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91.
Erik G.P. da Silva Ana Carolina do N. Santos Antnio C.S. Costa Dalva M. da N. Fortunato Ndia M. Jos Maria G.A. Korn Walter N.L. dos Santos Srgio L.C. Ferreira 《Microchemical Journal》2006,82(2):159-162
In the present work, a slurry sampling flame atomic absorption spectrometric method to determine directly manganese and zinc in powdered chocolate samples is proposed. The optimization step was performed using univariate methodology involving the following factors: nature and concentration of the acid solution, sonication time, and particle size. The established conditions led to the use of a sample mass of 150 mg, 2.0 mol L− 1 nitric acid solution, sonication time of 15 min, and a slurry volume of 50 mL. This method allows the determination of manganese and zinc with detection limit of 52 and 61 ng g− 1, respectively, and a precision expressed as relative standard deviation (RSD) of 2.6% and 3.2% (both, n = 10) for contents of manganese and zinc of 52.4 and 100.0 μg g− 1, respectively. The proposed method was applied for determination of manganese and zinc in five powdered chocolate samples. In these, the manganese content varied from 42.8 to 52.7 and from 88.6 to 102.4 μg g− 1 of zinc. The analytical results were compared with the results obtained by analysis of these samples after digestion using open vessel and acid bomb digestion procedures and determination using FS-FAAS. The statistical comparison by t-test (95% confidence level) showed no significant difference between these results. 相似文献
92.
Valfredo Azevedo Lemos Douglas Gonalves da Silva Anaildes Lago de Carvalho Dbora de Andrade Santana Geisiane dos Santos Novaes Adenilde Souza dos Passos 《Microchemical Journal》2006,84(1-2):14-21
A new chelating sorbent has been developed using Amberlite XAD-2 resin anchored with pyrocatechol through –N=C– group. This sorbent, characterised by elemental analysis and infrared (IR) spectra, was used as packing for the minicolumn in an on-line system preconcentration system for cadmium, cobalt, copper and nickel determination. Metal ions were sorbed in the minicolumn, from which it could be eluted directly to the nebulizer–burner system of the flame atomic absorption spectrometer (FAAS). Elution of all metals from minicolumn can be made with 0.50 mol L− 1 HCl or HNO3. The enrichment factors obtained were 16 (Cd), 24 (Co), 15 (Cu) and 19 (Ni), for 60 s preconcentration time, and 39 (Cd), 69 (Co), 36 (Cu) and 41 (Ni), if used 180 s preconcentration time. Under the optimum conditions, the proposed procedure allowed the determination of cadmium, cobalt, copper and nickel with detection limits of 0.31, 0.32, 0.39 and 1.64 μg L− 1, respectively, when used preconcentration periods of 180 s. The accuracy of the developed procedure was sufficient and evaluated by the analysis of the certified reference materials NIST 1515 apple leaves and NIST 1570a spinach leaves. The method was applied to the analysis of food samples (spinach, black tea and rice flour). 相似文献
93.
Pinto SS Diogo HP Guedes RC Costa Cabral BJ Minas da Piedade ME Martinho Simões JA 《The journal of physical chemistry. A》2005,109(42):9700-9708
The energetics of the phenolic O-H bond in the three hydroxybenzoic acid isomers and of the intramolecular hydrogen O-H- - -O-C bond in 2-hydroxybenzoic acid, 2-OHBA, were investigated by using a combination of experimental and theoretical methods. The standard molar enthalpies of formation of monoclinic 3- and 4-hydroxybenzoic acids, at 298.15 K, were determined as Delta(f)(3-OHBA, cr) = -593.9 +/- 2.0 kJ x mol(-1) and Delta(f)(4-OHBA, cr) = -597.2 +/- 1.4 kJ x mol(-1), by combustion calorimetry. Calvet drop-sublimation calorimetric measurements on monoclinic samples of 2-, 3-, and 4-OHBA, led to the following enthalpy of sublimation values at 298.15 K: Delta(sub)(2-OHBA) = 94.4 +/- 0.4 kJ x mol(-1), Delta(sub)(3-OHBA) = 118.3 +/- 1.1 kJ x mol(-1), and Delta(sub)(4-OHBA) = 117.0 +/- 0.5 kJ x mol(-1). From the obtained Delta(f)(cr) and Delta(sub) values and the previously reported enthalpy of formation of monoclinic 2-OHBA (-591.7 +/- 1.3 kJ x mol(-1)), it was possible to derive Delta(f)(2-OHBA, g) = -497.3 +/- 1.4 kJ x mol(-1), Delta(f)(3-OHBA, g) = -475.6 +/- 2.3 kJ x mol(-1), and Delta(f)(4-OHBA, cr) = -480.2 +/- 1.5 kJ x mol(-1). These values, together with the enthalpies of isodesmic and isogyric gas-phase reactions predicted by density functional theory (B3PW91/aug-cc-pVDZ, MPW1PW91/aug-cc-pVDZ, and MPW1PW91/aug-cc-pVTZ) and the CBS-QMPW1 methods, were used to derive the enthalpies of formation of the gaseous 2-, 3-, and 4-carboxyphenoxyl radicals as (2-HOOCC(6)H(4)O(*), g) = -322.5 +/- 3.0 kJ.mol(-1) Delta(f)(3-HOOCC(6)H(4)O(*), g) = -310.0 +/- 3.0 kJ x mol(-1), and Delta(f)(4-HOOCC(6)H(4)O(*), g) = -318.2 +/- 3.0 kJ x mol(-1). The O-H bond dissociation enthalpies in 2-OHBA, 3-OHBA, and 4-OHBA were 392.8 +/- 3.3, 383.6 +/- 3.8, and 380.0 +/- 3.4 kJ x mol(-1), respectively. Finally, by using the ortho-para method, it was found that the H- - -O intramolecular hydrogen bond in the 2-carboxyphenoxyl radical is 25.7 kJ x mol(-1), which is ca. 6-9 kJ x mol(-1) above the one estimated in its parent (2-OHBA), viz. 20.2 kJ x mol(-1) (theoretical) or 17.1 +/- 2.1 kJ x mol(-1) (experimental). 相似文献
94.
dos Reis EO Vianna-Jorge R Suarez-Kurtz G Lima EL Azevedo Dde A 《Rapid communications in mass spectrometry : RCM》2005,19(12):1666-1674
A sensitive and specific assay for detection of busulfan in human plasma was developed. The assay is based on rapid isolation of busulfan by liquid-liquid extraction with ethyl acetate, and detection by high-performance liquid chromatography with electrospray ionization and tandem mass spectrometry. 1,6-Bis(methanesulfonyloxy)hexane, a synthesized analogue of busulfan, was used as the internal standard (IS). The acquisition was performed in the multiple reaction monitoring mode; busulfan and the IS were detected with no interferences from plasma matrix. The method was linear over the range 5-2500 ng mL(-1), with r2 > 0.99 and a run time of only 3.5 min. The intra- and inter-assay precisions were in the ranges 2.1-11.9% and 3.2-10.1%, respectively, and the intra- and inter-assay accuracies were 92.2-107.6% and 94.7-104.1%, respectively. The absolute recoveries were 82.0% (20 ng mL(-1)), 90.6% (1000 ng mL(-1)) and 80.0% (2000 ng mL(-1)) for busulfan, and 89.1% for the IS (1000 ng mL(-1)). The limits of detection and quantification were 2 and 5 ng mL(-1), respectively. The validated method was successfully applied to analyze plasma samples obtained from six adults receiving doses of 1 mg kg(-1) in a conditioning regimen prior to bone marrow transplantation. A marked intra-patient variation in busulfan concentrations during the steady state was observed, which limits the application of pharmacokinetic modeling and suggests that continuous therapeutic monitoring is necessary for adequate individualized dosing. In this regard, the present assay brings important advantages relative to other methods described in the literature, i.e., it is highly specific and simple to perform, with a rapid chromatographic run time (3.5 min), and the whole procedure can be completed in 4-5 h, which would permit dose corrections after the third dose allowing earlier and better dosing adjustments towards the target level of busulfan. 相似文献
95.
The partial hydrogenation of benzene to cyclohexene by nanoscale ruthenium catalysts in imidazolium ionic liquids 总被引:3,自引:0,他引:3
Silveira ET Umpierre AP Rossi LM Machado G Morais J Soares GV Baumvol IJ Teixeira SR Fichtner PF Dupont J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(15):3734-3740
The controlled decomposition of an Ru(0) organometallic precursor dispersed in 1-n-butyl-3-methylimidazolium hexafluorophosphate (BMI.PF(6)), tetrafluoroborate (BMI.BF(4)) or trifluoromethane sulfonate (BMI.CF(3)SO(3)) ionic liquids with H(2) represents a simple and efficient method for the generation of Ru(0) nanoparticles. TEM analysis of these nanoparticles shows the formation of superstructures with diameters of approximately 57 nm that contain dispersed Ru(0) nanoparticles with diameters of 2.6+/-0.4 nm. These nanoparticles dispersed in the ionic liquids are efficient multiphase catalysts for the hydrogenation of alkenes and benzene under mild reaction conditions (4 atm, 75 degrees C). The ternary diagram (benzene/cyclohexene/BMI.PF(6)) indicated a maximum of 1 % cyclohexene concentration in BMI.PF(6), which is attained with 4 % benzene in the ionic phase. This solubility difference in the ionic liquid can be used for the extraction of cyclohexene during benzene hydrogenation by Ru catalysts suspended in BMI.PF(6). Selectivities of up to 39 % in cyclohexene can be attained at very low benzene conversion. Although the maximum yield of 2 % in cyclohexene is too low for technical applications, it represents a rare example of partial hydrogenation of benzene by soluble transition-metal nanoparticles. 相似文献
96.
97.
Érika Pinto Marinho A. G. Souza Danniely S. de Melo Iêda M. G. Santos Dulce M. A. Melo Walquíria J. da Silva 《Journal of Thermal Analysis and Calorimetry》2007,87(3):801-804
Because
of their electrical, magnetic and catalytic properties rare earth and transition
metal mixed oxides are important compounds. Lanthanum chromites have been
extensively used as solid oxide fuel cell (SOFC) interconnect materials. In
this work, lanthanum chromites partially substituted by alkaline earth metals
were synthesized by the urea combustion process. TG and DSC techniques were
used to evaluate the presence of the organic material in the powder after
reaction on the hot plate. The powders were calcinated at 900°C and characterized
by XRD and SEM. The results show that the particles have nanometric dimensions
and the perovskite structure was formed. 相似文献
98.
Ferreira AR de A Vilela GV Amorim MB Perry KP da Silva AJ Dias AG Costa PR 《The Journal of organic chemistry》2004,69(12):4013-4018
The conjugate addition of benzylic phenylsulfonyl carbanions (2a'-d') to enoates derived from d-(+)-mannitol (E- or Z-1a-c) was studied using THF and THF/HMPA as solvent. Under kinetic conditions (-78 degrees C), enoate E-1a,b led to a mixture of syn-(R,S) and anti-(S,S) adducts (55/45), and syn-(R,S) adducts were the main product obtained ( approximately 90/10) from enoate Z-1a. Under thermodynamic conditions (-78 degrees C to room temperature) syn-(R,S) adducts were also preferentially formed ( approximately 90/10), despite the geometry at the double bond in the acceptor. Enoate 1c (E/Z = 57/43), bearing an additional benzyl group at the alpha-position, also reacted with carbanions 2'a,b, under thermodynamic conditions, leading to syn-adducts in excellent de (control at the three newly generated stereogenic centers). The adducts were quantitatively transformed into the corresponding beta-gamma-disubstituted gamma-butyrolactones and alpha,beta,gamma-trisubstituted gamma-butyrolactones. (1)H NMR studies (NOE and J-coupling) of these lactones allowed us to determine their configuration at the newly generated chiral centers. The reduction of the C-S bond in adducts syn-(R,S) with Na/Hg, followed by treatment of the resulting products in aqueous acid media, led to enantioenriched beta-benzyl-gamma-hydroxymethyl-gamma-butyrolactones. The conformational equilibrium of enoates E- and Z-1b was evaluated by theoretical calculations (ab initio, MP2/6-31G), and a mechanistic rationale was proposed to explain the observed stereoselectivities. 相似文献
99.
Mrcia Sousa Bispo Maria das Graas Andrade Korn Elane Santos da Boa Morte Leonardo Sena Gomes Teixeira 《Spectrochimica Acta Part B: Atomic Spectroscopy》2002,57(12):2175-2180
An analytical method for separation and pre-concentration of lead in seawater for determination by inductively coupled plasma optical emission spectrometry has been investigated. Lead was retained in the solid phase (0.5 g) composed of co-precipitated naphthalene and alizarin red. The solid phase quantitatively sorbs Pb(II) at pH 8–9, and the metal was eluted using 5.0 ml of 2 mol l−1 nitric acid. The effect of NaCl, KCl, BaCl2, CaCl2, Na2SO4, MgCl2 and Na3PO4 on the sorption of Pb(II) in the solid phase was studied. A set of solutions containing varying amounts of electrolytes (0.5; 1.0; 3.0 and 5.0% m/v) with Pb (50 μg) was prepared and the recommended procedure applied. The Na3PO4 was found to interfere; the other electrolytes did not interfere up to 5% m/v. A pre-concentration factor of 40 was obtained in this analytical procedure. The limit of detection and limit of quantification for Pb(II) were 53 and 176 μg l−1, respectively. Lead was determined in seawater samples collected in Salvador city, Bahia, Brazil. The precision, expressed as R.S.D., was 1.8–4.6%, and the recovery of lead added to seawater samples was 95–97%. 相似文献
100.
A new steroidal saponin was isolated from the leaves of Agave attenuata. Its structure was established as (3beta,beta,25S)-spirostan-3-yl O-beta-D-glucopyranosyl-(1 --> 2)-beta-D-glucopyranosyl-(1 --> 2)-O-[beta-D-glucopyranosyl-(1 --> 3)]-beta-D-glucopyranosyl-(1 --> 4)-beta-D-galactopyranoside. The structural identification was performed using detailed analyses of 1H- and 13C-NMR spectra including 2D NMR spectroscopic techniques (COSY, HETCOR, and COLOC) and chemical conversions. The hemolytic activity of the steroidal saponin was evaluated using an in vitro assay. 相似文献