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991.
Marín JM Sancho JV Pozo OJ López FJ Hernández F 《Journal of chromatography. A》2006,1133(1-2):204-214
Two on-line SPE-LC-ESI-MS/MS methods have been developed for the rapid determination and confirmation of 18 polar pesticides and nine transformation products (TPs) in water samples. Given the very different physico-chemical characteristics of the analytes, it was not feasible the simultaneous determination of all selected compounds in only one method. Thus, it was necessary to use heptafluorobutyric acid and formic acid in order to obtain good retention in the SPE cartridge for basic and acidic analytes, respectively. The developed analytical methodology based on the direct injection of 2 mL of water sample in the system allowed the quantification of all analytes at the 25 ng/L level (LOQ) with limits of detection normally lower than 5 ng/L. Satisfactory recoveries (70-110%) were obtained for most compounds in ground and surface water samples. Some exceptions were found mainly in surface water, due to the ion suppression produced by the higher amount of matrix interferents in these samples. The acquisition of two MS/MS transitions for each compound allowed the reliable confirmation of positive findings even at the LOQ level. The developed methodology was applied to real ground and surface water samples showing the interest of including TPs in monitoring methods, as several of them were found at concentrations higher than that of parent compounds. 相似文献
992.
Mondragón-Parada ME Nájera-Martínez M Juárez-Ramírez C Galíndez-Mayer J Ruiz-Ordaz N Cristiani-Urbina E 《Applied biochemistry and biotechnology》2006,134(3):223-232
The main purpose of this work was to isolate and characterize lactic acid bacteria (LAB) strains to be used for biomass production using a whey-based medium supplemented with an ammonium salt and with very low levels of yeast extract (0.25 g/L). Five strains of LAB were isolated from naturally soured milk after enrichment in whey-based medium. One bacterial isolate, designated MNM2, exhibited a remarkable capability to utilize whey lactose and give a high biomass yield on lactose. This strain was identified as Lactobacillus casei by its 16S rDNA sequence. A kinetic study of cell growth, lactose consumption, and titratable acidity production of this bacterial strain was performed in a bioreactor. The biomass yield on lactose, the percentage of lactose consumption, and the maximum increase in cell mass obtained in the bioreactor were 0.165 g of biomass/g of lactose, 100%, and 2.0 g/L, respectively, which were 1.44, 1.11, and 2.35 times higher than those found in flask cultures. The results suggest that it is possible to produce LAB biomass from a whey-based medium supplemented with minimal amounts of yeast extract. 相似文献
993.
Santos RC Bernardes CE Diogo HP Piedade MF Canongia Lopes JN Minas da Piedade ME 《The journal of physical chemistry. A》2006,110(6):2299-2307
The energetics of the thermal dimerization of acenaphthylene to give Z- or E-heptacyclene was investigated. The standard molar enthalpy of the formation of monoclinic Z- and E-heptacyclene isomers at 298.15 K was determined as Delta(f)H(m)o (E-C24H16, cr) = 269.3 +/- 5.6 kJ x mol(-1) and Delta(f)H(m)o (Z-C24H16, cr) = 317.7 +/- 5.6 kJ x mol(-1), respectively, by microcombustion calorimetry. The corresponding enthalpies of sublimation, Delta(sub)H(m)o (E-C24H16) = (149.0 +/- 3.1) kJ x mol(-1) and Delta(sub)H(m)o (Z-C24H16) = (128.5 +/- 2.3) kJ x mol(-1) were also obtained by Knudsen effusion and Calvet-drop microcalorimetry methods, leading to Delta(f)H(m)o (E-C24H16, g) = (418.3 +/- 6.4) kJ x mol(-1) and Delta(f)H(m)o (Z-C24H16, g) = (446.2 +/- 6.1) kJ x mol(-1), respectively. These results, in conjunction with the reported enthalpies of formation of solid and gaseous acenaphthylene, and the entropies of acenaphthylene and both hepatcyclene isomers obtained by the B3LYP/6-31G(d,p) method led to the conclusion that at 298.15 K the thermal dimerization of acenaphthylene is considerably exothermic and exergonic in the solid and gaseous states (although more favorable when the E isomer is the product), suggesting that the nonobservation of the reaction under these conditions is of kinetic nature. A full determination of the molecular and crystal structure of the E dimer by X-ray diffraction is reported for the first time. Finally, molecular dynamics computer simulations on acenaphthylene and the heptacyclene solids were carried out and the results discussed in light of the corresponding structural and Delta(sub)H(m)o data experimentally obtained. 相似文献
994.
995.
Tejedor D Santos-Expósito A García-Tellado F 《Chemical communications (Cambridge, England)》2006,(25):2667-2669
A novel ABB' 3 component reaction (3-CR) system based on the organocatalyzed homoaldolic condensation of alpha-ketoesters in the presence of terminal conjugated alkynoates is described. 相似文献
996.
In this work, we analyze a series of o-hydroxyaryl aldehydes to discuss the interrelation between the resonance-assisted hydrogen bond (RAHB) formation and the aromaticity of the adjacent aromatic rings. As compared to the nonaromatic reference species (malonaldehyde), the studied compounds can be separated into two groups: first, the set of systems that have a stronger RAHB than that of the reference species, for which there is a Kekulé structure with a localized double CC bond linking substituted carbon atoms; and second, the systems having a weaker RAHB than that of the reference species, for which only pi-electrons coming from a localized Clar pi-sextet can be involved in the RAHB. As to aromaticity, there is a clear reduction of aromaticity in the substituted ipso ring for the former group of systems due to the formation of the RAHB, while for the latter group of species only a slight change of local aromaticity is observed in the substituted ipso ring. 相似文献
997.
Bustamante-Rangel M Delgado-Zamarreño MM Sánchez-Pérez A Carabias-Martínez R 《Journal of chromatography. A》2006,1125(2):270-273
A microemulsion electrokinetic chromatographic method was used to separate fat-soluble vitamins. The separation of retinol, cholecalciferol, and delta- and alpha-tocopherol was performed using a microemulsion containing 0.75% (v/v) n-heptane, 30 mM bis(2-ethylhexyl)sodium sulfosuccinate (AOT), 5% (v/v) 1-butanol, 15% (v/v) 1-propanol and 15% (v/v) methanol in 20mM boric acid-sodium borate buffer. The effect of the different microemulsion constituents was studied, including the type and concentration of surfactant, buffer, oil and co-surfactants. The presence of methanol in the microemulsion was found to be necessary to achieve the separation of the tocopherols. Detection was carried out at 200, 265 and 325 nm for the tocopherols, cholecalciferol and retinol, respectively. Calibration curves and precision data were obtained for each analyte. Good linear relationships were found between the analytical signal and the analytes concentration in the 25-500 mg L(-1) for retinol and cholecalciferol, and 25-300 mg L(-1) for tocopherols ranges. The precision of the method afforded relative standard deviations in the 4.0-10% range. 相似文献
998.
Febles M Pérez-Hernandez N Pérez C Rodríguez ML Foces-Foces C Roux MV Morales EQ Buntkowsky G Limbach HH Martín JD 《Journal of the American Chemical Society》2006,128(31):10008-10009
Water molecules confined inside narrow pores are of great importance in understanding the structure, stability, and function of water channels. Here we report that besides the H-bonding water that structures the pore, the permanent presence of a significant, fast-moving fraction of incompletely H-bonded water molecules inside the pore should control the free entry and exit of water. This is achieved by means of complementary DSC and solid-state NMR studies. We also present compelling evidence from X-ray diffraction data that the cluster formed by six water molecules in the most stable cage-like structure is sufficiently hydrophobic to be stably adsorbed in a nonpolar environment. 相似文献
999.
Bekesová S Kovácik V Chmelík J Kovác P 《European journal of mass spectrometry (Chichester, England)》2006,12(1):43-50
Saccharides (mono through hexasaccharides) that mimic the terminal epitopes of O-antigens of Vibrio cholerae O:1, serotypes Ogawa and Inaba, were studied by electrospray ion trap (ESI IT) mass spectrometry (MS) in the negative mode. Anionized adducts are the characteristic ions formed by the capture of H(3)O(2)(-) under the condition of ESI MS analysis. The reactive species are produced by reaction of hydroxyl anions with the molecule of water. Thus the [M + H(3)O(2)](-) have the highest m/z value in the ESI IT negative mass spectra. After dissociation of adducts by loss of 2H(2)O the [M-H](-) ions are produced. The fragmentation pathways were confirmed by multistage measurements (MS(n)). The predominant pathway of fragmentation of the mono- and oligomers is the elimination of a molecule of alpha- hydroxy--gammabutyrolactone from the 4-(3-deoxy-L-glycero-tetronamido) group. The other characteristic pathway occurs by shortening the length of oligosaccharides. In this way, conversion of the Ogawa to Inaba fragments takes place under the conditions of measurement. Negative ESI MS/MS provided sufficient information about molecular mass, the number of saccharide residues, basic structure of saccharides, about the tetronamide part of the compounds investigated and allowed Ogawa and Inaba serotypes to be distinguished. 相似文献
1000.
Wang J Scampicchio M Laocharoensuk R Valentini F Gonzalez-García O Burdick J 《Journal of the American Chemical Society》2006,128(14):4562-4563
Nanowires have received considerable attention owing to their broad potential applications. We report here on the application of nanowires for magnetic control of the electrochemical reactivity and demonstrate how one can modulate the electrocatalytic activity by orienting catalytic nanowires at different angles. Unlike early "on/off" magnetic switching studies based on functionalized magnetic spheres, the present magnetoswitchable protocol relies on modulating the electrochemical reactivity without removing the magnetic material from the surface. Such behavior is attributed to the reversible blocking of the redox processes and to changes in the tortuosity-dependent flux rate. The nanowire-based magnetoswitchable protocol may be extremely useful for adjusting the electrochemical reactivity, such as for tuning the power output of fuel cells (rather than switching the power on/off). 相似文献