全文获取类型
收费全文 | 222篇 |
免费 | 9篇 |
国内免费 | 5篇 |
专业分类
化学 | 130篇 |
力学 | 11篇 |
数学 | 48篇 |
物理学 | 47篇 |
出版年
2022年 | 2篇 |
2020年 | 2篇 |
2019年 | 3篇 |
2018年 | 6篇 |
2017年 | 2篇 |
2016年 | 9篇 |
2014年 | 4篇 |
2013年 | 7篇 |
2012年 | 7篇 |
2011年 | 11篇 |
2010年 | 5篇 |
2009年 | 6篇 |
2008年 | 12篇 |
2007年 | 18篇 |
2006年 | 5篇 |
2005年 | 8篇 |
2004年 | 9篇 |
2003年 | 12篇 |
2002年 | 6篇 |
2001年 | 4篇 |
2000年 | 3篇 |
1999年 | 4篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1996年 | 3篇 |
1995年 | 4篇 |
1994年 | 3篇 |
1993年 | 5篇 |
1992年 | 10篇 |
1991年 | 4篇 |
1990年 | 6篇 |
1988年 | 4篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 4篇 |
1984年 | 2篇 |
1983年 | 4篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1980年 | 4篇 |
1977年 | 2篇 |
1975年 | 3篇 |
1974年 | 3篇 |
1968年 | 1篇 |
1967年 | 1篇 |
1964年 | 1篇 |
1963年 | 2篇 |
1940年 | 2篇 |
1938年 | 2篇 |
1932年 | 2篇 |
排序方式: 共有236条查询结果,搜索用时 15 毫秒
1.
2.
Alastair C. Lewis Sarah A. Askey Krystyna M. Holden Keith D. Bartle Michael J. Pilling 《Journal of separation science》1997,20(2):109-114
The composition and concentration of polycyclic aromatic compounds (PAC) in fuels. Theier combustion products and in the atmosphere remains a topic of considerable interest. Despite the wealth of literature on the identification of PAC, speciation at low concentrations remains difficult due to instrument limitation and the complexity of fuel and environmental samples. Consequently on line sample preparation procedures (SPE, SFE, LC, etc.) are becomeing an increasingly important step in the analysis procedure particularly where sample clean-up and fractionation are essential for improving analytical resolution. In this study a normal phase high pressure analytical resolution. In this study a normal phase high pressure liquid chromatography-gas chromatography (LC-GC) system has been developed to provide quantitative analysis of samples, as diverse as coal liquids, petroleum fuels, diesel exhaust particulates, and urban air particulates. Separation and identification of parent and alkylated PAH, hetercycline nitro-and oxy-PAC can be achieved by direct coupling to an atomic emission detector and a bech top mass spectrometer. For both systems the primary LC separation combined with the large sample volume transferred to GC vastly improves detection limits. Furthermore the complimentary nature of the two detectors used enables the positive indentification of many unknowns. 相似文献
3.
The total synthesis of a 3-thia- and a 3-aza-1-dethiacepham ( and ) are described. Neither compound possessed antibacterial activity . . An unsaturated analog, a 3-aza-1-dethiaceph-1-em exhibited weak antibacterial activity. 相似文献
4.
Jung SY Lim SM Albertorio F Kim G Gurau MC Yang RD Holden MA Cremer PS 《Journal of the American Chemical Society》2003,125(42):12782-12786
The molecular level details of the displacement of surface adsorbed fibrinogen from silica substrates were studied by atomic force microscopy, immunochemical assays, fluorescence microscopy, and vibrational sum frequency spectroscopy. The results showed that human plasma fibrinogen (HPF) can be readily displaced from the interface by other plasma proteins near neutral pH because the positively charged alpha C domains on HPF sit between the rest of the macromolecule and the underlying surface. The alpha C domains make weak electrostatic contact with the substrate, which is manifest by a high degree of alignment of Lys and Arg residues. Upon cycling through acidic pH, however, the alpha C domains are irreversibly removed from this position and the rest of the macromolecule is free to engage in stronger hydrogen bonding, van der Waals, and hydrophobic interactions with the surface. This results in a 170-fold decrease in the rate at which HPF can be displaced from the interface by other proteins in human plasma. 相似文献
5.
Dimethylphosphoramides react with -chloroperoxybenzoic acid (MCPBA) in anhydrous acetone to yield the previously unknown -dimdethylamino-oxyphosphonous derivatives -oxidation and rearrangement. Further MCPBA oxidation yields formaldehyde and nitrosomethane, isolated as its -dimer. These reactions provide a possible biomimetic model for the metabolic activation of hexamethylphosphoramide as a mutagen and carcinogen. 相似文献
6.
We consider a random Schrödinger operator onL
2(v) of the form
, {C
i} being a covering of
v
with unit cubes around the sites of
v
and {q
i} i.i.d. random variables with values in [0, 1]. We assume that theq
i's are continuously distributed with bounded densityf(q) and that 0<P(q
0<1/2)=<1. Then we show that an ergodic mean of the quantity dx|x|2|(exp(itH
))(x)|2t
–1 vanishes provided =g
E(H
), where is well-localized around the origin andg
E is a positiveC
-function with support in (0,E),EE*(, |f|). Our estimate ofE*(, |f|) is such that the set {x
v
|V
(x) E*(, |f|)} may contain with probability one an infinite cluster of cubes {C
i} which are nearest neighbours. The proof is based on the technique introduced by Fröhlich and Spencer for the analysis of the Anderson model.Work supported in part by C.N.R. (Italy) and NAVF (Norway)On leave of absence from Instituto di Fisica Università di Roma, Italia 相似文献
7.
Leone AM Tibodeau JD Bull SH Feldberg SW Thorp HH Murray RW 《Journal of the American Chemical Society》2003,125(22):6784-6790
Polypyridyl complexes of Co decorated with 350-Da polyether chains (Co(350)(2+)) form molten phases of nucleic acids when paired with DNA counterions (Co(350)DNA) or 25-mer oligonucleotides. Analysis of voltammetry and chronoamperometry of mixtures of these phases with complexes having ClO(4)(-) counterions (Co(350)(ClO(4))(2)) and no other diluent provides charge transport rates from the oxidation and reduction currents for the complexes. As the mole fraction of the Co(350)(ClO(4))(2) complex in the mixture is varied from ca. 0.25 to 1, the physical diffusion constants derived from the Co(III/II) wave increase from 1 x 10(-11) cm(2)/s to 5 x 10(-10) cm(2)/s, and apparent diffusion constants dominated by the Co(II/I) electron self-exchange increase from 1 x 10(-10) cm(2)/s to 2 x 10(-8) cm(2)/s. Pure Co(350)DNA melts, containing no Co(350)(ClO(4))(2) complex, do not exhibit recognizable voltammetric waves; DNA suppresses the Co(II/I) electron transfer reactions of Co complexes for which it is the counterion. There are therefore two microscopically distinct kinds of Co(350) complexes, those with DNA and those with ClO(4)(-) counterions, with respect to their Co(II/I) electron-transfer dynamics, leading to percolative behavior in their mixtures. The electron-transfer rates of the Co(II/I) couple are controlled by the diffusive relaxation of the ionic atmosphere around the reaction pair, and the inactivity of the bound Co complexes can be attributed to the very low mobility of the anionic phosphate groups in the DNA counterion. Substitution of sulfonated polystyrene for DNA produced similar results, suggesting that this phenomenon is general to other polymer counterions of low mobility. We conclude that the measured Co(II/I) charge transport and electron-transfer rate constants reflect more the diffusive mobility of the perchlorate counterion than the intrinsic Co(II/I) electron hopping rate. 相似文献
8.
Reipa V Mayhew MP Holden MJ Vilker VL 《Chemical communications (Cambridge, England)》2002,(4):318-319
Spectroelectrochemistry measurements are used to demonstrate that active site mutation and binding of an non-natural substrate to P450cam (CYP101) reduces the shift in the redox potential caused by substrate-binding, and thereby results in slower catalytic turnover rate relative to wild-type enzyme with the natural camphor substrate. 相似文献
9.
Providing consistent and objective evaluation of published data on nutrient composition is critical for planning future analytical studies and for effective use of data. Based on a commercial expert system shell, a computer system of approximately 200 rules has been created to evaluate and ratre quantitatively published data on selenium in foods. The evaluation scheme uses five general categories for its rule-making process: number of samples, analytical method, sample handling, sampling plan, and analytical quality control. For each selenium value to be evaluted, rating ar assigned in each category by the expert system based on input which is derived from the information reportedin a given paper. A quality index, which is derived from the ratings, is a measure of the reliability of a given selenium value over all categories for a given study. The concepts used in developing SELEX have the potential of establishing criteria for evaluation of proposed analytical methods prior to their publication. 相似文献
10.
C. Glidewell G.S. Harris H.D. Holden D.C. Liles J.S. McKechnie 《Journal of fluorine chemistry》1981,18(2):143-154
Fluorination of triphenylarsine oxide by aqueous hydrogen fluoride (1–40%) in the absence of glass readily gives triphenylarsine difluoride. When the reaction with dilute (1%) aqueous hydrogen fluoride is carried out in borosilicate glass apparatus, the glass participates in the reaction resulting in the formation of the crystalline 2:1 adduct 2Ph3AsO·HBF4. Crystals of this compound are monoclinic, 21/, = 12.926(4), = 17.819(6), = 14.994(4) Å, β = 98.97(3)°, Z = 4. The structure contains cations [(Ph3AsO)2H]+ in which O is 2.44(2)Å, and anions BF4?. 相似文献