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231.
Adrián Alvarez-Diaz José M. Costa Rosario Pereiro Alfredo Sanz-Medel 《Analytical and bioanalytical chemistry》2009,394(6):1569-1576
A highly selective molecularly imprinted polymer (MIP) for the recognition of the pesticide carbaryl in water has been synthesized
using halogenated bisphenol A compounds as one of the polymeric precursors and carbaryl as the template molecule. On the basis
of the heavy-atom effect, both the brominated and the iodinated MIPs allowed analyte detection by room-temperature-phosphorescence
measurements. In the presence of an oxygen scavenger (sodium sulphite) the halide, included in the polymeric structure, induced
efficient room-temperature phosphorescence of the analyte (once it had been selectively retained by the MIP). The MIP cavity
can be easily regenerated for subsequent sample injections with 2 mL methanol. The optosensing system developed has demonstrated
high selectivity for carbaryl, even in the presence of other luminophores that could be unspecifically adsorbed onto the MIP
surface. Under optimal experimental conditions, the detection limit for the target molecule was 4 μg/L (3-mL sample injection
volume), and the linear range extended up to 1 mg/L of the analyte. Good reproducibility was achieved (a relative standard
deviation of 3% was obtained for ten replicates of 150 μg/L carbaryl). The synthesized sensing material showed good stability
for at least 3 months after preparation. Finally, the applicability to carbaryl determination in real samples was evaluated
through the successful determination of the pesticide in spiked mineral and tap water samples.
Figure Schematic diagram of carbaryl recognition process by an halogenated molecularly imprinted polymer for room temperature phosphorescence
detection of the analyte. 相似文献
232.
Monaco G Viglione RG Zanasi R Fowler PW 《The journal of physical chemistry. A》2006,110(23):7447-7452
In an axial magnetic field, coronene, corannulene and kekulene support disjoint paratropic-hub and diatropic-rim ring currents. Bond-order and orbital arguments suggest [10,5]-coronene, C30H10, comprising 10 fused pentagons around a central decagon, as a system that should support an inverted diatropic-hub/paratropic-rim pattern of induced currents. The proposal is verified by ipsocentric ab initio mapping of currents, reproduced with the economical pseudo-pi method, thus validating a powerful toolkit for design of (induced) molecular magnets. 相似文献
233.
Ruiz-Guerrero R Vendeuvre C Thiébaut D Bertoncini F Espinat D 《Journal of chromatographic science》2006,44(9):566-573
The monitoring of total sulfur content and speciation of individual sulfur-containing compounds in middle distillates is required for efficient catalyst selection and for a better understanding of the kinetics of the reactions involved in hydrotreament processes. Owing to higher resolution power and enhanced sensitivity, comprehensive two-dimensional gas chromatography (GCxGC) hyphenated to sulfur chemiluminescence detection (SCD) has recently evolved as a powerful tool for improving characterization and identification of sulfur compounds. The aim of this paper is to compare quantitatively GCxGC-SCD and various other methods commonly employed in the petroleum industry, such as X-ray fluorescence, conventional GC-SCD, and high-resolution mass spectrometry, for total sulfur content determination and speciation analysis. Different samples of middle distillates have been analyzed to demonstrate the high potential and important advantages of GCxGC-SCD for innovative and quantitative analysis of sulfur-containing compounds. More accurate and detailed results for benzothiophenes and dibenzothiophenes are presented, showing that GCxGC-SCD should become, in the future, an essential tool for sulfur speciation analysis. 相似文献
234.
The new solvent-free technique called headspace sorptive extraction (HSSE) was used to determine 2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol, 2,4,6-trichloroanisole, 2,3,4,6-tetrachloroanisole, 2,4,6-tribromoanisole, pentachloroanisole in cork stoppers, without grinding them, as these may be responsible for the cork taint off-flavour in wine. The best HSSE sorption kinetics for the target analytes were obtained after submitting the spiked corks to 100 degrees C for 1h, followed by a 30 min stabilization time at room temperature. The stir bar was desorbed in a thermal desorption system coupled to a gas chromatograph-mass spectrometer. The method proposed showed good linearity over the concentration range tested, 1-70 ngg(-1), and correlation coefficients ranged from 0.90 to 0.99 for all the analytes. The reproducibility and repeatability of the method were estimated between 4.91 and 12.67%. The effect of the different cork matrixes on the extraction recovery of the target compounds was studied, with the natural corks showing the higher recovery percentage in relation to agglomerate ones. 相似文献
235.
The Rh2(OAc)4-catalyzed reactions of o-(methoxycarbonyl)-alpha-diazoacetophenone with enantiomerically pure 5-ethoxy-3-p-tolylsulfinylfuran-2(5H)-ones 1a and 1b afford 4,10-epoxybenzo[4,5]cyclohepta[1,2-c]furan-3,9-diones 6a and 6b, in good or moderate yields and in a completely regioselective way. The pi-facial selectivity is complete for 1a, which only yields anti-6a adducts, and very high for 1b. The endo stereoisomers are favored with respect to the exo ones in both reactions. The sulfinyl group significantly increases the reactivity of the dipolarophile as it has been demonstrated by studying the behavior of 5-methoxyfuran-2(5H)-one (3). 相似文献
236.
Martínez R Ratera I Tárraga A Molina P Veciana J 《Chemical communications (Cambridge, England)》2006,(36):3809-3811
Taking advantage of the properties of the ferrocene as a redox and electron donor active unit and the pyrene as a fluorescent unit, dyad 2 shows a fast and reversible redox-switchable fluorescence emission. 相似文献
237.
Photochromic naphthopyran derivatives have been embedded in sol-gel prepared organically modified thin films. The introduction of organic functional groups into a silica matrix allows tailoring the surface of its pores and the polarity of the environment of the embedded host molecules. The photochromic properties of the naphthopyran molecules, such as the spectral properties of the coloured forms and the kinetics of the thermal bleaching, depend strongly on the polarity of the pores where the molecules are located and, hence, on the nature and loading of organic functional groups in the composition of the ormosil matrix. Important changes in the photochromic properties of the films have also been induced by modifications in the sol-gel preparation and processing parameters. The photostability of the photochromic molecules upon prolonged exposition to UV light is strongly related to the nature of the embedding ormosil matrix. The introduction of organic functional groups into the inner pore surface of the matrix, where the dye molecules will be located, affects the stability of the molecules, in terms of the effectiveness of the interaction between the photochromic molecules and the pore surface. 相似文献
238.
Monika Moeder Steffi Schrader Ursula Winkler Rosario Rodil 《Journal of chromatography. A》2010,1217(17):2925-2932
An at-line analysis protocol is presented that allows the determination of four UV filters, two polycyclic musk compounds and caffeine in water at concentration level of ng L−1. The fully automated method includes analytes enrichment by Microextraction by packed sorbent (MEPS) coupled directly to large volume injection-gas chromatography–mass spectrometry. Two common SPE phases, C8 and C18, were examined for their suitability to extract the target substances by MEPS. The analytes were extracted from small sample volumes of 800 μL with recoveries ranging from 46 to 114% for the C8-sorbent and 65–109% for the C18-sorbent. Limits of detection between 34 and 96 ng L−1 enable the determination of the analytes at common environmental concentration levels. Both sorbents showed linear calibration curves for most of the analytes up to a concentration level of 20 ng mL−1. Carryover was minimized by washing the sorbents 10 times with 100 μL methanol. After this thorough cleaning, the MEPS are re-used and up to 70 analyses can be performed with the same sorbent. The fully automated microextraction GC–MS protocol was evaluated for the influence of matrix substances typical for wastewater. Dilution of samples prior to MEPS is recommended when the polar caffeine is present at high concentration. Real water samples were analyzed by the MEPS-GC–MS method and compared to standard SPE. 相似文献
239.
Vibrational analysis of molecular interactions in aqueous glucose solutions. Temperature and concentration effects 总被引:1,自引:0,他引:1
Gallina ME Sassi P Paolantoni M Morresi A Cataliotti RS 《The journal of physical chemistry. B》2006,110(17):8856-8864
A vibrational analysis using FTIR and Raman spectroscopies was carried out on aqueous glucose solutions with a wide range of solute molar fractions and temperatures. The analysis was aimed at revealing structural changes in the local hydrogen-bonding (HB) network of liquid water, correlating these with the conservative properties of biomolecules, and comparing them with those of other sugars. The results of our measurements clearly show that the action of glucose is 2-fold; on one hand, there is a linkage with free hydroxyls of water; on the other, there is a slight lessening of the ordered (tetrahedral) H-bonded assembly of bulk H(2)O. These opposite effects do not balance each other, so the average HB interaction strength decreases on increasing glucose concentration. As a result, there is a reduction in the temperature dependence of solutions structure. In our opinion, this could be related to the low bioprotective action of this carbohydrate. 相似文献
240.
Fernández MC Sánchez CC Niño RR Patino JM 《The journal of physical chemistry. B》2006,110(47):24212-24221
In this work we have analyzed the penetration of betalactoglobulin into a monoglyceride monolayer (monopalmitin or monoolein) spread at the air-water interface and its effects on the structural, dilatational, and topographical characteristics of mixed films. Dynamic tensiometry, surface film balance, Brewster angle microscopy (BAM), and surface dilatational rheology have been used, maintaining the temperature constant at 20 degrees C and the pH and ionic strength at 7 and 0.05 M, respectively. The initial surface pressure (mN/m) of the spread monoglyceride monolayer (pii(MONOGLYCERIDE)) at 10, 20, and the collapse point is the variable studied. Beta-lactoglobulin can penetrate into a spread monoglyceride monolayer at every surface pressure. The penetration of beta-lactoglobulin into the monoglyceride monolayer with a more condensed structure, at the collapse point of the monoglyceride, requires monoglyceride molecular loss by collapse and/or desorption. However, the structural, topographical, and dilatational characteristics of monoglyceride penetrated by beta-lactoglobulin mixed monolayers are essentially dominated by the presence of monoglyceride (either monopalmitin or monoolein) in the mixed film. In fact, monoglyceride molecules have the capacity to re-enter the monolayer after expansion and recompression of the mixed monolayer. Thus, monoglyceride molecular loss by collapse and/or desorption is reversible. The topography of the monolayer under dynamic conditions corroborates these conclusions. 相似文献