The application of NMR and MS methods for detection of adulteration of wine,fruit juices,and olive oil. A review

This review covers two important techniques, high resolution nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry (MS), used to characterize food products and detect possible adulteration of wine, fruit juices, and olive oil, all important products of the Mediterranean Basin. Emphasis is placed on the complementary use of SNIF-NMR (site-specific natural isotopic fractionation nuclear magnetic resonance) and IRMS (isotope-ratio mass spectrometry) in association with chemometric methods for detecting the adulteration.     

A study of low level selenium determination by hydride generation atomic fluorescence spectrometry in water soluble protein and peptide fractions

Development of a method for very low level selenium determination in water soluble protein and peptide fractions, obtained after various separation procedures, is presented. A hydride generation atomic fluorescence spectrometry (HG-AFS) detection system was optimised and the influence of Cu(II), Sb(V), As(III) and HNO₃ interferences in the measurement of Se by HG-AFS was investigated. A destruction procedure using HNO₃ and H₂O₂ was also optimised and the average recovery of the digestion of a solution of selenomethioneine was 92 ± 4% (n=14). Combination of this digestion with the detection system gave reliable results. Accuracy was tested by comparison with two independent methods. A very low detection limit (DL) of 0.2 ng/g of measuring solution was achieved. The whole procedure from weighing to measuring was performed in the same Teflon tube. The addition of HNO₃ to the fractions before long term storage at -20°C was necessary to prevent adsorption on the test tubes.Selenium was measured in water soluble protein and peptide fractions obtained after extraction, and Sephadex G-75 chromatography performed on liver samples from: i) hens exposed to As₂O₃, ii) hens fed with a high fat feed and iii) the certified reference material dogfish liver (CRM DOLT-2). Because of the very low DL we were able to observe the Se distribution in chromatographic fractions of samples of organisms which were not exposed to excess amounts of Se. The presence of selenium associated with metallothioneins was observed.     

Parallel solution-phase synthesis of (Z)-3-(arylamino)-2,3-dehydroalanine derivatives and solid-phase synthesis of fused pyrimidones

N-Protected (Z)-3-(arylamino)-2,3-dehydroalanine esters 5 and 10 were prepared in one step from methyl (Z)-2-acylamino-3-(dimethylamino)prop-2-enoates 3 and 9 and anilines 4 employing a parallel solution-phase synthetic approach. In most cases, analytically pure products 5 and 10 were obtained. On the other hand, a three-step parallel solid-phase synthesis of 2-acetylamino-4H-azino[1,2-x]pyrimidin-4-ones 15 via the polymer-bound methyl (Z)-2-acetylamino-3-(dimethylamino)prop-2-enoate (12) was also developed.     

In situ Fourier transform infrared spectroscopy as an efficient tool for determination of reaction kinetics

The performance of new FTIR-based monitoring technology to representatively determine reaction kinetics has been demonstrated on an example of homogeneously catalyzed liquid-phase sucrose hydrolysis to fructose and glucose. The reaction kinetics were investigated by using the ReactIR 1000 reaction analysis system, which enables determination of the component concentration from its characteristic FTIR spectrum. During the sucrose inversion, the ReactIR 1000 instrument connected to a computer controlled standard glass batch reactor provided the required operating conditions and information about the component concentration in real-time. We have studied the influence of hydrogen ion concentration, temperature and initial concentration of sucrose on the sucrose disappearance rate. It was found out that the inversion of sucrose is an irreversible reaction, which is not affected by the formation of fructose and glucose in the liquid-phase. Then, the parameters of the kinetic model (i.e., reaction rate constant and activation energy) were calculated. A comparison of the model output and the measured data showed that the kinetics of the sucrose inversion could be well described by means of the pseudo first-order kinetic model. Finally, the method of determining the kinetic model by FTIR spectroscopy was verified by comparing the results obtained in the batch reactor with the results obtained in the continuously stirred tank reactor.     

Excluded volume driven counterion condensation inside nanotubes in a concave electrical double layer model

The physical properties of organic nanotubes attract increasing attention due to their potential benefit in technology, biology and medicine. We study the effect of ion size on the electrical properties of cylindrical nanotubes filled with electrolyte solution within a modified Poisson-Boltzmann (PB) approach. For comparison purposes, small hollow nanospheres filled with electrolyte solution are considered. The finite size of the particles in the inner electrolyte solution is described by the excluded volume effect within a lattice statistics approach. We found that an increased ion size reduces the number of counterions near the charged inner surface of the nanotube, leading to an enlarged electrostatic surface potential. The concentration of counterions close to the inner surface saturates for higher surface charge densities and larger ions. In the case of saturation, the closest counterion packing is achieved, all lattice sites near the surface are occupied and an actual counterion condensation is observed. By contrast, the counterion concentration at the axis of the nanotube steadily increases with increasing surface charge density. This growth is more pronounced for smaller nanotube radii and larger ions. At larger nanotube radii for small ion size counterion condensation may also be observed according to the Tsao criterion, i.e. the counterion concentration at the centre is independent of the number of counterions in the system. With decreasing radius the Tsao condensation effect is shifted towards physiologically unrealistic surface charge densities.     

Investigation of the Declared Value of Selenium in Food Supplements by HG-AFS

The method of hydride generation atomic fluorescence spectrometry (HG-AFS) was optimised for determination of selenium in food supplements. Due to the high and varied content of Cu, Mg and Zn in the samples, the standard addition method was found to be the most appropriate. The reliability of the method was checked by the independent method of radiochemical neutron activation analysis, and good agreement was found between the two methods. HG-AFS is simple and rapid for Se determination in food supplements based on minerals. Agreement between the selenium values found and declared was worse than 10% in 9 out of 13 supplements. Furthermore, 2 of the 14 supplements did not comply with the recommendations stated in the 27^th edition of the U.S. Pharmacopoeia, which states that minerals and vitamins in food supplements should be in the range of 90 and 200% of the declared value.     

Determination of mechanism of thermal decomposition of Mg,Ca and Zn hydrazidocarbonates by evolved gas analysis

Hydrazo-carbonates are complex compounds and products of the reactions between solutions of metal ion and solutions of hydrazido-carbonic acid. The decomposition of Mg(N₂H₃COO)₂. 2H₂O, Ca(N₂H₃COO)₂·H₂O and Zn(N₂H₃COO)₂ in inert atmosphere were studied. By classical thermoanalytical methods and data on the composition of the intermediates and final products the mechanisms of the thermal decomposition could not be resolved therefore also evolved gas analysis was used (EGA). The first step of thermal decomposition of Ca and Mg hydrazidocarbonates is dehydration. With the heating the decomposition of the hydrazido-carbonates proceeds under evolution of the ammonia, carbon monoxide and/or nitrogen and carbon dioxide giving as the intermediates for calcium and magnesium compounds the corresponding carbonates oxides as the final products. The zinc compound decomposes to the oxide, ZnO but also zinc cyanamide was detected during to the thermal treatment.     

Photocatalytic TiO2 Coatings: Effect of Substrate and Template

Summary. Transparent TiO₂ films with a high photodegradation activity towards an azo dye in aqueous solution were prepared by sol–gel processing. Films on soda–lime glass supports protected with a thin silica barrier layer exhibited better crystallization and monodisperse nanoparticles, higher absorption of light below 370 nm, and higher photocatalytic activity than those films deposited on bare glass supports proving the detrimental effect of interdiffused sodium ions on the development of the anatase nanostructure. The effect of substrate was more pronounced in thinner films (300 nm) than in thicker ones (1200 nm), which were achieved by adding a template (i.e. Pluronic F127) to the sol.     

Synthesis and Structure Investigations of Potential Sedative and Anticonvulsant Hydroxy- and Acetoxy-N-(3-oxobutyl)-pyrido[2,3-d]pyridazinonesa

Summary.  Novel N-(3-oxobutyl)-hydroxy- and acetoxypyrido[2,3-d]pyridazinones were synthesized and tested in vivo for their sedative and anticonvulsant activity. The Michael-type reaction of quinolinic acid hydrazide and methyl vinyl ketone afforded a mixture of two isomers, 5-hydroxy-N ⁷-(3-oxobutyl)-pyrido[2,3-d]pyridazin-8(7H)-one and 8-hydroxy-N ⁶-(3-oxobutyl)-pyrido[2,3,-d]pyridazin-5-(6H)-one, in a ratio of 2:1 which were separated by crystallization. Subsequent acetylation of both isomers yielded the corresponding 5- and 8-acetoxy compounds. The structures of the compounds were proven and completely assigned on the basis of ¹H, ¹³C, ¹⁵N NMR, and 1D NOE difference spectra as well as 2D C,H-correlation experiments. Preliminary pharmacological tests showed low acute toxicity with a LD ₅₀ > 1000 mg/kg in the mouse and sedative activity for the title compounds. 5-Acetoxy-N ⁷- (3-oxobutyl)-pyrido[2,3-d]pyridazin-8(7H)-one displayed a borderline anticonvulsant activity in the metrazole test model. Corresponding author. E-mail: edith.goessnitzer@uni-graz.at Received March 20, 2002; accepted April 3, 2002     

Ba(SbF(6))(2).5XeF(2): first xenon(II) compound with barium. Synthesis,vibrational spectra,and crystal structure

The reaction between Ba(SbF(6))(2) and excess XeF(2) in anhydrous HF at room temperature yields the white solid Ba(SbF(6))(2).5XeF(2) after the excess XeF(2) and the solvent have been removed under vacuum. Ba(SbF(6))(2).5XeF(2) crystallizes in the monoclinic space group C2/m, with a = 13.599(6) A, b = 12.086(4) A, c = 9.732(5) A, beta = 134.305(6) degrees, V = 1144.7 (8) A(3), and Z = 2. The coordination sphere of each barium atom consists of 12 fluorine atoms. The structure consists of alternating layers of Ba(SbF(6))(2).XeF(2) and 4 XeF(2) molecules. The Ba atoms in the Ba(SbF(6))(2).XeF(2) layer are in a nearly rhombic-net array and are linked with trans F-bridging ligands of SbF(6)(-). A XeF(2) molecule is placed in the center of each rhombus of the Ba(2+) array so that its symmetry axis is perpendicular to the plane of the Ba(SbF(6))(2).XeF(2) layer. This layer is linked to its neighbors by a layer of centrosymmetric XeF(2) molecules. Raman spectra are in accord with all XeF(2) molecules being symmetrical.