Solid-state13C NMR investigations of insoluble deposits in aromatic bitters

Insoluble deposit formed in aromatic bitters produced from alcoholic extracts of about 30 different botanical materials with a dry matter content of 1.67% and 38 vol% alcohol and a characteristic astringent flavour was shown by¹³C NMR spectroscopy to be a coprecipitate of plant polyphenols, proteins and carbohydrates. The polyphenols in the deposit were flavonoids such as anthocyanidins and anthocyanins, with glucose as the principal carbohydrate and derivatives of cinnamic acid. The deposit formation in the aromatic bitters was accelerated by addition of the radical initiator 2,2′-azobis(2-amidinopropane) dihydrochloride or by addition of hydrogen peroxide in combination with iron(III) nitrate and ascorbic acid as a Fenton reagent. Polymerization of catechin and pelargonidin was shown, in model experiments, to be oxidative and to be accelerated by exposure to light. A mechanism involving oxidative polymerization of polyphenols followed by coprecipitation of polymerized polyphenols, proteins and carbohydrates is proposed for formation of deposits in alcoholic beverages of the bitters type.     

Storage life of frozen salmonoids Effect of light and packaging conditions on carotenoid oxidation and lipid oxidation

Summary The combined effect of oxygen transmission of packaging material and of exposure to light with different spectral distribution on the oxidative degradation of carotenoids and lipids in frozen salmonoids has been characterized in a storage experiment with steaks of rainbow trout. The degradation of the carotenoid astaxanthin, as followed by HPLC analysis and tristimulus colorimetric measurement, was sensitive to the radiant flux density of UV light and less sensitive to the oxygen transmission rate of the packaging material, in agreement with previous findings for photooxidation of carotenoids in food model systems. This is in contrast to the lipid oxidation, which was found to be dependent on the accessability of oxygen rather than on exposure to UV light. Formation of peroxides in the product culminated after 3 months of storage (up to 8.4 mEq kg^–1 oil), and preceded the formation of thiobarbituric-acid-reactive substances. The product in packaging material with a high oxygen transmission rate (60 cm³ m^–2 bar^–1 per 24 h) reached a level of approximately 5 mol malonaldhyde/kg^–1 product, when stored exposed to standard fluorescent light or fluorescent light with a high UV component. Rancid taste was not detected by sensory evaluation for any of the products after 6 months of storage, whereas a bitter taste was noted for the product exposed to UV light.

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Die Haltbarkeit von Lachsforellen Einfluß von Licht und Verpackung auf die Carotenoid- und Fettoxydation

Zusammenfassung Der kombinierte Effekt von Sauerstoffdurchgang durch Verpackungsmaterial und der Lichteinwirkung verschiedener spektraler Verteilung auf den oxidativen Abbau der Carotinoide und Fette in gefrorenen Lachsforellen wurde in einem Lagerungsversuch untersucht. Der Abbau des Carotenoids Astaxanthin wurde mit HPLC undTristimulus-Calorimetrie beobachtet, und war empfindlich gegenüber UV-Licht und weniger empfindlich gegenüber der Sauerstoffdurchlässigkeit der Verpackung, was mit früheren Ergebnissen für Photooxidation der Carotinoide in Modellsystemen übereinstimmt. Dies widerspricht der Fettoxidation, die mehr von Sauerstoffzugang abhängig ist als von der Entwicklung des UV-Lichtes. Die Bildung von Peroxiden des Produktes kuliminierte nach 3monatiger Lagerung (bis 8,4 meq/kg Öl) und ging der Bildung von Thiobarbitursäure-aktiven Substanzen voraus. Das Produkt im Material mit hohem Sauerstoffdurchgang (60 cm³ m^–2 bar^–1 pro 24 h), das bei normalen fluorescierendem Licht oder bei fluorescierendem Licht mit hohem UV-Anteil aufbewahrt wurde, erreichte einen TBS-Wert von ungefähr 5 mol Malonaldehyd/kg Fleisch. Ein ranziger Geschmack wurde durch sensorische Bewertung nach 6monatiger Lagerung nicht erkannt, wohl aber ein bitterer Geschmack bei dem UV-Licht ausgesetzten Proben.

     

Spatial distribution of light-induced lipid oxidation in semi-hard yellow cheese as detected by confocal microscopy

The migration of oxidative damage in semi-hard yellow cheese resulting from surface exposure to 436 nm monochromatic light with an intensity of 2.5 × 10¹⁷ quanta min⁻¹ cm⁻² for 0, 5, 10, and 15 min was followed by confocal laser scanning microscopy using labelling with the lipophilic fluorescence ratio probe C₁₁-Bodipy (581/591). From 5 × 5 × 5 mm cubes of cheese exposed to light on one plane 35 μm was sliced off and fluorescence of oxidised and non-oxidised probe recorded simultaneously on the surface of the slice reaching 250 μm inwards from the exposed surface. From the emission of the fluorescence ratio probe light-induced lipid oxidation could be followed with time of exposure to light. The penetration of light inwards in the cheese with time expressed as quanta cm⁻², as calculated from light transmittance at 436 nm determined spectrophotometrically for cheese slices of up to 300 μm thickness, together with light intensity as determined by actinometry, could alone account for the inwards migration of oxidation. Diffusion of radicals seems of less importance for spatial dispersion of light-induced oxidation in semi-hard cheese.     

Parallel enzymatic and non-enzymatic formation of zinc protoporphyrin IX in pork

Zinc protoporphyrin is formed in pork homogenates in both enzymatic and non-enzymatic reactions. Ferrochelatase is active in formation of the highly fluorescent pigment known from Parma ham as demonstrated by inhibition with N-methylmesoporphyrin and by thermal inactivation. A non-enzymatic transmetallisation reaction, exchange of iron in myoglobin by zinc(II), is demonstrated by Pb(II) inhibition of zinc protoporphyrin formation at low Pb(II) concentrations, but promoted at higher Pb(II) concentrations. The non-enzymatic reaction is characterised as a slow bimolecular reaction between protoporphyrin IX and zinc(II) with a second-order rate constant of 0.63 l mol⁻¹ s⁻¹ at 35 °C and a high energy of activation of 98 kJ mol⁻¹ for acetone:water (3:1, v/v) as solvent. Zinc protoporphyrin formation is concluded to be thermodynamically controlled with a formation constant of 4 × 10⁵ M (35 °C, acetone:water (3:1)). An efficient inhibition of formation of zinc protoporphyrin by nitrite is related to myoglobin as substrate and involves both enzymatic and non-enzymatic reactions.     

Angiotensin-I converting enzyme inhibitory and antioxidant activity of bioactive peptides produced by enzymatic hydrolysis of skin from grass carp (Ctenopharyngodon idella)

Grass carp skin pieces were homogenized in water and hydrolyzed by Alcalase®, collagenase, proteinase K, and/or trypsin at their optimum conditions. Samples were taken at various degrees of hydrolysis and were evaluated for antioxidant, antimicrobial, and angiotensin-converting enzyme inhibitory activities. Alcalase and collagenase completely hydrolyzed the skin with different rates, and released peptides with antioxidant and angiotensin-converting enzyme-inhibitory activity. These activities increased linearly with increasing degrees of hydrolysis. Subsequent incubation of the collagenase hydrolysates with trypsin slightly increased the antioxidant activity. Proteinase K, although only partially hydrolyzing the skin, also catalyzed the release of peptides with antioxidant and angiotensin-converting enzyme-inhibitory activities. These results show that skin by-products from grass carp can be a source of bioactive peptides produced by a one-step reaction. Such hydrolysates may be applied in food products to prolong shelf life and provide beneficial effects on blood pressure.     

Occurrence of pharmaceuticals in river water and their elimination in a pilot-scale drinking water treatment plant

The occurrence of four beta blockers, one antiepileptic drug, one lipid regulator, four anti-inflammatories, and three fluoroquinolones was studied in a river receiving sewage effluents. All compounds but two of the fluoroquinolones were observed in the water above their limit of quantification concentrations. The highest concentrations (up to 107 ng L(-1)) of the compounds were measured during the winter months. The river water was passed to a pilot-scale drinking water treatment plant, and the elimination of the pharmaceuticals was followed during the treatment. The processes applied by the plant consisted of ferric salt coagulation, rapid sand filtration, ozonation, two-stage granular activated carbon filtration (GAC), and UV disinfection. Following the coagulation, sedimentation, and rapid sand filtration, the studied pharmaceuticals were found to be eliminated only by an average of 13%. An efficient elimination was found to take place during ozonation at an ozone dose of about 1 mg L(-1) (i.e., 0.2-0.4 mg of O3/ mg of TOC). Following this treatment, the concentrations of the pharmaceuticals dropped to below the quantification limits with the exception of ciprofloxacin. Atenolol, sotalol, and ciprofloxacin, the most hydrophilic of the studied pharmaceuticals, were not fully eliminated during the GAC filtrations. All in all, the treatment train was found to very effectively eliminate the pharmaceuticals from the rawwater. The only compound that was found to pass almost unaffected through all the treatment steps was ciprofloxacin.     

Quantifying unfrozen water in frozen soil by high-field 2H NMR

To understand wintertime controls of biogeochemical processes in high latitude soils it is essential to distinguish between direct temperature effects and the effects of changes in water availability mediated by freezing. Efforts to separate these controls are hampered by a lack of adequate methods to determine the proportion of unfrozen water. In this study we present a high-field 2H2O NMR method for quantifying unfrozen water content in frozen soil. The experimental material consisted of the humic layer of a boreal spruce forest soil mixed with varying proportions of quartz sand and humidified with deuterium-enriched water. The relative standard deviation of unfrozen water content (measured as NMR signal integral) was less than 2% for repeated measurements on a given sample and 3.5% among all samples, based on a total of 16 measurements. As compared to 1H NMR, this 2H NMR method was found to be superior for several reasons: it is less sensitive to field inhomogeneity and paramagnetic impurities, it gives a bigger line shape difference between the ice and liquid signal, it shows a sharper response to water fusion, and it excludes the possibility of hydrogen in the organic material interfering with the measurement.     

A comparison of methods for linear prediction of apple flavour from gas chromatographic measurements

A comparative study of linear methods for prediction of sensory profiles from gas chromatography (GC) measurements was performed. The data used came from an experiment on the effect of storing apples at various oxygen concentrations. Partial least-squares regression and continuum regression showed the best performance, measured by a two-step cross-validation principle. The traditional prediction error sum of squares (PRESS) overestimated the predictive ability of a multiple linear regression approach. The quality of the predictions of sensory properties from GC analyses was measured in terms of a ‘panel size equivalent’. Thus, the predictions obtained in the present study were as accurate as predictions from an assessor panel consisting of 4–9 assessors, depending on the sensory property in question.