Photoluminescence of Gallate Glass-Ceramics: Al2O3 Influence

Glass and Ceramics - The influence of Al2O3 as an additive and the heat-treatment regime on the luminescence spectra of gallate glass-ceramics was investigated. It is shown that its luminescence...     

On-line coupled liquid chromatography-gas chromatography (LC-GC) and LC-LC-GC for detecting irradiation of fat-containing foods

Summary On-line coupled liquid chromatography-gas chromatography-flame ionisation detection (LC-GC-FID) enables efficient and unambiguous determination of irradiation for some fat-containing foods (e.g. meat). Other products, however, contain interfering components or are contaminated, e.g., with mineral oil. Since more selective detection by mass spectrometry has limited success, the determination was improved by a more selective isolation of some key components among the fat degradation products, e.g. the dienes or trienes, by LC-LC-GC-FID. Applications are shown for soup mixes, some spices, fish, and shrimps.

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Nachweis der Bestrahlung fetthaltiger Lebensmittel durch direkt gekoppelte LC-GC und LC-LC-GC

Zusammenfassung Die Bestrahlung einiger fetthaltiger Lebensmittel, z. B. Fleisch, kann mit direkt gekoppelter LC-GC-FID rationell und eindeutig nachgewiesen werden. In anderen Proben wird die Analyse aber durch Inhaltsstoffe des Produktes oder durch Verunreinigungen (z. B. mit Mineralöl) gestört. Da selektivere Detektion durch Massenspektrqmetrie wenig verspricht, wurde der Nachweis durch selektivere Isolierung von Schlüsselkomponenten unter den Bestrahlungsprodukten, z. B. der Diene oder Triene, mittels LC-LC-GC yerbessert. Anwendungen werden gezeigt für Suppenpulver, einige Gewürze, Fisch und Garnelen.

     

GC–MS characterization of oligomers in polyadipates used as plasticizers for PVC in food contact

Fourteen commercial polyadipates and a polysebacate were analysed for their components of a molecular mass below 1000 Da, primarily with the aim of generating the background data for measuring the migration of this type of polymeric additives from plasticized PVC (e.g. cling films and gaskets of lids) into foods or food simulants. Since the composition of the material <1000 Da varies between the polyadipates, the main components must be identified to enable a correct quantification. Polyadipates differ in the diol used as linker, their termination (acid or alcohol) and in the end‐capping (free alcohols, acetylation, acylation with fatty acids, esterification with octanol/decanol). Gas chromatography (GC) provides good separation, but the material remaining in the column up to high temperatures decomposes and forms a hump in the rear part of the chromatogram. Examples of mass spectra are shown, the most indicative fragments pointed out and spectra of 159 components listed. The polyadipates and the sebacate are characterized by their structure, the main components <1000 Da and the fraction of material <1000 Da. Copyright © 2006 John Wiley & Sons, Ltd.     

Enrichment for reducing the detection limits for the analysis of mineral oil in fatty foods

A German draft for a regulation requires that there must be no migration of mineral oil aromatic hydrocarbons (MOAH) from recycled paperboard into food. The Federal Institute for Risk Assessment (BfR) is requested to establish the detection limit. It was previously shown that the detection limit of the commonly used methods is below 0.1 mg/kg for the majority of the foods, but substantially higher in fatty products because of limited capacity of the liquid chromatographic preseparation to retain fat, interference by olefins and, if also the mineral oil saturated hydrocarbons (MOSH) should be analyzed, the natural paraffins primarily consisting of odd-numbered n-alkanes. A method is described for the enrichment of the MOSH and MOAH conceived as an auxiliary tool for fatty foods analyzed by the conventional methods, such as on-line HPLC–GC. In a double bed liquid chromatographic column, the lower packing consists of a mixture of activated aluminum oxide, silica gel with silver nitrate and activated silica gel, the upper of activated silica gel. The technical detection limit in edible oils is below 0.3 mg/kg, which translates to less than 0.1 mg/kg in the dry foods packed in recycled paperboard. The distinction between migrated mineral oil and that present before packaging often presupposes the availability of the food prior to packaging.     

The two options for sample evaporation in hot GC injectors: thermospray and band formation. optimization of conditions and injector design.

Although classical split and splitless injection is more than 30 years old, we only start to understand the vaporization process in the injector. Solvent evaporation determines much of the process and is the first obstacle to overcome. Videos recorded on devices imitating injectors showed that sample (solvent) evaporation is often a violent process which is poorly controlled and might well explain many of the puzzling quantitative results often obtained. We do not adequately take into account that two vaporization techniques are in use. Partial solvent evaporation inside the syringe needle (optimized as "hot needle injection") produces thermospray: the sample liquid is nebulized upon leaving the needle. The resulting fog is rapidly slowed and moves with the gas. Solute evaporation largely occurs from microparticles suspended in the gas phase. Empty liners are most suitable. Fast autosamplers suppress vaporization in the needle, i.e., nebulization, and shoot a band of liquid into the chamber that must be stopped by a packing or obstacles suitable to hold the liquid in place during the 0.2-5 s required for solvent evaporation. Solute evaporation largely occurs from the surfaces onto which the sample is deposited. Insights into these mechanisms help optimize conditions in a more rational manner. Methods should specify whether they were optimized and validated for injection with thermospray or band formation. The insights should also enable a significant improvement of the injector design, particularly for splitless injection.     

Phenolic resins for can coatings: I. Phenol-based resole analysed by GC-MS, GC×GC, NPLC-GC and SEC

Phenolic resins (resoles) are used for curing expoxy and polyester coatings, e.g., for food cans. They consist of oligomeric materials prepared from phenols (phenol, cresol, tert.-butyl phenol), formaldehyde and butanol and are an analytical challenge because of the complexity of their composition. A phenol-based resole was selected for a first investigation of various analytical techniques: gas chromatography (GC)-mass spectrometry (MS), comprehensive two-dimensional GC (GC×GC), normal phase high-performance liquid chromatography (NPLC, primarily of interest for preseparation for GC analysis), and size exclusion chromatography (SEC). Mass spectra are discussed for some selected compounds and a list of spectra is added. GC×GC was the most powerful method for separating and visualizing the composition of the complex mixture, but the whole battery of methods might be needed to characterize resoles and to analyse their migration into food or food simulants.     

Migration of Mineral Oil into Noodles from Recycled Fibres in the Paperboard Box and the Corrugated Board Transport Box as well as from Printing Inks: A Case Study

From the toxicological evaluation of mineral oils as used in offset printing inks by the Joint Food and Agriculture Organization of the United Nations/World Health Organization Expert Committee on Food Additives (JECFA), a specific migration limit of 0.6 mg/kg in food can be derived. Experimental packs for taglioline (fine noodles) were investigated, aiming at respecting this limit. This ended with four conclusions. First, during the 65 day test (shelf life of 2 years), the transport box of corrugated board contaminated the bottom packs in the box with 6.1 mg/kg mineral oil saturated hydrocarbons (MOSH) and had the potential of contaminating all the 10 packs on average at about 10 mg/kg. Second, the migration from an improved recycled paperboard (five times less mineral oil than average) still amounted to 4.9 mg/kg, indicating that optimization of recycling is not promising to respect the 0.6 mg/kg limit. Third, a printing ink containing 3 g/kg MOSH (about 100 times less than conventional offset inks) still contaminated the taglioline with 0.6 mg/kg MOSH. Finally, the taglioline were contaminated with 2.5 mg/kg MOSH already before packing, illustrating that there are other sources of mineral oil violating the 0.6 mg/kg limit. Copyright © 2011 John Wiley & Sons, Ltd.     

Determination of epoxidized soy bean oil (ESBO) in oily foods by GC–FID or GC–MS analysis of the methyl diepoxy linoleate

A simplified method is presented for determining epoxidized soy bean oil (ESBO) in food or food simulants, such as olive oil. ESBO is transesterified with methoxide/methanol directly in the homogenated food, i.e. without prior extraction, and analyzed on a cyanopropyl or phenyl polysiloxane stationary phase without formation of dioxolanes. For most foods, flame ionization detection (FID) was appropriate, but for samples with interfering components, GC–MS was needed. Chemical ionization (CI) with ammonia is more sensitive and more selective than electron impact ionization (EI). In CI, positive and negative ion monitoring (PCI and NCI) are similar in sensitivity, but different in selectivity, i.e. the combination of the two is well suited for confirmation. Results are shown to be in agreement with on-line LC–GC–FID.     

The proximal ligand variant His93Tyr of horse heart myoglobin

The spectroscopic and structural properties of the His93Tyr variant of horse heart myoglobin have been studied to assess the effects of replacing the proximal His residue of this protein with a tyrosyl residue as occurs in catalases from various sources. The variant in the ferric form exhibits electronic spectra that are independent of pH between pH 7 and 10, and it exhibits changes in absorption maxima and intensity that are consistent with a five-coordinate heme iron center at the active site. The EPR spectrum of the variant is that of a high-spin, rhombic system similar to that reported for bovine liver catalase. The 1D 1H-NMR spectrum of the variant confirms the five-coordinate nature of the heme iron center and exhibits a broad resonance at 112.5 ppm that is attributable to the meta protons of the phenolate ligand. This result indicates that the new Tyr ligand flips at a significant rate in this protein. The thermal stability of the Fe(III) derivative is unchanged from that of the wild-type protein (pH 8) while the midpoint reduction potential [-208 mV vs SHE (pH 8.0, 25 degrees C)] is about 250 mV lower. The three-dimensional structure of the variant determined by X-ray diffraction analysis confirms the five-coordinate nature of the heme iron center and establishes that the introduction of a proximal Tyr ligand is accommodated by a shift of the F helix (residues 88-99) in which this residue resides away from the heme pocket. Additional effects of this change are small shifts in the positions of Leu29, a heme propionate, and a heme vinyl group that are accompanied by altered hydrogen bonding interactions with the heme prosthetic group.(ABSTRACT TRUNCATED AT 250 WORDS)