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.     

Colour and colour stability of hot processed frozen minced beef. Results from chemical model experiments tested under storage conditions

Minced beef based on hot processed meat was found to show an improved red colour and, more significantly, to show a better colour stability with respect to brown discoloration, when compared to minced beef resulting from a traditional (cold) process. The colour was followed by tristimulus colorimetry during freezer storage (product temperature -18°C) in a display cabinet illuminated by fluorescent tubes. The development of brown discoloration seems to indicate other oxidative changes and to relate to rancidity as judged from a determination of thiobarbituric acid reactive substances in the mince surface. Fluorescent light and added salt, both known from chemical models to increase the autoxidation rate of red oxymyoglobin to brown metmyoglobin, greatly reduced the colour stability, especially for cold deboned meat. pH of the hot deboned meat was significantly higher (pH > 6·0) than that of the cold deboned meat (pH ranged from 5·5 to 5·8). The observations are discussed in relation to kinetic salt effect on the acid catalyzed autoxidation of oxymyoglobin and its role in the initiation of oxidative rancidity.     

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.

     

Acid-catalysed reduction of ferrylmyoglobin: product distribution and kinetics of autoreduction and reduction by NADH

The pH dependence of iron(II)/iron(III) product distribution, following reduction of the hypervalent iron in equine ferrylmyoglobin by the protein moiety of the pigment (so-called autoreduction) and by NADH (nicotinamide adenine dinucleotide, reduced) and the rate of reduction was found to depend different on pH. Autoreduction is specific acid catalysed and has a more modest temperature dependence than autoxidation of oxymyoglobin, with the activation parameters H ^#=58.5±0.4 kJ·mol^–1 and S ^#=2.7±0.1 J·mol^–1·K^–1 in 0.16 mol·1^–1 NaCl. The product of autoreduction is the iron(III) pigment metmyoglobin, which is slightly modified in the protein moiety. The reaction has a positive kinetic salt effect from which it is deduced that the reactive centre of ferrylmyoglobin has a charge of +1 in agreement with the structure Fe(IV)=O. Reduction by NADH involves parallel reactions of two pigment forms in acid/base equilibrium with each other with a pK _a equal to 4.9, both forms yielding metmyoglobin as well as the iron(II) pigment, oxymyoglobin, as products. The protonated form reacts faster than the deprotonated form, and two-electron transfer has greater importance for the protonated form with a limiting Fe(II)/Fe(III) product ratio of 0.6 in acidic solution compared to 0.12 in alkaline solution. A square root dependence of rate on NADH concentration suggests involvement of NAD·radicals with a disproportionation as the termination reaction.

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Säure-katalysierte Reduktion von Ferrylmyoglobin. Produktdistribution und Kinetik der Autoreduktion und Reduktion von NADH

Zusammenfassung Die Reaktionsgeschwindigkeit und das Eisen(II)/Eisen(III)-Verhältnis des Produkts nach Reduktion von hypervalentem Eisen in Ferrylmyoglobin aus Pferden zeigt eine unterschiedliche pH-Abhängigkeit der sogenannten Autoreduktion (Reduktion am Proteinteil des Pigments) sowie der Reduktion durch NADH. Die Autoreduktion weist eine spezifische Säure-Katalyse auf sowie eine moderate Temperaturabhängigkeit im Vergleich zur Autooxidation von Oxymyoglobin mit den Aktivierungsparametern H ^#=58.5±0.4 kJ·mol^–1 und S ^#=2.7±0.1 J·mol^–1·K^–1 in 0.16 mol·1^–1 NaCl. Das Produkt der Autoreduktion ist das Eisen(III)-Pigment Metmyoglobin mit leicht modifiziertem Proteinanteil. Die Reaktion hat einen positiv kinetischen Salzeffekt, woraus zu erschließen ist, daß das reaktive Zentrum im Ferrylmyoglobin die Ladung +1 übereinstimmend mit der Struktur Fe(IV)=O besitzt. Die Reduktion durch NADH weist auf parallele Reaktionen von zwei Pigmentformen in einem Säure/Base-Gleichgewicht mit pk _a=4.9 hin, beide Formen ergeben Metmyoglobin sowie das Eisen(II)-Pigment Oxymyoglobin als Produkt. Die protonisierte Form reagiert schneller als die deprotonisierte Form, und eine zwei-Elektronenübertragung hat größere Bedeutung für die protonisierte Form mit einem Fe(II)/Fe(III) Produktverbrauch von 0.6 in der Säurelösung und 0.12 in der Baselösung. Die Quadratwurzel Abhängigkeit der Geschwindigkeit von NADH deutet auf eine Teilnahme von NAD-Radikalen mit Disproportionierung als Schlußreaktion.

     

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.     

Synthesis and thermal decomposition of potassium tetraamidoboranealuminate,K[Al(NH2BH3)4]

A new potassium tetraamidoboranealuminate, K[Al(NH₂BH₃)₄], has been synthesized by a mechanochemical reaction between KAlH₄ and NH₃BH₃. The compound, K[Al(NH₂BH₃)₄], crystallizes in a triclinic unit cell with space group symmetry P?1. The crystal structure consists of [K(NH₂BH₃)₆]^5? octahedra which facilitate the bridging between K⁺ in 1D chains, while also bridging K⁺ to Al³⁺ to connect the 1D chains in a 3D network. Thermal analysis reveals that K[Al(NH₂BH₃)₄] decomposes in two exothermic steps at T ～ 94 and 138 °C and releases primarily hydrogen. The total gas release amounts to ～6.0 wt% H₂. The decomposition products are investigated ex situ by powder X-ray diffraction, infrared spectroscopy, and ¹¹B and ²⁷Al NMR and identified as KBH₄ and amorphous phases, possibly BN₃, N₂BH, and/or NBH₂ whereas aluminum is found in four-, five-, and six-fold coordination. Unfortunately, the decomposed sample shows no hydrogen absorption at T = 260 °C and p(H₂) = 110 bar.     

New indicator for optimal preprocessing and wavelength selection of near-infrared spectra

Preprocessing of near-infrared spectra to remove unwanted, i.e., non-related spectral variation and selection of informative wavelengths is considered to be a crucial step prior to the construction of a quantitative calibration model. The standard methodology when comparing various preprocessing techniques and selecting different wavelengths is to compare prediction statistics computed with an independent set of data not used to make the actual calibration model. When the errors of reference value are large, no such values are available at all, or only a limited number of samples are available, other methods exist to evaluate the preprocessing method and wavelength selection. In this work we present a new indicator (SE) that only requires blank sample spectra, i.e., spectra of samples that are mixtures of the interfering constituents (everything except the analyte), a pure analyte spectrum, or alternatively, a sample spectrum where the analyte is present. The indicator is based on computing the net analyte signal of the analyte and the total error, i.e., instrumental noise and bias. By comparing the indicator values when different preprocessing techniques and wavelength selections are applied to the spectra, the optimal preprocessing technique and the optimal wavelength selection can be determined without knowledge of reference values, i.e., it minimizes the non-related spectral variation. The SE indicator is compared to two other indicators that also use net analyte signal computations. To demonstrate the feasibility of the SE indicator, two near-infrared spectral data sets from the pharmaceutical industry were used, i.e., diffuse reflectance spectra of powder samples and transmission spectra of tablets. Especially in pharmaceutical spectroscopic applications, it is expected beforehand that the non-related spectral variation is rather large and it is important to remove it. The indicator gave excellent results with respect to wavelength selection and optimal preprocessing. The SE indicator performs better than the two other indicators, and it is also applicable to other situations where the Beer-Lambert law is valid.