首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   1985篇
  免费   277篇
  国内免费   194篇
化学   876篇
晶体学   23篇
力学   322篇
综合类   24篇
数学   69篇
物理学   1142篇
  2024年   4篇
  2023年   14篇
  2022年   55篇
  2021年   76篇
  2020年   71篇
  2019年   70篇
  2018年   51篇
  2017年   80篇
  2016年   107篇
  2015年   77篇
  2014年   131篇
  2013年   160篇
  2012年   145篇
  2011年   138篇
  2010年   105篇
  2009年   114篇
  2008年   130篇
  2007年   125篇
  2006年   108篇
  2005年   94篇
  2004年   66篇
  2003年   82篇
  2002年   73篇
  2001年   39篇
  2000年   49篇
  1999年   40篇
  1998年   54篇
  1997年   32篇
  1996年   25篇
  1995年   23篇
  1994年   28篇
  1993年   13篇
  1992年   14篇
  1991年   10篇
  1990年   17篇
  1989年   6篇
  1988年   8篇
  1987年   7篇
  1985年   2篇
  1984年   2篇
  1983年   1篇
  1982年   6篇
  1979年   1篇
  1977年   3篇
排序方式: 共有2456条查询结果,搜索用时 31 毫秒
31.
A new salicylic-based open-chain crown ether ligand, 1,10-bis(2′-carboxylphenyl)-1,4,7,10-tetraoxadecane (BCPTD) was synthesized. Solutions of its complex with Tb3+ can emit the intrinsic fluorescence of Tb3+. The fluorescence intensity of the complex in KCl solution was enhanced by the addition of silver(I), leading to a new fluorescence enhancement phenomenon. The spectrofluorimetric determination of traces of silver(I) based on the above phenomenon was carried out. The excitation and emission wavelengths are 298 and 545 nm, respectively. Under optimal conditions, the differential value of fluorescence intensity in the absence and presence of Ag+ was proportional to the concentration of silver(I) in the range 0.5-20 μg ml−1. The method was applied to the determination of silver(I) in a standard ore sample. The analytical performance is investigated in detail by using common aromatic carboxylic acids or synthetic analogues of BCPTD as ligands to replace BCPTD. It was found that Tb-aromatic acid complexes did not result in fluorescence enhancement of Tb3+ in AgCl collosol. The phenomenon was only observed in Tb(III) with BCPTD or its open-chain crown ether analogues solutions.In addition, the enhancement of the fluorescence intensity of terbium(III) in these complexes depends on the extent of formation of the AgCl collosol.  相似文献   
32.
Summary The solubility enhancement of triflumizole, a systemic fungicide, by -cyclodextrin inclusion complexation was investigated by electron absorption spectroscopy. The respective association constant determined by different methods was estimated to 470±20M –1 in aqueous solution. A model for the host-guest complexation was deduced by molecular calculations.
Löslichkeitsverbesserung von Triflumizole durchHost-Guest-Complexierung mit -Cyclodextrin
Zusammenfassung Die Löslichkeitsverbesserung des systemischen Fungizids Triflumizole durch Komplexierung mit -Cyclodextrin wurde mittels Elektronenabsorptionsspektroskopie untersucht. Die entsprechende Stabilitätskonstante wurde durch verschiedene Methoden erfaßt und betrug im wäßrigen Medium 470±20M –1. Ein Model für denHost-Guest-Complex wurde durch Molekülrechnungen erstellt.
  相似文献   
33.
Sample/spectrum relationships are investigated using both a low resolution rapid-scanning NIR monochromator and a Fourier transform instrument capable of high resolution and are evaluated in terms of whether or not the resolution of the instrument is sufficient for measuring the natural bandwidths corresponding to the sample. Based on the sample/spectrum relationship a criterion is developed which must be followed in order to apply either derivative spectroscopy or deconvolution to enhance the resolution of overlapped bands without generating spectral artifacts.  相似文献   
34.
The filtration performance of yeast cell harvesting was greatly improved by using an oscillatory flow mixing technique in both tubular and flat sheet membrane systems; flux increases of several fold were achieved. The effects of various operating parameters such as frequency, amplitude and ratio of net forward flow rate to oscillatory flow rate were investigated. A simple alternative to the dual head pump, which involved the use of solenoid valves for producing flow reversal, was developed. The flux was significantly increased using this new operating mode. As the only increase of power consumption was from inertia loss due to change of flow direction the additional power consumption is minimal.  相似文献   
35.
酞菁氧钛/卟啉氧钒复合体系光导性能的协同增强效应   总被引:9,自引:0,他引:9  
在酞菁氧钛(TiOPc)/卟啉氧钒(VOTPP)复合光生材料中发现了光敏性的非线性增强现象,对复合体系的电子跃迁光谱和X射线衍射图的研究结果表明,在基态下两种材料之间没有明显相互作用,光致放电研究说明,该现象来自光激发状态下复合体系中的隙间态跃迁对光导的贡献,XPS测试结果表明酞菁氧钛与卟啉氧钒分子之间存在着定向的部分电荷转移,光致激发状态下的电荷转移是协同增强效应的起因,这种协同增强效应为利用弱的电子给体与弱的受体复合体系设计新型光导材料与器件提供了新方法。  相似文献   
36.
Complexation of AlIIIby 8-hydroxyquinoline and fluorescence behavior of the quinolinate(s) were studied in reverse micellar systems at low water content, and compared to aqueous media. Two surfactants were used: one was cationic (CTAC: cetyltrimethylammonium chloride) and the other was anionic (AOT: sodium bis(2-ethylhexyl)sulfosuccinate). The results obtained in the CTAC/dichloromethane system (W= [H2O]/[surfactant] = 0.9) showed that complexation occurred very likely in the oil phase and no micellar effect was observed. On the contrary, in the presence of AOT, specific micellar effects were observed due to the presence of the anionic polar heads: stabilization of the positively charged 1:1 and 1:2 chelates, at the expense of the neutral water-insoluble 1:3 chelate which is formed in aqueous solutions under similar conditions;drastic fluorescence enhancement factorsof 120 and 100 in AOT/heptane (W= 1.5) and AOT/dichloromethane (W= 1.6), respectively. Such factors have never been reported so far in either hydroorganic or direct micellar systems. In return, the length of time for the production of the complex(es) is increased because of the microheterogeneity of the medium and the small sizes of the water pools.  相似文献   
37.
The digital filter described provides optimal enhancement of the signal-to-noise ratio by using prior information about peak shape and type of noise. The filter, based onthe matched-filter principle, is applied to chromatographic data, but is also suitable for optimal processing of similar noisy signals. The current implementation of the filter permits the specific reduction of different types of noise. Several theoretical aspects concerning the interpretation and use of this advanced filter are discussed. Some calculations on peaks with Gaussian and Gamma distribution shape are given.  相似文献   
38.
In the present study, we demonstrate the benefits of a shear-driven rotating microchamber system for the enhancement of microarray hybridizations, by comparing the system with two commonly used hybridization techniques: purely diffusion-driven hybridization under coverslip and hybridization using a fully automated hybridization station, in which the sample is pumped in an oscillating manner. Starting from the same amount of DNA for the three different methods, a series of hybridization experiments using mouse lung and testis DNA is presented to demonstrate these benefits. The gain observed using the rotating microchamber is large: both in terms of analysis speed (up to tenfold increase) and in final spot intensity (up to sixfold increase). The gain is due to the combined effect of the hybridization chamber miniaturization (leading to a sample concentration increase if comparing iso-mass conditions) and the transport enhancement originating from the rotational shear-driven flow induced by the rotation of the chamber bottom wall.  相似文献   
39.
EstimationoflocaldensityofsolventaboutthesoluteSolvatochromicbehaviorsofspectroscopicprobesarewidelyusedtoestimatethesol-ventstrengthofsupercriticalfluids(SCF,).i-3lnthiswork,thesolvatochrondcshiftofthen-n*transitionbandforacetone(O.o37mo1.L-')insupercrihcal(SC)CO2wasde-terminedbyUVspectroscopytostUdythesolvationeffect.TheMcRae-BaylissexpressionbasedonthedielectriccontinUUInmodelgivestherelahonshipbetWeenso1vatochromicshiftandpo1arizabilityofnonPolarsolvents4-5asfollows:wherevisthewave…  相似文献   
40.
Paramagnetic metal ions bound to proteins generate a dipolar field that can be accurately probed by pseudocontact shifts (PCS) displayed by the protein's nuclear spins. PCS are highly useful for determining the coordinates of individual spins in the molecule and for rapid structure determinations of entire protein-protein and protein-ligand complexes. However, PCS measurements require reliable resonance assignments for the molecule in its paramagnetic state and in a diamagnetic reference state. This article discusses different approaches for pairwise resonance assignments, with emphasis on a strategy which exploits chemical exchange between the two states.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号