31P NMR spectroscopy in the quality control and authentication of extra-virgin olive oil: a review of recent progress

This review is a brief account on the application of a novel methodology to the quality control and authentication of extra-virgin olive oil. This methodology is based on the derivatization of the labile hydrogens of functional groups, such as hydroxyl and carboxyl groups, of olive oil constituents with the phosphorus reagent 2-chloro-4,4,5,5-tetramethyldioxaphospholane, and the use of the (31)P chemical shifts to identify the phosphitylated compounds. Various experimental aspects such as pertinent instrumentation, sample preparation, acquisition parameters and properties of the phosphorus reagent are reviewed. The strategy to assign the (31)P signals of the phosphitylated model compounds and olive oil constituents by employing 1D and 2D NMR experiments is presented. Finally, the capability of this technique to assess the quality and the genuineness of extra-virgin olive oil and to detect fraud is discussed.     

Non-Kramers' behavior of the chain local dynamics of PVC in dilute solution. Carbon-13 NMR relaxation study

Carbon-13 spin-lattice, spin-spin relaxation times, and NOE values were measured as a function of temperature at two magnetic fields for poly(vinyl chloride) (PVC) in three solvents: chloroform, dioxane, and dimethyl sulfoxide. The relaxation data were interpreted in terms of chain local motions by using the bimodal time-correlation function of the Dejean-Laupretre-Monnerie (DLM) model. Using this model, the correlation times obtained in this study, as well as those from an earlier study in dibutyl phthalate and 1,1,2,2-tetrachloroethane did not follow a linear relationship with solvent viscosity. Instead, the chain local dynamics showed a 0.60 power dependence on solvent viscosity, indicating that PVC deviates from the hydrodynamic Kramers' theory. © 1997 John Wiley & Sons, Inc.     

Detection of refined olive oil adulteration with refined hazelnut oil by employing NMR spectroscopy and multivariate statistical analysis

NMR spectroscopy was employed for the detection of adulteration of refined olive oil with refined hazelnut oil. Fatty acids and iodine number were determined by ¹H NMR, whereas ³¹P NMR was used for the quantification of minor compounds including phenolic compounds, diacylglycerols, sterols, and free fatty acids (free acidity). Classification of the refined oils based on their fatty acids content and the concentration of their minor compounds was achieved by using the forward stepwise canonical discriminant analysis (CDA) and the classification binary trees (CBTs). Both methods provided good discrimination between the refined hazelnut and olive oils. Different admixtures of refined olive oils with refined hazelnut oils were prepared and analyzed by ¹H NMR and ³¹P NMR spectroscopy. Subsequent application of CDA to the NMR data allowed the detection of the presence of refined hazelnut oils in refined olive oils at percentages higher than 5%. Application of the non-linear classification method of the binary trees offered better possibilities of measuring adulteration of the refined olive oils at a lower limit of detection than that obtained by the CDA method.     

On the equations defining toric l.c.i.-singularities

Based on Nakajima's Classification Theorem we describe the precise form of the binomial equations which determine toric locally complete intersection (``l.c.i.') singularities.

     

Mesomorphic-like character of long-chain amine salts formed by template neutralization on polyacids

Several examples of monomeric and polymerized surfactants exhibiting liquid-crystalline behaviour have recently been reported. In the present investigation a novel process for the formation of liquid crystals is introduced, according to which certain functionalized polymers induce mesomorphism when they react with appropriate amines. For instance, neutralization of polyacrylic or polymaleic acid with long-chain amines forms alkylammonium salt surfactants which exhibit mesomorphic-like character. In this type of experiment, however, the known lamellar structure of alkylammonium salts was modified by this so-called template neutralization. The carboxylate groups, due to their location on the polymeric chain, appear to exert a topochemical effect on alkylammonium moieties which in turn affect the mesomorphic behaviour compared with that of common surfactants. The mesomorphic behaviour of these materials was established by optical microscopy and differential scanning calorimetry.     

Ge quantum dot molecules and crystals: Preparation and properties

Templated self-organization has been used to prepare two-dimensional arrays as well as three-dimensional quantum dot crystals (QDC) containing Ge dots in a Si host crystal. Si(1 0 0) substrates have been patterned with two-dimensional hole gratings using extreme ultra-violet interference lithography (EUV-IL) and reactive ion etching. The EUV-IL was realized by multiple beam diffraction using Cr gratings on SiN_x membranes fabricated by e-beam lithography. Si/Ge overgrowth was performed by molecular beam epitaxy. The impact of the microscopic shape and size of the prepattern using the mask design and the EUV-IL exposure dose as parameters on the Ge dot nucleation has been studied with atomic force microscopy, transmission electron microscopy and photoluminescence measurements. Adjusting the growth parameters in multiple layer deposition the initial two-dimensional configuration was transferred into three-dimensional QDC.