Monitoring of Polymerized Triglycerides in Deep-Frying Oil by On-Line GPC-FTIR Spectrometry Using the Science Based Calibration Multivariate Approach

On-line gel permeation chromatography Fourier transform infrared (GPC-FTIR) is proposed as detection technique for the determination of the total polymer triacylglyceride (PTG) content in olive oil as an alternative to other conventional detectors such as the evaporative light scattering detector (ELSD) or the refraction index detector (RID). FTIR detection allowed confirmation additionally to quantification of the analytes via their characteristic infrared spectra. For the extraction of chromatograms, a multivariate method called science based calibration (SBC) was used. The SBC method employed a reference spectrum of triacylglycerides (TG) extracted from the injection of a fresh olive oil sample and data obtained from a blank injection as ‘noise’ matrix, to estimate a regression vector subsequently used to predict the relative concentration of the analyte during the GPC run. Results found evidenced that the use of SBC improved the selectivity, sensitivity and repeatability of the GPC-FTIR measurements as compared to the ‘classical’ approach based on the measurement of the spectral area in a defined spectral range. The developed method provided a limit of detection for PTGs of 0.19 mg mL^?1, which corresponds to a 0.65% w/w for an oil sample mass of 300 mg.     

Modeling flexible pharmacophores with distance geometry, scoring, and bound stretching

The study of pharmacophores, i.e., of common features between different ligands, is important for the quantitative identification of "compatible" enzymes and binding species. A pharmacophore-based technique is developed that combines multiple conformations with a distance geometry method to create flexible pharmacophore representations. It uses a set of low-energy conformations combined with a new process we call bound stretching to create sets of distance bounds, which contain all or most of the low-energy conformations. The bounds can be obtained using the exact distances between pairs of atoms from the different low-energy conformations. To avoid missing conformations, we can take advantage of the triangle distance inequality between sets of three points to logically expand a set of upper and lower distance bounds (bound stretching). The flexible pharmacophore can be found using a 3-D maximal common subgraph method, which uses the overlap of distance bounds to determine the overlapping structure. A scoring routine is implemented to select the substructures with the largest overlap because there will typically be many overlaps with the maximum number of overlapping bounds. A case study is presented in which 3-D flexible pharmacophores are generated and used to eliminate potential binding species identified by a 2-D pharmacophore method. A second case study creates flexible pharmacophores from a set of thrombin ligands. These are used to compare the new method with existing pharmacophore identification software.     

Silica-Supported Tantalum Catalysts for Asymmetric Epoxidations of Allyl Alcohols

Tantalum good, titanium bad: This appears to be the case for silica-supported catalysts for the asymmetric epoxidation of allyl alcohols. Complexes such as [SiO-Ta(OEt)(4)] were prepared from silica and [Ta(=CHCMe(3))(CH(2)CMe(3))(3)], and in the presence of a tartrate and an alkyl hydroperoxide, these surface tantalum compounds lead to efficient and convenient catalysts for the asymmetric epoxidation of 2-propen-1-ol (R=H) and trans-2-hexen-1-ol (R=nPr; see reaction).     

Characterization of active species in alumina and silica supported CuCl2 catalysts by EPR

In a recent paper [1] we proposed that a Cu²⁺ species interacting with the support was responsible for maintaining the catalytic activity of CuCl₂ catalysts used in the methane oxyhydrochlorination reaction (CH₄+HCl+O₂ chloromethanes). This species was detected on Al₂O₃ and TiO₂ supports but it did not appear on SiO₂. In this paper we report EPR results which provide a direct characterization of this species and correlate well with the observed trends in activity.

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[1] , Cu²⁺, , CuCl₂, (CH₄+HCl+O₂ ). Al₂O₃ TiO₂, SiO₂. , .

     

A bridge between hyperspherical and integro-differential approaches to the many-body bound states

The solution of the Schrödinger equation can be obtained from the one of a system of coupled differential equations generated from the potential harmonic expansion of the bound-state wave function of a system of identical particles governed by two-body central interactions. It is shown that the system of coupled equations can be transformed into an equivalent integro-differential equation. For three bosons inS states this equation is identical to the Faddeev equation as written by Noyes. The integro-differential equations describing the triton for non-central realisticN-N forces are explicitly given.Laboratoire associé au C.N.R.S.     

Superfluid3He in high magnetic fields: New results

The superfluid A₁ an A₂ transitions have been studied by means of vibrating wire viscosimeters in magnetic fields up to 9.3 T. Using the technique of quick melting of polarized solid (Castaing-Nozières effect) we have succeeded in increasing the superfluid transition temperature from 2.86 to 3.23 mK, which is the highest up to now. Using this method, with some improvements, it should be possible to test some of the present theoretical models for³He. A minimum of the viscosity in the A₁ phase has been observed for the first time. Very close to the A₂ transition an anomaly in the amplitude of the viscometers seems to indicate the presence of a new phase, or some textural change due to dipole locking.Invited talk at the International Conference on Macroscopic Quantum Phenomena, Smolenice Castle, Czechoslovakia, September 18–22, 1989.The authors wish to thank C. C. Kranenburg and C. M. C. M. van Woerkens for their various contributions to the experiments. Very helpful discussions with K. S. Bedell, B. Castaing, H. Capel, P. Nozières, D. Rainer, A. Schakel, and G. A. Vermeulen are gratefully acknowledged. This work was financially supported by the Stichting voor Fundamenteel Onderzoek der Materie F. O. M.     

Area-preserving diffeomorphisms and supermembrane Lorentz invariance

The Lie algebra of area-preserving diffeomorphisms on closed membranes of arbitrary topology is investigated. On the basis of a harmonic decomposition we define the structure constants as well as two other tensors which appear in the supermembrane Lorentz generators. We derive certain identities between these tensors and analyze their validity when the areapreserving diffeomorphisms are approximated bySU(N). One of the additional tensors can then be identified with the invariant symmetric three-index tensor ofSU(N), while the second has no obvious analog. We prove that the Lorentz generators are classically conserved in the light-cone gauge for arbitrary membrane topology, as a consequence of these tensor identities. This formulation allows a systematic study of the violations of Lorentz invariance in theSU(N) approximation.     

Phase diagrams of the transverse Ising antiferromagnet in the presence of the longitudinal magnetic field

In this paper we study the critical behavior of the two-dimensional antiferromagnetic Ising model in both uniform longitudinal (H$H$) and transverse (Ω$\Omega$) magnetic fields. Using the effective-field theory (EFT) with correlation in single site clusters we calculate the phase diagrams in the H−T$H-T$ and Ω−T$\Omega -T$ planes for the square lattice. We have only found second order phase transitions for all values of fields and reentrant behavior was not observed.     

Photoluminescence properties of Co-doped ZnO nanocrystals

We performed photoluminescence experiments on colloidal, Co²⁺-doped ZnO nanocrystals in order to study the electronic properties of Co²⁺ in a ZnO host. Room temperature measurements showed, next to the ZnO exciton and trap emission, an additional emission related to the Co²⁺ dopant. The spectral position and width of this emission does not depend on particle size or Co²⁺ concentration. At 8 K, a series of ZnO bulk phonon replicas appear on the Co²⁺-emission band. We conclude that Co²⁺ ions are strongly localized in the ZnO host, making the formation of a Co²⁺d-band unlikely. Magnetic measurements revealed a paramagnetic behaviour.