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51.
Cerchiaro Giselle Saboya Patrícia Lopes da Costa Ferreira Ana Maria Tomazela Daniela Maria Eberlin Marcos Nogueira 《Transition Metal Chemistry》2004,29(5):495-504
An interesting isatin-Schiff base copper(II) complex, [Cu(isapn)](ClO4)2 where isapn= N,N-[bis-(3,3-indolin-2-one)]-1,3-diiminepropane, was prepared and characterized by different techniques, both in the solid state and in solution, and its reactivity toward carbohydrate oxidation was verified. The positive ion electrospray mass spectrum detects the complex as an isotopologue cluster of singly charged intact isatin-copper(I) ions of m/z 395 (for 65Cu) with an isotopic pattern identical to that calculated for C19H16CuN4O2
+. Tandem mass spectrometry reveals an interesting and structurally diagnostic collision-induced dissociation behavior for this ionized complex, which is dominated by the cleavage of the N—(CH2)3—N propylene bridge. In aqueous solution, this complex undergoes a peculiar keto-enolic equilibrium, verified at different pH's by spectroscopic methods (u.v.–vis. and e.p.r.), with a corresponding pK
a determined as 9.5. The e.p.r. parameter ratio g
/A
for this complex, in frozen MeOH/H2O (4:1, v/v) solution at 77 K, changes from 188 cm in acidic medium (pH 2.5–3.0) to 118 cm in basic medium (pH 11), indicating a significant structural change from a distorted tetrahedral to a more tetragonal geometry around the copper ion. This compound was shown to catalyze the oxidation of hexoses (glucose, fructose and galactose), in alkaline media, via reactive oxygen species, which were detected by using specific enzymes, and by e.p.r. spin trapping. The reaction was monitored at (25.0 ± 0.1)°C by the consumption of oxygen, and showed first-order dependence on catalyst, followed by a saturation effect. First-order kinetics with respect to [OH–] concentration was also observed, indicating that enolization of the substrate as well as the metal-catalyzed enediol oxidation are the rate-determining steps. 相似文献
52.
Ana P. F. M. de Urzedo Clésia C. Nascentes Maria E. R. Diniz Rodrigo R. Catharino Marcos N. Eberlin Rodinei Augusti 《Rapid communications in mass spectrometry : RCM》2007,21(12):1893-1899
The degradation of the dye Indigo Carmine by hypochlorite in aqueous solution was monitored by electrospray ionization mass spectrometry in the negative ion mode (ESI(—)‐MS). Hypochlorite was highly efficient in removing the color of aqueous solutions of the dye. ESI(—)‐MS monitoring showed that concomitant with the Indigo Carmine consumption two transient species appeared (detected as doubly charged anions) probably formed via a net insertion of two hydroxyl groups at the exocyclic C?C bond followed by the incorporation of two (mainly) or one oxygen atoms at the indolic rings of the dye. Structures of these products were proposed based on the ESI(—)‐MS/MS data and high accuracy mass measurements. These two transient intermediates quickly decomposed, both in the condensed and in the gas phase, to yield mono‐charged anions. Based on these results, a route for the Indigo Carmine degradation by hypochlorite in aqueous solution has been proposed. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
53.
Giovana A. Bataglion Gustavo Henrique Martins Ferreira Souza Gabriel Heerdt Nelson H. Morgon José Diogo Lisboa Dutra Ricardo Oliveira Freire Marcos N. Eberlin Alessandra Tata 《Journal of mass spectrometry : JMS》2015,50(2):336-343
Traveling wave ion mobility mass spectrometry (TWIM‐MS) is shown to be able to separate and characterize several isomeric forms of diterpene glycosides stevioside (Stv) and rebaudioside A (RebA) that are cationized by Na+ and K+ at different sites. Determination and characterization of these coexisting isomeric species, herein termed catiomers, arising from cationization at different and highly competitive coordinating sites, is particularly challenging for glycosides. To achieve this goal, the advantage of using CO2 as a more massive and polarizable drift gas, over N2, was demonstrated. Post‐TWIM‐MS/MS experiments were used to confirm the separation. Optimization of the possible geometries and cross‐sectional calculations for mobility peak assignments were also performed. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
54.
Valérien Eberlin 《代数通讯》2013,41(1):183-191
Résumé: i1 s'agit d'étudier 1es algèbres de Lie dimensionnellement nilpotentes, en abrégé ADN, c'est à dire celles qui admettent une dérivation nilpotente de corang 1. Quand ces algèbres ne sont pas nilpotentes, Leger et Manley ont montré que ce sont des algèbres résolubles d'idéal maximal nilpotent ou sl 2. Nous montrons alors qu'il n'y a que quatre types possibles pour l'idéal maximal nilpotent et que la structure de l'idéal maximal nilpotent est presque connue. Dans le cas o[ugrave] ces ADN sont nilpotentes, nous étudions le cas o[ugrave] elles sont 2-nilpotentes. Nous décrivons les constantes de structures sur une base dite adaptée, des ADN 2-nilpotentes d'idéal dérivé de dimension 2, puis nous donnons une classification en dimension inférieure a 8 des ADN 2-nilpotentes dont l'idéal dérivé, égal au centre, est de dimension 2. Les résultats présentés sont tirés de Ia thése de l'auteur ([1]). 相似文献
55.
JIANG DiHua NIEN ChuFeng & QIN YuJun School of Mathematics University of Minnesota Minneapolis MN USA 《中国科学 数学(英文版)》2010,(3)
In this paper, we summarize the basic structures and properties of irreducible symplectic supercuspidal representations of GLn(F) over a p-adic local field F with characteristic zero, and explore possible topics for further investigation. 相似文献
56.
Dalmázio I de Urzedo AP Alves TM Catharino RR Eberlin MN Nascentes CC Augusti R 《Journal of mass spectrometry : JMS》2007,42(10):1273-1278
The degradation of the dye indigo carmine in aqueous solution induced by two oxidative processes (H(2)O(2)/iodide and O(3)) was investigated. The reactions were monitored by electrospray ionization mass spectrometry in the negative ion mode, ESI(-)-MS, and the intermediates and oxidation products characterized by ESI(-)-MS/MS. Both oxidative systems showed to be highly efficient in removing the color of the dye aqueous solutions. In the ESI(-)-MS of the indigo carmine solution treated with H(2)O(2) and H(2)O(2)/iodide, the presence of the ions of m/z 210 (indigo carmine in its anionic form, 1), 216, 226, 235, and 244 was noticeable. The anion of m/z 235 was proposed to be the unprecedented hydroperoxide intermediate 2 formed in solution via an electrophilic attack by hydroxyl and hydroperoxyl radicals of the exocyclic C=C bond of 1. This intermediate was suggested to be rapidly converted into the anionic forms of 2,3-dioxo-1H-indole-5-sulfonic acid (3, m/z 226), 2-amino-alpha-oxo-5-sulfo-benzeneacetic acid (4, m/z 244), and 2-amino-5-sulfo-benzoic acid (5, m/z 216). In the ESI(-)-MS of the indigo carmine solution treated with O(3), two main anions were detected: m/z 216 (5) and 244 (4). Both products were proposed to be produced via an unstable ozonide intermediate. Other anions in this ESI(-) mass spectrum were attributed to be [4 - H + Na](-) of m/z 266, [4 - H](2-) of m/z 121.5, and [5 - H](2-) of m/z 107.5. ESI-MS/MS data were consistent with the proposed structures for the anionic products 2-5. 相似文献
57.
A titrimetric method for determination of lead(II), based on the reaction between plumbite and silver ions, is described. Sodium hydroxide solution is added to the sample until the precipitate of lead hydroxide has redissolved. The solution is then made 0.025M in sodium chloride and titrated with silver nitrate. The titration is monitored with a silver electrode. An error smaller than 0.5% has been obtained for 0.05M lead (II). 相似文献
58.
Sparrapan R Mendes MA Carvalho M Eberlin MN 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(2):321-326
Two ortho-hetarynium ions, the 2-pyridyl and 2-pyrimidyl cations, react promptly with 1,3-dienes in the gas phase by annulation, formally by fusion, onto the ions of a pyrrole ring. This novel reaction proceeds through an initial polar [4 + 2+] cycloaddition across the C[triple bond]N+ bond, followed by fast ring opening, a [1,4-H] shift, and finally a recyclization that results in a contraction of a six- to a five-membered ring and dissociation by the loss of a methyl radical. For the 2-pyridyl cation, this reaction yields ionized indolizines (pyrrolo[1,2-a]pyridines), while for the 2-pyrimidyl cation, it gives ionized pyrrolo[1,2-a]pyrimidines. The annulation reaction, performed in the rf-only collision quadrupole of a pentaquadrupole (QqQqQ) mass spectrometer, occurs readily with both 1,3-butadiene and isoprene, and is thermodynamically and kinetically favored as predicted by ab initio calculations. Ortho-hetarynium ions and 1,3-dienes provide, therefore, the two building blocks for the efficient one-step gas-phase synthesis of ionized bicyclic pyrrolo[1,2-a]pyridine (indolizine) and pyrrolo[1,2-a]pyrimidine, as well as their analogues and derivatives. 相似文献
59.
Gas-phase reactions of four acylium ions and a thioacylium ion with three isomeric alpha-, beta- and gamma-hydroxy ketones are performed by pentaquadrupole mass spectrometric experiments. Novel structurally diagnostic reactions are observed, and found to correlate directly with interfunctional group separation. All five ions tested (CH(3)CO(+), CH(2)(double bond)CHCO(+), PhCO(+), (CH(3))(2)NCO(+) and (CH(3))(2)NCS(+)) react with the gamma-hydroxy ketone (5-hydroxy-2-pentanone) to form nearly exclusively a cyclic oxonium ion of m/z 85 that formally arises from hydroxy anion abstraction. With the beta-hydroxy ketone (4-hydroxy-2-pentanone), CH(2)(double bond)CHCO(+), PhCO(+) and (CH(3))(2)NCO(+) form adducts that undergo fast cyclization via intramolecular water displacement, yielding resonance-stabilized cyclic dioxinylium ions. With the alpha-hydroxy ketone (3-hydroxy-3-methyl-2-butanone), PhCO(+), (CH(3))(2)NCO(+) and (CH(3))(2)NCS(+) form stable adducts. Evidence that these adducts display cyclic structures is provided by the triple-stage mass spectra of the (CH(3))(2)NCS(+) adduct; it dissociates to (CH(3))(2)NCO(+) via a characteristic reaction-dissociation pathway that promotes sulfur-by-oxygen replacement. If cyclizations are assumed to occur with intramolecular anchimeric assistance, relationships between structure and reactivity are easily recognized. 相似文献
60.
The intrinsic reactivity of eight gaseous, mass-selected 2-azabutadienyl cations toward polar [4(+) + 2] cycloaddition with ethyl vinyl ether has been investigated by pentaquadrupole mass spectrometric experiments. Cycloaddition occurs readily for all the ions and, with the only exception of those from the N-acyl 2-azabutadienyl cations (N-acyliminium ions), the cycloadducts are found to dissociate readily upon collision activation (CID) both by retro-Diels-Alder reaction and by a characteristic loss of an ethanol (46u) neutral molecule. Ethanol loss from the intact polar [4(+) + 2] cycloadduct functions therefore as a structurally diagnostic test: 72 u neutral gain followed by 46 u neutral loss, i.e., as a combined ion-molecule reaction plus CID 'signature' for N-H, N-alkyl and N-aryl 2-azabutadienyl cations. The two N-acyliminium ions tested are exceptional as they form intact cycloadducts with ethyl vinyl ether which dissociate exclusively by the retro-Diels-Alder pathway. 相似文献