Response surface methodology for the optimization of dispersive liquid–liquid microextraction of chloropropanols in human plasma

Chloropropanols are processing toxicants with a potential risk to human health due to the increased intake of processed foods. A rapid and efficient method for the determination of three chloropropanols in human plasma was developed using ultrasound‐assisted dispersive liquid–liquid microextraction. The method involved derivatization and extraction in one step followed by gas chromatography with tandem mass spectrometry analysis. Parameters affecting extraction, such as sample pH, ionic strength, type and volume of dispersive and extraction solvents were optimized by response surface methodology using a pentagonal design. The linear range of the method was 5–200 ng/mL for 1,3‐dichloro‐2‐propanol, 10–200 ng/mL for 2,3‐dichloro‐2‐propanol and 10–400 ng/mL for 3‐chloropropane‐1,2‐diol with the determination coefficients between 0.9989 and 0.9997. The limits of detection were in the range of 0.3–3.2 ng/mL. The precision varied from 1.9 to 10% relative standard deviation (n = 9). The recovery of the method was between 91 and 101%. Advantages such as low consumption of organic solvents and short time of analysis make the method suitable for the biomonitoring of chloropropanols.     

Extrapolation results for <Emphasis Type="Italic">q</Emphasis> < 1

Given a sublinear operator T such that is bounded, it can be shown that is bounded, with constant C/(1−q), for every 0 < q < 1. In this paper, we study the converse result, not only for sequence spaces, but for general measure spaces proving that, if T : L ^q (μ) → X is bounded, with constant C/(1−q), for every and X is Banach, then T : L log (1/L)(μ) → X is bounded. Moreover, this result is optimal. We also show that things are quite different if the Banach condition on X is dropped. This work has been partially supported by MTM2004-02299 and by 2005SGR00556.     

Convolution Operators on Discrete Hardy Spaces

We establish the connection between the boundedness of convolution operators on H^p(ℝ^N) and some related operators on H^p(ℤ^N). The results we obtain here extend the already known for L^p spaces with p > 1. We also study similar results for maximal operators given by convolution with the dilation of a fixed kernel. Our main tools are some known results about functions of exponential type already presented in [BC1] that, in particular, allow us to prove a sampling theorem for functions of exponential type belonging to Hardy spaces     

Functional properties of rearrangement invariant spaces defined in terms of oscillations

Function spaces whose definition involves the quantity f^**-f^*, which measures the oscillation of f^*, have recently attracted plenty of interest and proved to have many applications in various, quite diverse fields. Primary role is played by the spaces S_p(w), with 0<p<∞ and w a weight function on (0,∞), defined as the set of Lebesgue-measurable functions on R such that f^*(∞)=0 and

     

Electrocatalytic and magnetic properties of ultrathin nanostructured iron-melanin films on Au(111)

We have prepared ultrathin, nanostructured melanin films on Au(111) by means of electrochemical self-assembly. These films were characterized by using Auger electron spectroscopy, X-ray absorption near-edge structure spectroscopy, scanning tunneling microscopy, magnetic force microscopy, and electrochemical techniques. Two types of nanostructures are present in the film: melanin nanoparticles and Fe(3)O(4) nanoparticles. The melanin nanoparticles contain Fe bonded to oxygen-containing phenolic groups in an octahedral configuration similar to that found in Fe(2)O(3). The inorganic-organic composite exhibits magnetic properties and catalyzes the electroreduction of hydrogen peroxide in alkaline and neutral electrolyte solutions. The electrocatalytic activity depends on the Fe-bound melanin and appears to be similar to that found for Fe-porphyrins.     

Simultaneous optimization of the solid-phase extraction of organochlorine and organophosphorus pesticides using the desirability function

In a multi-response situation [solid-phase extraction (SPE) of 18 organochlorine and nine organophosphorus pesticides from aqueous solution], several response variables are considered, and the optimization problem is more complex than in the single response case. Experimental design combined with desirability function was applied for the optimization of the SPE of these pesticides in order to obtain optimum operating conditions for routine work. This multi-criterion approach was developed for the simultaneous optimization of multiple responses and it is simple, easy to apply and permits the user to make subjective judgments on the importance of each response. The desirability function is based on the search for a global optimum [D = f (Y1, Y2, ..., Yn)] by the transformation of the measured property to a dimensionless scale for each criterion. The experimental design strategy involved a central composite design. A compromise between conflicting goals, such as achievement of good yields with SPE recoveries of ca. 100% for a large number of analytes with inherent chemical differences, was found by means of the desirability function D.     

PCB separation by HRGC-MS. Fourier analysis for characterizing Aroclor chromatograms

Aroclor and Aroclor mixture chromatograms obtained using temperature programmed high resolution capillary GC coupled with mass spectrometric selective detection have been investigated by Fourier analysis developed for the study of multicomponent chromatograms. The experimental autocorrelation function (EACF), i.e. peak shape and position correlation, showed a retention - structure pattern which could be associated with both the type of Aroclor and the ion used for selective ion monitoring (m/z value). In particular, o-m and m-m isomerization effects were singled out by EACF analysis. By fitting EACF with previously developed theoretical models, it was possible to characterize a specific Aroclor in terms of the number of PCB congeners present in it. The results obtained agreed closely with the typical Aroclor content. For the Aroclor mixture, the distribution of inter-distance between successive peaks was derived. The two first distribution moments obtained agreed with those derived from retention data reported in the literature. The consequences on the separation performance, i.e. the number of singlets, doublets, etc. in the chromatogram, are discussed.     

Comparison of the performances of a particle beam LC-MS interface obtained by standard and modified skimmers

Stainless steel skimmers were made in the technical workshop of our Department and mounted on a commercial Particle Beam interface. Their performances were compared with the standard ones, using three different compounds: benzidine, caffeine and perylene. Library searchable EI spectra were collected with a high quality match and remarkable improvements in the sensitivity were obtained (detection limit of 20 pg for perylene and benzidine), probably due to their better tightness that allowed to widen the skimmer orifices without significantly compromising the ion source vacuum. Also calibration curves showed a good linearity, in the concentration range 10-200 ng/ml.     

Electrochemical self-assembly of alkanethiolate molecules on Ni(111) and polycrystalline Ni surfaces

In this work, the electrochemical formation of alkanethiolate self-assembled monolayers (SAMs) on Ni(111) and polycrystalline Ni surfaces from alkanethiol-containing aqueous 1 M NaOH solutions was studied by combining Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), electrochemical techniques, and density functional theory (DFT) calculations. Results show that alkanethiolates adsorb on Ni concurrent with NiO electroreduction. The resulting surface coverage depends on the applied potential and hydrocarbon chain length. Electrochemical and XPS data reveal that alkanethiolate electroadsorption at room temperature takes place without S-C bond scission, in contrast to previous results from gas-phase adsorption. A complete and dense monolayer, which is stable even at very high cathodic potentials (-1.5 V vs SCE), is formed for dodecanethiol. DFT calculations show that the greater stability against electrodesorption found for alkanethiolate SAMs on Ni, with respect to SAMs on Au, is somewhat related to the larger alkanethiolate adsorption energy but is mainly due to the larger barrier to interfacial electron transfer present in alkanethiolate-covered Ni. A direct consequence of this work is the possibility of using electrochemical self-assembly as a straightforward route to build stable SAMs of long-chained alkanethiolates on Ni surfaces at room temperature.