Liquid chromatography with mass spectrometry in tandem mode applied for the identification of wine markers in residues from ancient Egyptian vessels

Presented in this paper is a new method for the identification of tartaric acid as a wine marker in archaeological residues from Egyptian vessels using liquid chromatography with mass spectrometry in tandem mode (LC/MS/MS). Owing to the special characteristics of these samples, such as the dryness and the small quantity available for analysis, it was necessary to have a very sensitive and highly specific analytical method to detect tartaric acid at trace levels in the residues. Furthermore, an alkaline fusion was carried out to identify syringic acid derived from malvidin as a red wine marker, in a deposit residue from a wine jar found at the tomb of king Tutankhamun. Malvidin-3-glucoside, the main anthocyanin that gives young wines their red color, polymerizes with aging into more stable pigments. However, the presence of malvidin in ancient residues can be proved by alkaline fusion of the residue to release syringic acid from the pigment, which has been identified, here for the first time, by using the LC/MS/MS method revealing the red grape origin of an ancient Egyptian wine residue.     

Second-order advantage achieved with four-way fluorescence excitation-emission-kinetic data processed by parallel factor analysis and trilinear least-squares. Determination of methotrexate and leucovorin in human urine

Four-way fluorescence data recorded by following the kinetic evolution of excitation-emission fluorescence matrices (EEMs) have been analyzed by parallel factor analysis and trilinear least-squares algorithms. These methodologies exploit the second-order advantage of the studied data, allowing analyte concentrations to be estimated even in the presence of an uncalibrated fluorescent background. They were applied to the simultaneous determination of the components of the anticancer combination of methotrexate and leucovorin in human urine samples. Both analytes were converted into highly fluorescent compounds by oxidation with potassium permanganate, and the kinetics of the reaction was continuously monitored by recording full EEM of the samples at different reaction times. A commercial fast scanning spectrofluorometer has been used for the first time to measure the four-way EEM kinetic data. The rapid scanning instrument allows the acquisition of a complete EEM in 12 s at a wavelength scanning speed of 24 000 nm/min. The emission spectra were recorded from 335 to 490 nm at 5-nm intervals, exciting from 255 to 315 nm at 6-nm intervals. Ten successive EEMs were measured at 72-s intervals, to follow the fluorescence kinetic evolution of the mixture components. Good recoveries were obtained in synthetic binary samples and also in spiked urine samples. The excitation, emission, and kinetic time profiles recovered by both chemometric techniques are in good agreement with experimental observations.     

Decoding two-dimensional complex multicomponent separations by autocovariance function

A new method for decoding two-dimensional (2D) multicomponent separations based on the use of the 2D Autocovariance function (2D-ACVF) has been developed. Theoretical models of single component (SC) spot distributions in 2D separations, both random and structured, are developed as the basis for a nonlinear estimation of both sample and separation system parameters from experimental 2D separations. The number of SCs, the average spot size, the spot capacity, and the saturation factor can be evaluated in the case of random SC spot patterns. The procedure was validated by extensive numerical simulation under conditions close to those usually found in GC x GC or 2D-polyacrylamid gel electrophoresis of proteins. The worse precision degree was no greater than 10% in the case of maximum spot density. This imprecision was fully accounted for, and it seems acceptable owing to the intrinsic statistical character of the estimation method. Structured multicomponent 2D separations, where SCs are linked by linear relationships, give rise to specific structured patterns in 2D-ACVF plots from which the parameters (phase and frequency) of the structured SC sequences can be evaluated: the study of 2D-ACVF makes it possible to decode multicomponent 2D separation, that is, to determine the number, relative abundance, and structural similarities of the single components. Pertinent expressions of the theoretical 2D-ACVF were derived for simple cases, and a procedure for decoding cases of structured 2D separations was developed and applied. It was shown that 2D separations containing both random and structured patterns of SC spots give rise to 2D-EACVF, which is the superimposition of the two component parts. This feature allows one, in principle, to decode the two components. The relevance of these results for Giddings sample dimensionality and separation dimensionality and their effective experimental evaluation is discussed.     

An optical spot test for the detection of dopamine in human urine using stabilized in air lipid films

The present technique describes a simple, sensitive spot test for the rapid one-shot detection of dopamine in human urine using lipid films with incorporated resorcin[4]arene receptor that are synthesized by a chemical reaction with a methacrylate polymer on a glass fiber filter. The lipid films without the receptor provided fluorescence under a UV lamp. The use of the receptor in these films quenched this fluorescence, and the color became similar to that of the filters without the lipid films. A drop of dopamine or urine containing this stimulant provided a "switching on" of the fluorescence, which allows the rapid detection of this stimulant in human urine at 10(-8) M concentrations. The novelty of the present work is that it opens new routes in the field of biosensing, i.e., development of sensitive, rapid, and simple methods for detecting species based on the fluorescence of the lipid membranes on a polymer film, and provides a spot test technique for the rapid detection of dopamine. The effect of potent interferences including a wide range of compounds usually found in human urine (i.e., ascorbic aid, glucose, leucine, glycine, tartrate, citrate, bicarbonate, and caffeine) was examined using an aqueous buffered solution that contained the potent interference and dopamine at two lower concentration levels (i.e., 3 x 10(-8)-10(-8) M). The effect of proteins and lipids was also investigated at these two lower dopamine concentration levels in aqueous buffered solution. The results showed no interferences from all these constituents at concentrations usually found in human urine samples; for example, albumin up to 3.22 g/L concentration levels did not provide any interference (i.e., no fluorescence). A drop of urine containing this stimulant provided similar results, i.e., a "switching on" of the fluorescence that allows a technique for the rapid detection of this stimulant in human urine at 10(-8) M concentrations. The technique is not based on a calibration graph but is a semiquantitative method for the detection of dopamine in real samples of urine that can be complimentary to HPLC methods. The difference in color between the samples containing dopamine at concentration levels of 10(-8)-10(-7) M can be easily distinguished by naked eye and a digital camera. An increase of dopamine concentration from 10(-8) to 10(-7) M makes the color more blue whereas the color of the filters remains purple in the blank test (i.e., addition of a urine sample without dopamine or dopamine at concentration levels of 10(-9) M to the filters that contain the lipid membranes with incorporated receptor). The reproducibility of the method was checked in approximately 100 samples, and all of them were found to provide similar results. Note that it was also found that the colors remain stable in the samples containing dopamine for periods of more than two months.     

MIPAS-ENVISAT limb-sounding measurements: trade-off study for improvement of horizontal resolution

The Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) is a limb-scanning spectrometer that has operated onboard the Environmental Satellite since the end of March 2002. Common features of limb-scanning experiments are both high vertical resolution and poor horizontal resolution. We exploit the two-dimensional geo-fit retrieval approach [Appl. Opt. 40, 1872-1875 (2001)] to investigate the possibility of improving the horizontal resolution of MIPAS measurements. Two different strategies are considered for this purpose, one exploiting the possibility (offered by the geo-fit analysis method) for an arbitrary definition of the retrieval grid, the other based on the possibility of saving measurement time by degrading the spectral resolution of the interferometer. The performances of the two strategies are compared in terms of the trade-off between the attained horizontal resolution and the retrieval precision. We find that for ozone it is possible to improve by a factor of 2 the horizontal resolution, which in the nominal measurement plan is approximately 530 km. This improvement corresponds to a degradation of the retrieval precision, which on average varies from a factor of 1.4 to 2.5, depending on the adopted spectral resolution.     

Imaginary refractive-index effects on desert-aerosol extinction versus backscatter relationships at 351 nm: numerical computations and comparison with Raman lidar measurements

A numerical model is used to investigate the dependence at 351 nm of desert-aerosol extinction and backscatter coefficients on particle imaginary refractive index (mi). Three ranges (-0.005 < or = mi < or = -0.001, -0.01 < or = mi < or = -0.001, and -0.02 < or = mi < or = -0.001) are considered, showing that backscatter coefficients are reduced as /mi/ increases, whereas extinction coefficients are weakly dependent on mi. Numerical results are compared with extinction and backscatter coefficients retrieved by elastic Raman lidar measurements performed during Saharan dust storms over the Mediterranean Sea. The comparison indicates that a range of -0.01 to -0.001 can be representative of Saharan dust aerosols and that the nonsphericity of mineral particles must be considered.     

Gated fiber-optic-coupled detector for in vivo real-time radiation dosimetry

Gated detection of the output of a fiber-optic-coupled radiation dosimeter effectively eliminated the direct contribution of Cerenkov radiation to the signal. The radiation source was an external beam radiotherapy machine that provided pulses of 6-MeV x rays. Gated detection was used to discriminate the signal collected during the radiation pulses, including Cerenkov interference, from the signal collected between the radiation pulses due only to phosphorescence from the Cu(1+)-doped glass detector. Gated detection of the long-lived phosphorescence of the Cu(1+)-doped glass provided real-time dose measurements that were linear with the absorbed dose and that were accurate for all field sizes studied.     

Flexible Multibody Systems Models Using Composite Materials Components

The use of a multibody methodology to describe the large motion of complex systems that experience structural deformations enables to represent the complete system motion, the relative kinematics between the components involved, the deformation of the structural members and the inertia coupling between the large rigid body motion and the system elastodynamics. In this work, the flexible multibody dynamics formulations of complex models are extended to include elastic components made of composite materials, which may be laminated and anisotropic. The deformation of any structural member must be elastic and linear, when described in a coordinate frame fixed to one or more material points of its domain, regardless of the complexity of its geometry. To achieve the proposed flexible multibody formulation, a finite element model for each flexible body is used. For the beam composite material elements, the sections properties are found using an asymptotic procedure that involves a two-dimensional finite element analysis of their cross-section. The equations of motion of the flexible multibody system are solved using an augmented Lagrangian formulation and the accelerations and velocities are integrated in time using a multi-step multi-order integration algorithm based on the Gear method.     

Laplace Plane Analysis of Transient Impedance Between Acupuncture Points Li-4 and Li-12

AC impedance between two acupuncture points (Li-4 and Li-12) and two pairs of anatomically similar points with the same separation was studied via Laplace plane analysis of the time domain current response to a predetermined voltage perturbation. The series resistance between the two acupuncture points was found to be significantly lower than between either pair of control points. The characteristic impedance of an equivalent transmission line was lower and the signal propagation velocity higher for the acupuncture point system as compared to both controls.