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31.
Perfluoro oxymethylene vinyl ethers have been formed by a multi-step synthesis. The key intermediates are low molecular weight perfluoropolyether (PFPE) fluoroformates CF3O(CF2O)nCOF (I) n=1-6 obtained from the photo-oxidation of perfluoro propene (HFP) in perfluorohexane. Under certain conditions the light-mediated fluorination of PFPE fluoroformates (I) gives PFPE hypofluorites CF3O(CF2O)nCF2OF (II), which can be added to sym dichlorodifluoroethene to form the dichloro adduct CF3O(CF2O)nCF2OCFClCF2Cl (III) which, after dechlorination, gives the desired vinyl ethers CF3O(CF2O)nCF2OCFCF2 (IV). Every reaction step has to be properly controlled as far as the reaction variables are concerned. A mechanistic scheme is presented that is consistent with the observed experimental data. 相似文献
32.
芳香酸淋洗液的单柱阳离子色谱法测定碱金属,铵离子和烷基胺 总被引:7,自引:0,他引:7
研究了邻苯二甲酸、苯甲酸和对羟基苯甲酸3种芳香酸分别做淋洗液的单柱阳离子色谱法分离测定Li+、Na+、NH4+、K+、甲胺、乙胺和正丙胺7种物质。3种芳香酸做淋洗液均可将7种物质分离开,且分离结果差异不大。在淋洗液浓度相同的条件下,邻苯二甲酸做淋洗液测定的检出限较低。选择3.0 mmol/L邻苯二甲酸做淋洗液测得了上述7种物质的检出限和线性范围,并进行了叶面肥试样分析,7种物质的加标回收率在96.4%~98.6%之间。 相似文献
33.
Quaternization reactions of poly(vinylpyridines) with alkyl halides show retardation in excess of that predicted by the classical second-order kinetics. Based on the classical collision and transition state theories, a kinetic model has been developed to quantify such retardation, in which the overall reaction rate is characterized by a rate constant k0 of the intrinsic reactivity between a pyridyl group and an alkyl halide group, and by a steric hindrance effect parameter α. The latter accounts for the degree to which the rate of collisions of reactants is reduced, or to which the freedom of movement of the reactants in the transition state is restricted as the reaction proceeds. The resulting kinetic expression has been validated using experimental results reported in the literature and those of our own. The functional dependence of k0 and α values on the nature of poly(vinylpyridines) and that of alkyl halides is explained. Other factors affecting k0 and α, including changes in macromolecular dimensions and/or in the distribution of residue environment, quality of solvent, and reaction temperature, are discussed. © 1993 John Wiley & Sons, Inc. 相似文献
34.
The separation, characterization, and determination of mixtures of alkyl ether sulfates (AES) and fatty acids (C10-C16) in background electrolytes (BGEs) containing acetonitrile (ACN)-water mixtures is addressed. Due to inhibition of the ionization of the carboxylate groups, the migration time and the resolution between the fatty acids decreased when the water content of the BGE was reduced, but efficiency and resolution between the AES oligomers improved. The migration times increased and resolution improved by substituting 5% ACN by an equivalent amount of dioxane. A complete separation of the two surfactant classes, up to the AES oligomers with 8 ethylene oxide units (EOs) with respect to C10, with excellent resolution between the AES oligomers, while preserving a satisfactory resolution between the fatty acids, was achieved with a BGE containing 5 mM trimethoxybenzoic acid, 7 mM dipentylamine, 85% ACN, 5% dioxane, and 10% water. The two surfactant classes were increasingly resolved by further reducing the water content of the BGE. Thus, C2 (acetate) was resolved from the AES oligomers up to 7 EOs using 90% ACN and 5% dioxane, but the resolution between the heavier fatty acids was poor with this BGE. Identification of the AES oligomers was eased by the excellent regularity of the successive migration times; thus, within each AES subclass or series of oligomers with the same number of carbon atoms in the alkyl chain, the migration times decreased following a mild curve as the number of EOs increased. The way how the data obtained by indirect photometry (corrected peak areas that are proportional to the molar concentrations) should be managed to avoid systematic error when the calibration curve is constructed using an AES standard with an oligomer distribution different from that of the samples is discussed and equations are given. Decyl sulfate was successfully used as internal standard. The detection limits (S/N = 3) were of ca. 2 microM for individual AES oligomers. 相似文献
35.
O. I. Dyubchenko V. V. Nikulina E. I. Terakh A. E. Prosenko I. A. Grigor’ev 《Russian Chemical Bulletin》2007,56(6):1149-1155
The reaction of ω-(4-hydroxyaryl)haloalkanes with various nitrogen-containing agents afforded primary, secondary, and tertiary
amino derivatives of 2,6-dialkylphenols. For the compounds synthesized, the reaction rate constants with peroxide radicals
were measured for cumene and methyl oleate oxidation. The total inhibitory activity in the model reactions of thermal autooxidation
of lard and hexadecane was studied. The rate constants of alkyl(hydroxylaryl)amines are the same as those of the corresponding
alkylphenols, whereas the total inhibitory activity of some alkyl(hydroxylaryl)amines exceeds substantially that for alkylphenols.
Dedicated to the memory of Academician N. N. Vorozhtsov on the 100th anniversary of his birth.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1107–1112, June, 2007. 相似文献
36.
N. Suryakiran 《Tetrahedron letters》2006,47(23):3853-3856
An efficient and convenient synthesis of β-ketosulfones is described. Reaction of an α-haloketone with sodium alkyl/aryl sulphinate yields the corresponding β-ketosulfone promoted by polyethylene glycol (PEG-400) as an efficient reaction medium. 相似文献
37.
Ricardo Castanedo 《Tetrahedron letters》2006,47(6):973-976
The Birch reduction-dialkylation reaction has been studied with different aromatic carboxylic acids and primary and secondary bromides. From these results it can be concluded that it is a reasonably general reaction. However, we found important exceptions with the primary bromides: allyl bromide, β-phenethyl bromide, and 5-bromo-2-methyl-2-pentene. The unusual behavior of allyl bromide is briefly discussed. 相似文献
38.
The modification of the triple helical structure in aqueous gelatin solutions by changing pH and adding alkyl sulphates at 298 K and after rechilling the solution to 283 K was investigated by CD-measurement. At 298 K the triple helical content at the IEP of the gelatin has its maximum value. It is only weakly affected by adding sodium dodecyl sulphate (SDDS) at concentrations <10–4 M/dm3. The unfolding of the triple helix affected by pH and SDDS is reversible by rechilling the solution. The triple helical content of gelatin solutions decreases at SDDS concentrations higher than 10–4 M/dm3. In all cases the decrease of the amount of triple helical structure is connected with an increase of the cis-configuration in single chains and leads to chain reversals. At sufficiently high SDDS concentrations-sheets are formed. These changes are thermally irreversible. Sodium decyl sulphate (SDS) has a more minor influence than SDDS except in the range of the c.m.c. of SDS. At sufficiently high SDS concentrations,-turns appear. 相似文献
39.
Treatment of 4-nitrophenyl chloroformate with alkylammonium hydrochloride salts and solid anhydrous Na2CO3 in either CH2Cl2 or CH3CN gave 4-nitrophenyl N-methylcarbamate and other N-alkylcarbamate analogues in excellent yields. Of particular interest is the observation that 4-nitrophenyl N-methylcarbamate, a safer alternative to the highly toxic methyl isocyanate, is obtained in quantitative yield (?95% pure as determined by 1H NMR) after simple filtration and solvent evaporation. 相似文献
40.
Phosphinophosphiniden-Phosphorane tBu2P?P = P(R)tBu2 aus Li(THF)2[η2-(tBu2P)2P] und Alkylhalogeniden
The Phosphinophosphinidene-phosphoranes tBu2P? P = P(R)tBu2 from Li(THF)2[η2-(tBu2P)2P] and Alkyl Halides We report the formation of tBu2P? P = P(R)tBu2 a and (tBu2)2PR b (with R = Me, Et, nPr, iPr, nBu, PhCH2, H2C = CH? CH2 and CF3) reactions of Li(THF)2[η2-(tBu2P)2P] 2 with MeCl, MeI, EtCl, EtBr, nPrCl, nPrBr, iPrCl, nBuBr, PhCH2Cl, H2C = CH? CH2Cl or CF3Br. In THF solutions the ylidic compounds a predominate, whereas in pentane the corresponding triphosphanes b are preferrably formed. With ClCH2? CH = CH2 only b is produced; CF3Br however yields both tBu2P? P = P(Br)tBu2 and tBu2P? P = P(CF3)tBu2, but no b . The ratio of a:b is influenced by the reaction temperature, too. The compounds tBu2P? P = P(Et)tBu2 4a and (tBu2P)2PEt 4 b , e. g., are produced in a ratio of 4:3 at ?70°C in THF, and 1:1 at 20°C; whereas 1:1 is obtained at ?70°C in pentane, and 1:2 at 20°C. Neither tBuCl nor H2C = CHCl react with 2 . The compounds a decompose thermally or under UV irradiation forming tBu2PR and the cyclophosphanes (tBu2P)nPn. 相似文献