全文获取类型
收费全文 | 850篇 |
免费 | 76篇 |
国内免费 | 154篇 |
专业分类
化学 | 1029篇 |
晶体学 | 9篇 |
力学 | 4篇 |
综合类 | 3篇 |
物理学 | 35篇 |
出版年
2023年 | 10篇 |
2022年 | 26篇 |
2021年 | 25篇 |
2020年 | 20篇 |
2019年 | 28篇 |
2018年 | 33篇 |
2017年 | 23篇 |
2016年 | 35篇 |
2015年 | 39篇 |
2014年 | 37篇 |
2013年 | 97篇 |
2012年 | 40篇 |
2011年 | 42篇 |
2010年 | 26篇 |
2009年 | 42篇 |
2008年 | 47篇 |
2007年 | 46篇 |
2006年 | 39篇 |
2005年 | 33篇 |
2004年 | 47篇 |
2003年 | 53篇 |
2002年 | 33篇 |
2001年 | 21篇 |
2000年 | 28篇 |
1999年 | 28篇 |
1998年 | 26篇 |
1997年 | 22篇 |
1996年 | 18篇 |
1995年 | 19篇 |
1994年 | 19篇 |
1993年 | 14篇 |
1992年 | 13篇 |
1991年 | 6篇 |
1990年 | 7篇 |
1989年 | 2篇 |
1988年 | 7篇 |
1987年 | 7篇 |
1986年 | 3篇 |
1985年 | 1篇 |
1984年 | 3篇 |
1982年 | 4篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1974年 | 1篇 |
1973年 | 4篇 |
排序方式: 共有1080条查询结果,搜索用时 15 毫秒
71.
K. S. Birdi 《Colloid and polymer science》1982,260(6):628-631
In microemulsions consisting of four components, i.e. detergent — water — oil — cosurfactant, the free energy of transfer from the continuous oil phase to the interfacial region for the cosurfactant is reported. From the effect of temperature on the free energy, the entropy and the enthalpy values are also reported. The effect of chain length of the alcohol (cosurfactant) is also described. It is further shown, that if the oil phase consists of hexadecane, then the free energy changes as a linear function of the number of carbon atoms in the cosurfactant. On the other hand, if the oil phase is benzene, the cosurfactant chain length has very little effect. These data are analyzed with respect to the microemulsion structure and stability. 相似文献
72.
Conductance measurements for fifteen uni-univalent salts in 2-methylpyridine-N-oxide (2-MPO) were made over the concentration range of 2–120×10–4 mol-dm–3 at 55°C. All conductance data were evaluated by the Lee-Wheaton equation. The results indicate that all of the salts studied are slightly associated in 2-MPO, which is, nevertheless, a reasonably good ionizing solvent compared to other solvents having a similar value for the dielectric constant. The tetraalkylammonium halides are weaker electrolytes than the tetraphenylborate salts in 2-MPO. Ionic limiting molar conductances were obtained by using as a reference electrolyte tris(iso-pentyl)butylammonium tetraphenylborate. Anions appear to be poorly solvated in this solvent but certain cations, particularly Na+ and K+, show evidence of specific ion-solvent interaction.This study was presented, in part, at the 6th Central Regional Meeting of the American Chemical Society, Detroit, Michigan, April 1974. 相似文献
73.
The cathodic electrolysis of esters of 1,1,2,2-ethane- or ethylenetetracarboxylic acids in the presence of dihaloalkanes leads to esters of 1,1,2,2-cycloalkanetetracarboxylic acids.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 217–220, January, 1992. 相似文献
74.
Rob J. Vreeken Maria E. Jager Rudy T. Ghijsen Udo A. Th. Brinkman 《Journal of separation science》1992,15(12):785-790
Fatty acids can be conveniently derivatized in less than one minute with (chloro)alkyl chloroformates such as methyl chloroformate, 2-chloroethyl chloroformate and 2,2,2-trichloroethyl chloroformate. 2,2,2-Trichloroethyl chloroformate is the most reactive reagent, and yields a reaction product which can be sensitively detected by GC ECD (detection limit 50 ng/ml, i.e. 25 pg/injection, for C8, C10, and C12 acids). In non-aqueous media 3-picoline, N-methylpiperidine, and dimethylaminopyridine show catalytic activity comparable with that of pyridine and can, therefore, replace it. N-methylpiperidine is the best basic catalyst in aqueous media (i.e. media containing up to 40 % water). 相似文献
75.
Contributions to the Chemistry of Transition Metal Alkyl Compounds. 58 On 2-(Dimethylaminomethyl)ferrocenyl Compounds of Vanadium, Molybdenum, Tungsten, Thorium, and Uranium Earlier results according to which dimethylaminomethylferrocenyl groups (FcN) are able to form stable organometallic chelate compounds were confirmed by synthesis of the heterobimetallic chelate compounds (FcN)2VO · Li(acac) II , (FcN)MoO2(acac) III , (FcN)WOCl3 IV , (FcN)Th(acac)3 V , and (FcN)UO2(acac) VI from the corresponding metal acetylacetonates or oxidchlorides and (FcN)Li I . The new compounds were characterized by elemental analysis, the i.r., 1H-n.m.r., and electron spectra and by their effective magnetic moments. 相似文献
76.
The reactivity of ethyl‐, propyl‐ and octylgallate towards diphenylpicryl hydracil radicals has been measured in homogeneous solution (ethanol) and in Triton X‐100 micellar solutions. Similar reactivities were measured in homogeneous solutions, indicating that the length of the alkyl chain does not influence the reactivity of the phenolic groups. On the other hand, different reactivities were measured in micellar solutions, particularly at low (5 mM) surfactant concentrations. Data obtained at different surfactant concentrations allow estimation of partitioning of the gallates and their intramicellar bimolecular rate constant. The values obtained indicate that all the observed differences in reactivity are attributable to differences in substrate partitioning between the micellar and aqueous pseudophases. In fact, similar values of the intramicellar rate constants were obtained, suggesting that the average location of the reactive groups inside the micelles is independent of the solute alkyl chain length. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
77.
C. Aymes‐Chodur S. Esnouf A. Le Moël 《Journal of Polymer Science.Polymer Physics》2001,39(13):1437-1448
The fluoropolymer poly(vinylidene fluoride) was irradiated with γ rays to induce a polystyrene (PS) radiation grafting via an indirect method. Electron spin resonance and Fourier transform infrared studies were performed to identify the species that initiated the PS grafting. Specific experiments were performed to prove separately the importance of each kind of radical. A localization of the radicals in this irradiated polymer is proposed, and a kinetic model of the grafting is given. © 2001 John Wiley & Sons, Inc. J Polym Sci B Part B: Polym Phys 39: 1437–1448, 2001 相似文献
78.
79.
By taking as an example the obtaining of the spectra of the gas phase over alkali metal iodides and calcium fluoride, we show the possibility of eliminating systematic errors of atomic absorption analysis which are due to nonselective absorption of light. It is been suggested that it makes sense to create a database that would contain molecular absorption spectra of the most abundant substances and would be intended for use by chemistsanalysts. 相似文献
80.
Christopher A. Paddon Farrah L. Bhatti Timothy J. Donohoe Richard G. Compton 《Journal of Physical Organic Chemistry》2007,20(2):115-121
Recent interest in the electrocatalytic activity of silver towards the reduction of alkyl iodides has led us to investigate whether the effect is observed in tetrahydrofuran (THF) at room temperature. Using platinum electrodes in THF for the reduction of alkyl halides at 298 K has been hampered by the solvent window, which ‘obscures’ the voltammetric signals of interest. In order to overcome these problems, voltammetry has been performed at low temperature and was shown to extend the voltammetric window, leading to accurate electrochemical analyses and even novel changes in mechanism(s) of the reactive species following electron‐transfer (ET). Herein, it is shown that for a primary and tertiary alkyl iodide in THF, electroreduction at silver leads to a significant shift in the reduction potential to more positive values compared to platinum. In addition, following reduction, a characteristic series of oxidation peaks are observed and are shown to be due to the specific activity of iodide ions towards silver following reductive cleavage of the parent alkyl iodide. This characteristic feature is not observed with other halide ions: bromide and chloride. Preparative electrolyses at controlled‐potential have suggested that the reduction of the above alkyl iodides is a one‐electron concerted process. The ‘free’ iodide ions act as a monitor of reaction progression, and the carbon‐centred radical either dimerises and/or abstracts a hydrogen atom from the electrolyte/solvent; 1‐iodoadamantane giving percentage yields of 58% adamantane and 39% 1,1'‐biadamantane, the primary alkyl iodide, prepared in‐house, giving 67% R‐H and 25% R‐R. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献