇 |
1994年 | 2篇 |
1992年 | 1篇 |
1986年 | 4篇 |
1985年 | 2篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有371条查询结果,搜索用时 265 毫秒
61.
A simple and rapid detection method of oligosaccharides using high-performance liquid chromatography with a charged aerosol detection (HPLC-CAD) was studied. The direct detection of a sialylglycopeptide (SGP) derived from egg yolk was accomplished by HPLC-CAD using an amido-silica column, and its limit of detection was 0.40 pmol [signal-to-noise ratio (S/N) = 3]. The sensitivity of this method was lower than that of the fluorescence detection; however, the method showed approximately 5 times higher sensitivity than that using the conventional UV absorbance detection. Furthermore, this method was used for the analysis of the acid hydrolysis products of SGP. Monosialo- and asialo-oligosaccharides as well as free sialic acid were detected without using fluorescent derivatization. These results indicate that the present method is a new tool for the analysis of oligosaccharides. 相似文献
62.
Sando S Abe K Sato N Shibata T Mizusawa K Aoyama Y 《Journal of the American Chemical Society》2007,129(19):6180-6186
There have been recent advances in the ribosomal synthesis of various molecules composed of nonnatural ribosomal substrates. However, the ribosome has strict limitations on substrates with elongated backbones. Here, we show an unexpected loophole in the E. coli translation system, based on a remarkable disparity in its selectivity for beta-amino/hydroxy acids. We challenged beta-hydroxypropionic acid (beta-HPA), which is less nucleophilic than beta-amino acids but free from protonation, to produce a new repertoire of ribosome-compatible but main-chain-elongated substrates. PAGE analysis and mass-coupled S-tag assays of amber suppression experiments using yeast suppressor tRNAPheCUA confirmed the actual incorporation of beta-HPA into proteins/oligopeptides. We investigated the side-chain effects of beta-HPA and found that the side chain at position alpha and R stereochemistry of the beta-substrate is preferred and even notably enhances the efficiency of incorporation as compared to the parent substrate. These results indicate that the E. coli translation machinery can utilize main-chain-elongated substrates if the pKa of the substrate is appropriately chosen. 相似文献
63.
The dynamic characteristics of a semiconductor laser with optical feedback are strongly dependent on the injection current and the reflectivity and position of the external feedback reflector. We investigated the relaxation oscillation enhancement and coherence collapse state of the laser oscillation based on the laser rate equations. It is well known that laser output power jumps with increase of the injection current due to external mode transition. But here for the first we time demonstrate the existence of a chaotic scenario within successive laser power jumps. The results calculated by numerical simulations based on the rate equations are compared with those of the experiments and good coincidence between them is found. 相似文献
64.
Katsuhiro Munakata Kenji Harada Nobukazu Yoshikawa Masahide Itoh Shinsuke Umegaki Toyohiko Yatagai 《Optical Review》1999,6(6):518-521
Two fabrication methods of surface relief electro-optic (EO) gratings in azo-polymer films are described: surface deformation by a continuous wave laser and laser ablation by a pulse laser. In the fabrication process, the periodic intensity modulation of laser beams is formed by an interference fringe or a phase mask. The surface relief EO grating is fabricated by poling the surface relief grating (SRG) after the SRG fabrication process. The linear dependence of an applied voltage in the modulation efficiency of the first-order diffraction beam is observed. The proposed methods are effective for highly-efficient surface relief EO grating fabrication. 相似文献
65.
Munehisa Yasuniwa Shinsuke Tsubakihara Masashi Yamaguchi 《Journal of Polymer Science.Polymer Physics》1997,35(4):535-543
Single crystal mat (SCM) samples of polyethylene (PE) were prepared from dilute solution of p-xylen, then they were annealed at pressures of 200 and 500 MPa. Lamellar thickness of the original and annealed SCM samples was measured by small-angle X-ray scattering method. Orientation of the molecular chain in those SCM samples was investigated by wide-angle X-ray diffraction pattern. From these X-ray measurements, annealing temperature dependence of the lamellar thickness, i.e., lamellar thickening, under high pressure was obtained. Melting process of the SCM samples was also investigated at 200 and 500 MPa by high pressure differential thermal analysis. Then correspondence between the lamellar thickening and the melting process was studied. The lamellar thickness increases markedly with approaching to the melting temperature of the orthorhombic crystal even in the high pressure region where the high pressure phase (hexagonal phase) appears. The annealing temperature dependence curve of the lamellar thickness at 200 MPa can be superimposed on the curve at 500 MPa by shifting the curve along the temperature scale by 47 K. Large scale lamellar thickening occurs in the orthorhombic crystal phase in the high pressure region. The formation process of extended-chain crystal is discussed. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 535–543, 1997 相似文献
66.
67.
Takagi S Eguchi M Tryk DA Inoue H 《Langmuir : the ACS journal of surfaces and colloids》2006,22(4):1406-1408
A novel energy-transfer system involving nonaggregated cationic porphyrins adsorbed on an anionic-type clay surface and the electron-transfer reaction that occurs after light harvesting are described. In the clay-porphyrin complexes, photochemical energy transfer from excited singlet zinc porphyrins to free-base porphyrins proceeds. The photochemical electron-transfer reaction from an electron donor in solution (hydroquinone) to the adsorbed porphyrin in the excited singlet state was also examined. Because the electron-transfer rate from the hydroquinone to the excited singlet free-base porphyrin is larger than that to the excited singlet zinc porphyrin, we conclude that the energy transfer accelerates the overall electron-transfer reaction. 相似文献
68.
Tamura R Mizuta M Yabunaka S Fujimoto D Ariga T Okuhara S Ikuma N Takahashi H Tsue H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(13):3515-3527
Both induction and inhibition of "preferential enrichment", an unusual symmetry-breaking enantiomeric-resolution phenomenon observed upon simple recrystallization of a certain kind of racemic crystals from organic solvents, have been successfully achieved by controlling the mode of the polymorphic transition during crystallization with appropriate seed crystals. Such control of the polymorphic transition can be interpreted in terms of a novel phenomenon consisting of 1) the adsorption of prenucleation aggregates, 2) the heterogeneous nucleation and crystal growth of a metastable crystalline form, and 3) the subsequent polymorphic transition into the more stable form; these three processes occur on the same surface of a seed crystal. We refer to this phenomenon as an "epitaxial transition", which has been confirmed by means of in situ attenuated total reflection (ATR) FTIR spectroscopy in solution and the solid state, differential scanning calorimetry (DSC) measurements of the deposited crystals, and X-ray crystallographic analysis of the single crystals or the direct-space approach employing the Monte Carlo method with the Rietveld refinement for the structure solution from the powder X-ray diffraction data. 相似文献
69.
Harada T Narazaki R Nagira S Ohwaki T Aoki S Iwamoto K 《Chemical & pharmaceutical bulletin》2006,54(8):1072-1075
The purpose of this study was to demonstrate the usefulness and broad-applicability of a simple disintegration test method for orally disintegrating tablets (ODT). Eight types of commercial famotidine 20 mg orally disintegrating tablets with different physical properties (formulation, manufacturing method, tablet weight, shape, diameter, thickness, etc.), were used. Disintegration times of these tablets were evaluated employing human sensory test, conventional disintegration test, and the new proposed disintegration test. The human sensory test was performed in 5 healthy volunteers. In the conventional disintegration test, the disintegration apparatus described in the Japanese Pharmacopeia (JP 1(st)) was used. Our proposed new test which is characterized by a rotating shaft with a low weight (10, 15 g) and rotation speed (10, 25, 50 rpm) was evaluated using tablets with and without storage under severe conditions (60 degrees C/75%RH for 1 week). The disintegration times of famotidine 20 mg orally disintegrating tablets in human sensory test varied from 9 to 32 s. In contrast, disintegration times in the conventional test were prolonged to over 300 s. Disintegration times in the new proposed test were close to those in human sensory test. Especially, when the new test was conducted with 15 or 10 g weight and 25 rpm, the slope (human sensory test vs. new proposed test) was almost 1. We were able to demonstrate that the new proposed test was useful to estimate the actual human disintegration time. 相似文献
70.
Yuki Kobayashi Shinsuke Matsuda Kentaro Imamura Hikaru Kobayashi 《Journal of nanoparticle research》2017,19(5):176
Si and its oxide are nonpoisonous materials, and thus, it can be taken for medical effects. We have developed a method of generation of hydrogen by use of reactions of Si nanopowder with water in the neutral pH region. Si nanopowder is fabricated by the simple bead milling method. Si nanopowder reacts with water to generate hydrogen even in cases where pH is set at the neutral region between 7.0 and 8.6. The hydrogen generation rate strongly depends on pH and in the case of pH 8.0, ~55 ml/g hydrogen which corresponds to that contained in approximately 3 L saturated hydrogen-rich water is generated in 1 h. The reaction rate for hydrogen generation greatly increases with pH, indicating that the reacting species is hydroxide ions. The change of pH after the hydrogen generation reaction is negligibly low compared with that estimated assuming that hydroxide ions are consumed by the reaction. From these results, we conclude the following reaction mechanism: Si nanopowder reacts with hydroxide ions in the rate-determining reaction to form hydrogen molecules, SiO2, and electrons in the conduction band. Then, generated electrons are accepted by water molecules, resulting in production of hydrogen molecules and hydroxide ions. The hydrogen generation rate strongly depends on the crystallite size of Si nanopowder, but not on the size of aggregates of Si nanopowder. The present study shows a possibility to use Si nanopowder for hydrogen generation in the body in order to eliminate hydroxyl radicals which cause various diseases. 相似文献