全文获取类型
收费全文 | 269篇 |
免费 | 4篇 |
国内免费 | 1篇 |
专业分类
化学 | 202篇 |
力学 | 4篇 |
数学 | 11篇 |
物理学 | 57篇 |
出版年
2021年 | 2篇 |
2019年 | 3篇 |
2018年 | 1篇 |
2017年 | 3篇 |
2016年 | 6篇 |
2015年 | 3篇 |
2014年 | 3篇 |
2013年 | 13篇 |
2012年 | 11篇 |
2011年 | 18篇 |
2010年 | 6篇 |
2009年 | 15篇 |
2008年 | 18篇 |
2007年 | 13篇 |
2006年 | 17篇 |
2005年 | 13篇 |
2004年 | 14篇 |
2003年 | 10篇 |
2002年 | 14篇 |
2000年 | 5篇 |
1999年 | 1篇 |
1998年 | 3篇 |
1997年 | 6篇 |
1996年 | 3篇 |
1995年 | 1篇 |
1994年 | 4篇 |
1993年 | 5篇 |
1992年 | 5篇 |
1991年 | 4篇 |
1990年 | 1篇 |
1989年 | 6篇 |
1987年 | 7篇 |
1986年 | 1篇 |
1985年 | 5篇 |
1984年 | 4篇 |
1983年 | 4篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1972年 | 1篇 |
1970年 | 2篇 |
1955年 | 1篇 |
1935年 | 1篇 |
1887年 | 2篇 |
1880年 | 2篇 |
排序方式: 共有274条查询结果,搜索用时 46 毫秒
71.
Ying Wang Carole Calas‐Blanchard Montserrat Cortina‐Puig Liu Baohong Jean‐Louis Marty 《Electroanalysis》2009,21(12):1395-1400
A simple and sensitive electrochemical method for the determination of antioxidant capacity has been studied. 4‐hydroxybenzoic acid (4‐HBA) was used as a trapping agent for photogenerated .OH radicals, leading to 3,4‐dihydroxybenzoic acid (3,4‐DHBA). Square‐wave voltammetry was used to quantify the amount of 3,4‐DHBA formed from the reaction between 4‐HBA and .OH. Addition of antioxidants induced the competition between 4‐HBA and antioxidants toward .OH elimination, resulting in a decrease of the measured current. The IC50 for different standard antioxidants was calculated and expressed in Trolox equivalent antioxidant capacity (TEAC). The proposed method was successfully compared to a fluorimetric one. 相似文献
72.
One reason that free energy difference calculations are notoriously difficult in molecular systems is due to insufficient conformational overlap, or similarity, between the two states or systems of interest. The degree of overlap is irrelevant, however, if the absolute free energy of each state can be computed. We present a method for calculating the absolute free energy that employs a simple construction of an exactly computable reference system which possesses high overlap with the state of interest. The approach requires only a physical ensemble of conformations generated via simulation and an auxiliary calculation of approximately equal central-processing-unit cost. Moreover, the calculations can converge to the correct free energy value even when the physical ensemble is incomplete or improperly distributed. As a "proof of principle," we use the approach to correctly predict free energies for test systems where the absolute values can be calculated exactly and also to predict the conformational equilibrium for leucine dipeptide in implicit solvent. 相似文献
73.
M. Villanueva-Ibañez C. Le Luyer S. Parola O. Marty J. Mugnier 《Journal of Sol-Gel Science and Technology》2004,31(1-3):277-281
We present for the first time the elaboration via sol gel route of cerium (1 mol%) doped SrHfO3 powders and films. The sol is elaborated using hafnium and strontium ethoxides as precursors and cerium nitrate as dopant. The structure of powders and films are characterized by convergent methods: Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy, Raman spectroscopy and optical measurements conducted by the prism coupling method. The powder crystallises from amorphous to pure SrHfO3 orthorhombic perovskite phase after a 800°C heat treatment. Nevertheless HfO2 monoclinic phase coexists with orthorhombic perovskite phase after a 1000°C heat treatment. The film is amorphous for annealing temperatures lower than 700°C and presents good waveguiding performances. The film heat-treated at 700°C exhibits a refractive index of 1.810 ± 0.001 (λ = 543.5 nm) for a thickness around 375 nm. The attenuation coefficient obtained on the 400°C heat-treated film is α = 4.0 ± 0.5 dB/cm (λ = 632.8 nm). The film starts to crystallize at 750°C into the SrHfO3 orthorhombic phase but HfO2 monoclinic phase is also detected after a heat treatment at 1000°C. The potentiality of sol gel Ce3+:SrHfO3 powders and films for scintillation applications are investigated. 相似文献
74.
Maurus Spescha 《Helvetica chimica acta》1993,76(5):1832-1846
Protected thiosugars were prepared as ligands for the metal-catalyzed enantioselective synthesis. The protecting groups in these ligands were varied to test a proposed new concept for the metal-catalyzed enantioselective synthesis. This new concept centres on the use of a stair-like ligand with a large substituent on one side and a small substitutent on the other rather than the commonly employed ligands which have C2 symmetry (see Fig.3). In such a ligand, both substituents should have a major influence on the coordination of a prochiral substrate. To test this proposal, 3-thio-α-D -glucofuranose derivatives with the following substituents were synthesized: 1,2-O-isopropylidene-5,6-O-methylidene (see 24 ), 1,2:5,6-di-O-isopropylidene (see 2 ), 5,6-O-cyclohexylidene-1,2-O-isopropylidene (see 23 ), 1,2-O-cyclohexylidene-5,6-O-isopropylidene (see 14 ), 1,2:5,6-di-O-cyclohexylidene (see 13 ), 5,6-O-(adamantan-2-ylidene)-1,2-O-isopropylidene (see 21 ), and 1,2:5,6-di-O-(adamantan-2-ylidene) (see 25 , Table 2). As a representative of the allofuranoses, 1,2:5,6-di-O-isopropylidene-3-thio-α-D -allofuranose ( 6 ) was chosen. The following derivatives of 1,2-O-isopropylidene-α-D -xylofuranose were also synthesized: 1,2-O-isopropylidene-5-deoxy-3-thio-α-D -xylofuranose ( 29 ), 1,2-O-isopropylidene-3-thio-α-D -xylofuranose ( 28 ) and 5-O-[(tert-butyl)-diphenylsilyl]-1,2-O-isopropylidene-3-thio-α-D -xylofuranose ( 15 , see Table 2). The proposed concept was tested using the copper-catalyzed 1,4-addition of BuMgCl to cyclohex-2-en-1-one. The enantioselectivity was very dependent on the ligand used and was up to 58%. 相似文献
75.
The reaction of [(3,5-Me(2)-C(5)H(3)N)(2)Zn(ESiMe(3))(2)] (E = Se, Te) with cadmium(II) acetate in the presence of PhESiMe(3) and P(n)Pr(3) at low temperature leads to the formation of single crystals of the ternary nanoclusters [Zn(x)()Cd(10)(-)(x)()E(4)-(EPh)(12)(P(n)()Pr(3))(4)] [E = Se, x = 1.8 (2a), 2.6 (2b); Te, x = 1.8 (3a), 2.6 (3b)] in good yield. The clusters [Zn(3)Hg(7)Se(4)(SePh)(12)(P(n)()Pr(3))(4)] (4) and [Cd(3.7)Hg(6.3)Se(4)(SePh)(12)(P(n)()Pr(3))(4)] (5) can be accessed by similar reactions involving [(3,5-Me(2)-C(5)H(3)N)(2)Zn(SeSiMe(3))(2)] or [(N,N'-tmeda)Cd(SeSiMe(3))(2)] (1) and mercury(II) chloride. The metal silylchalcogenolate reagents are efficient delivery sources of {ME(2)} in cluster synthesis, and thus, the metal ion content of these clusters can be readily moderated by controlling the reaction stoichiometry. The reaction of cadmium acetate with [(3,5-Me(2)-C(5)H(3)N)(2)Zn(SSiMe(3))(2)], PhSSiMe(3), and P(n)()Pr(3) affords the larger nanocluster [Zn(2.3)Cd(14.7)S(4)(SPh)(26)(P(n)()Pr(3))(2)] (6). The incorporation of Zn(II) into {Cd(10)E} (E = Se, Te) and Zn(II) or Cd(II) into {Hg(10)Se} nanoclusters results in a significant blue shift in the energy of the first "excitonic" transition. Solid-state thermolysis of complexes 2 and 3 reveals that these clusters can be used as single-source precursors to bulk ternary Zn(x)Cd(1)(-)(x)E materials as well as larger intermediate clusters and that the metal ion ratio is retained during these reactions. 相似文献
76.
Metal complexes with reactive [ESiR3]? (E = S, Se, Te) or [S(SiMe2)]2? ligands provide a means for the delivery of {MEn}m? units in the formation of heterometallic polynuclear complexes and clusters. These complexes can be reacted with M′ salts to promote M–E–M′ interactions via the elimination of a silane side product. This research report summarizes the recent developments in the synthesis of silylchalcogenolate complexes of the d‐block metals with emphasis directed to those for which reactivity studies for the formation of ternary clusters have been carried out. The effects of varying the groups on the silyl moiety on the stability and reactivity of these precursor molecules are also discussed. 相似文献
77.
A screen-printed biosensor for the detection of pesticides in water miscible organic solvents is described based on the use of p-aminophenyl acetate as acetylcholinesterase substrate. The oxidation of p-aminophenol, product of the enzymatic reaction was monitored at 100 mV vs. Ag/AgCl screen-printed reference electrode. Miscible organic solvents as ethanol and acetonitrile were tested. The acetylcholinesterase (AChE) was immobilised on a screen-printed electrode surface by entrapment in a PVA-SbQ polymer and the catalytic activity of immobilised AChE was studied in the presence of different percentages of organic solvents in buffer solution. The sensor shows good characteristics when experiments were performed in concentrations of organic solvents below 10%. No significant differences were observed when working with 1 and 5% acetonitrile in the reaction media. Detection limits as low as 1.91x10(-8) M paraoxon and 1.24x10(-9) M chlorpyrifos ethyl oxon were obtained when experiments are carried out in 5% acetonitrile. 相似文献
78.
de Vrij L. Schäfer O. Hesse N. van der Sleen G. Kerner Kremel Vulpius A. Weller Gallois J. J. André O. Schlickum E. Jungfleisch B. H. Paul Marty Ferrand Prunier Petit Masse Passmore A. R. Haslam Y. Shimoyama A. J. Swawing C. Leuken C.F. Boehringer & Sohne Gehe & Cie 《Analytical and bioanalytical chemistry》1887,26(1):654-668
79.
The dynamics of a bidimensional dense granular packing under cyclic shear is experimentally investigated close to the jamming transition. Measurement of multipoint correlation functions are produced. The self-intermediate scattering function, displaying slower than exponential relaxation, suggests dynamic heterogeneity. Further analysis of four point correlation functions reveal that the grain relaxations are strongly correlated and spatially heterogeneous, especially at the time scale of the collective rearrangements. Finally, a dynamical correlation length is extracted from a spatiotemporal pattern of mobility. Our experimental results open the way to a systematic study of dynamic correlation functions in granular materials. 相似文献
80.
A cholesteric imprinted elastomer was obtained by cross-linking a nematic side-chain polysiloxane around a chiral template. The template was first linked to some functionalised groups of the polymer via hydrogen-bound interactions, then was removed by washing. The sample was macroscopically oriented during the synthesis; so, both a molecular chirality and a supramolecular phase chirality were topologically imprinted inside the network. Batch rebinding experiments, performed in the presence of the template or of the other enantiomer, showed that the imprinted polymer has a pronounced stereo-selectivity towards the template enantiomer. The rebinding capacity appeared to be greater than an unimprinted mesogenic network as well as than an imprinted non mesogenic one. 相似文献