Reduction of irradiation off-odor and lipid oxidation in ground beef by α-tocopherol addition and the use of a charcoal pack

A combination of a charcoal pack during irradiation and α-tocopherol addition into ground beef was applied to eliminate an irradiation characteristic off-odor and to retard the lipid oxidation caused by the irradiation process. Ground beef was mixed with 200 ppm α-tocopherol and gamma irradiated with 0, 5, and 10 kGy with or without a charcoal pack present during the irradiation treatment. The pH of the control group was lower than that of α-tocopherol and charcoal pack treatment initially but increased rapidly and showed higher pH at day 7. Addition of α-tocopherol with or without charcoal pack addition showed lower 2-thiobarbituric acid reactive substances values in irradiated ground beef at days 3 and 7 compared to those without addition. The color of ground beef was not significantly affected by the treatment. However, odor preference result showed that 10 kGy-irradiated ground beef with a combination of charcoal pack and α-tocopherol addition had higher scores than the control group regardless of irradiation. Solid-phase microextraction (SPME) gas chromatograph/mass spectrometry (GC/MS) analysis identified various volatile compounds that were created by irradiation of ground beef. These compounds were reduced or eliminated when a charcoal pack was used during the irradiation process. The results of the present study imply that combination of packaging with a charcoal pack during the irradiation process and addition of α-tocopherol into ground beef is a good method to effectively eliminate an irradiation off-odor and retard the lipid oxidation development in ground beef caused by irradiation.     

Comparison of the photochemical behaviors of α-tocopherol and its acetate in organic and aqueous micellar solutions

Photoionization is known to take place when α-tocopherol (TOH) is excited to the S(1) state in a polar medium. It has been previously suggested that TO(?) is formed only as a result of proton release by TOH(?+), a process that is expected to occur, in a protic solvent, on the subnanosecond time scale. Recent redeterminations of the molar absorption coefficients of e(aq)(–) (Hare J. Phys. Chem. A 2010, 114, 1766) and of TOH(?+) and TO(?) (Naqvi J. Phys. Chem. A 2010, 114, 10795) have paved the way for testing the above suggestion, even if subnanosecond time resolution is not available, since it implies the equality of [e(aq)(–)](0) and [TO(?)](0), where [···](0) denotes the concentration of the enclosed species immediately after a nanosecond laser pulse. Nanosecond pump-probe spectroscopy of TOH in aqueous micellar solution (AMS) and two organic solvents with similar polarities (acetonitrile and methanol) has revealed that prompt formation of TO(?) through dissociation (TOH + hν → TO(?) + H(?)) is not negligible even in AMS. In acetonitrile, TOH(?+) and TO(?) are formed with comparable yields, and the former converts quantitatively into TO(?) within 15 μs. In methanol, TO(?) was observed, but no evidence was found for electron ejection from TOH. Only one photoproduct, namely TO(?), could be detected when α-tocopherol acetate (TOAc) was excited to the S(1) state in several polar and nonpolar solvents; TOAc has been found to be a more efficient energy degrader than TOH.     

Viscous and dielectric properties of α-tocopherol and α-tocopherol acetate

This article presents the results of the shear viscosity and the dielectric relaxation measurements performed for α-tocopherol and α-tocopherol acetate, two principal compounds from the vitamin E group. The temperature dependence of the viscosity and dielectric relaxation time of the compounds can be very well reproduced with the Vogel–Fulcher–Tammann equation. It was found that for both tocopherols, the viscosity and the relaxation time attain their infinite high value (solid-like state) at the temperature of ～60 K below the transition to the glass state.     

Determination of α-tocopherol in Cosmetic Products by Chronopotentiometry

Abstract

In the present study, a rapid chronopotentiometric method was developed for the determination of α-tocopherol in various cosmetic products. Determination of α-tocopherol is based on its irreverse oxidation by constant current at the planar glassy carbon electrode. The influence of the most important experimental parameters of chronopotentiometry was investigated. After optimization, an appropriate procedure for the sample preparation was developed. Under the defined experimental conditions, a detection limit of 7.5 mg L^?1 of α-tocopherol was obtained. The accuracy of the defined method was confirmed by means of recovery assay. The developed method was successfully applied to quantitation of α-tocopherol in various cosmetic products.     

Effects of α-tocopherol and its acetate on the hydrolytic activity of phospholipase D in egg yolk phosphatidylcholine bilayers

Effects of -tocopherol (Toc) and -tocopherol acetate (TocA) on the hydrolysis activity of phospholipase D (fromStreptomyces chromofuscus) were studied in small unilamellar vesicles (SUV) of egg yolk phosphatidylcholine (PC). Choline produced in the reaction was monitored by use of a choline oxidase — oxygen electrode. Addition of 18 mol% Toc into SUV (2 mM PC) brought about a twofold rate of choline production. On the other hand, the effect of 18 mol% TocA in SUV was very small. The apparent maximum velocity,V _max(app), increased by addition of Toc in SUV. The apparent Michaelis constant,K _m(app), was unchanged by addition of Toc and TocA in SUV. The Toc and TocA molecules did not have significant effects when PC was solubilized in the micelles of heptaethylene glycol dodecyl ether. The effects of Toc and TocA are, therefore, not due to specific ones on the enzyme itself, but rather upon the bilayer-organization of the substrate. Measurements of spreading pressure showed complete miscibility of PC and Toc, and limited mutual solubility of PC and TocA, suggesting stronger attractive interactions between Toc and PC than those between TocA and PC in the bilayers.     

The role of low levels of water in the electrochemical oxidation of α-tocopherol (vitamin E) and other phenols in acetonitrile

The phenol, α-tocopherol, can be electrochemically oxidised in a -2e(-)/-H(+) process to form a diamagnetic cation that is long-lived in dry organic solvents such as acetonitrile and dichloromethane, but in the presence of water quickly reacts to form a hemiketal. Variable scan rate cyclic voltammetry experiments in acetonitrile with carefully controlled amounts of water between 0.010 M-0.6 M were performed in order to determine the rate of reaction of the diamagnetic cation with water. The water content of the solvent was accurately determined by Karl Fischer coulometric titrations and the voltammetric data were modelled using digital simulation techniques. The oxidation peak potential of α-tocopherol measured during cyclic voltammetry experiments was found to shift to less positive potentials as increasing amounts of water (0.01-0.6 M) were added to the acetonitrile, which was interpreted based on hydrogen-bonding interactions between the phenolic hydrogen atom and water. Several other phenols were examined and they displayed similar voltammetric features to α-tocopherol, suggesting that interactions of phenols with trace amounts of water were a common occurrence in acetonitrile. The H-bonding interactions of α-tocopherol with water were also examined via NMR and UV-vis spectroscopies, with the voltammetric and spectroscopic studies extended to include other coordinating solvents (dimethyl sulfoxide and pyridine).     

Voltammetric determination of α-tocopherol in the presence of surfactants

As established, α-tocopherol is electrochemically active on glassy carbon electrode in the available range of anodic potentials in acetonitrile and its aqueous mixtures. However, an increase in the water percentage up to 50% and beyond leads to a substantial decrease and then the total disappearance of the analytical signal. A scheme of electrode reaction responsible for the signal formation is proposed. The effect of surfactants on the oxidation of α-tocopherol in aqueous acetonitrile is estimated. As found, surfactants (N-dodecylpyridinium bromide, Triton X-100 and N-cetylpyridinium bromide) enhance the current of α-tocopherol oxidation. The surfactants reduce the detection limit and extend the analytical range. Analytical methods for the voltammetric quantification of α-tocopherol in drugs in the presence of surfactants are elaborated and may be recommended for the control of pharmaceuticals.     

Synthesis of triterpene acids conjugates with α-tocopherol synthetic analogs

Heterodimers were synthesized of pharmacologically important α-tocopherol synthetic analogs with triterpene acids(betulonic, betulinic), potential polyfunctionsl drugs possessing antioxidant activity. The combination of the fragments of biologically active substances was performed through linkers (residues of succinic acid, hydrazine, glycine, tetramethylenediamine) binding the side chain of the antioxidant molecule with atoms C³ or C²⁸ of the terpenoid.     

Conia-ene annulation of the α-cyano β-TMS-capped alkynyl cycloalkanone system and its synthetic application

Under catalysis with ZnI(2), an effective annulation process of ω-silylacetylenic α-cyano ketones, leading to the formation of various bicyclic frameworks characterized with a TMS-containing methylenecyclopentane ring, has been developed.     

Bromination of α-tocopherol methano-dimer and ethano-dimer

Bromination of the ethano-dimer of α-tocopherol (6) afforded pyrano-spirodimer of α-tocopherol (7) quantitatively, while the methano-dimer of α-tocopherol (10) produced a mixture of products, including the furano-spirodimer 11, pyrano-spirodimer 7, and 5-bromo-γ-tocopherol (12), the latter two formed in an unusual dealkylative fragmentation step. The mechanisms were studied by a combination of trapping reactions as well as kinetic and computational studies.     

Radical chain mechanism of the oxidation of α-terpinene by molecular oxygen

The oxidation of -terpinene by molecular oxygen is shown to occur by a radical chain mechanism involving hydroperoxy radicals. The principal molecular reaction products are H₂O₂ and 1-methyl-4-isopropylbenzene. The rate constants for chain propagation and chain breaking measured at 35–70°C are (liter/mol·s) lgk₃ = 7.10– (6700±400)/4.57T and lgk₅ = 9.80– (2700±300)/4.57T respectively.Translated from Teoreticheskaya Éksperimental'naya Khimiya, Vol. 30, No. 3, pp. 143–146, May–June, 1994The authors thank the Ukraine National Committee for the Basic Research Fund for financing this work.     

Synthesis of palladium–polypyrrole nanocomposite and its electrocatalytic properties in the oxidation of formaldehyde

Three alternative methods were developed for the synthesis of modifying palladium–polypyrrole layers on the surface of an inert electrode. Their electrocatalytic activity toward formaldehyde under inert atmosphere was checked. All the suggested methods are one-stage and allow synthesis of a film on the electrode surface from a solution containing a palladium salt and pyrrole in the absence of other active reagents. The electrochemical methods (potentiodynamic and double cathodic and anodic pulses techniques) in an aqueous medium give films with poorly reproducible electrocatalytic properties, while the chemical redox synthesis affords films with reproducibly high electroactivity toward methylene glycolate.     

Impact of α-, γ-, and δ-tocopherol on the radiation induced oxidation of rapeseed oil triacylglycerols

Gamma-irradiation (doses: 2, 4, 7, and 10 kGy) was used as oxidation tool to study the antioxidant effects of α-, γ-, and δ-tocopherol (enrichments 500–5000 ppm) in purified rapeseed oil triacylglycerols (RSOTG). Fatty acid composition, tocopherol degradation, primary (conjugated dienes (CD) and peroxide value (POV)) and secondary (p-anisidine value) oxidation products were chosen as test parameters. Fatty acid composition did not change. While secondary oxidation products could not be found in the irradiated samples, the POVs and CDs showed a significant, dose-dependent increase. α-Tocopherol did not inhibit the formation of peroxides, whereas γ- and δ-tocopherol reduced the POVs by more than 30%. No uniform effect of the different tocopherol concentrations at the particular doses could be established. The influence of the individual tocopherols on the CD formation was not pronounced. The degradation of the tocopherols decreased with increasing concentration. None of the tocopherols showed a prooxidant effect.     

Enantiodivergence in the reduction of α-methyl and α-halomethyl enones by microorganisms

Enones (Z)-3-methyl-(Z)-3-chloromethyl- and (Z)-3-bromomethyl-4-R-3-buten-2-one (R = n-pentyl, phenyl, 2′- and 4′-chlorophenyl, 3′- and 4′-nitrophenyl, 4′-methoxyphenyl) were synthesized and subjected to reduction by the microorganisms Saccharomyces cerevisiae andGeotrichum candidum. Whereas the bioreduction of 3-methy-4-R-3-buten-2-ones afforded the corresponding (S)-4-R-3-methybutan-2-ones, the bioreduction of 3-chloromethyl- and 3-bromomethyl-4-R-3-buten-2-ones afforded the corresponding (R)-4-R-3-methybutan-2-ones.     

Investigation of the phosphinyl analog of α-ketoglutaric acid

It was shown by³¹P and¹³C NMR spectroscopy that methyl(3-carboxy-3-oxopropyl)phosphinic acid (4-methylhydroxyphosphinyl-2-oxobutyric acid) (1) and the amide (2) of the latter exist in keto forms in non-aqueous solutions. In aqueous solutions an equilibrium between the keto,gem-diol, and enol forms has been observed. The proportions of the diol and enol forms increase as the acidity of the media increases. Silylation of acid 1 with hexamethyldisilazane gives the tris(trimethylsilyl) derivative of enol form (3) (Z- andE-isomers).Translated fromIzyestiya Akadetnii Nauk. Seriya Khimicheskaya, No. 1, pp. 125–128, January, 1994.     

Hydrogenation of α-cyanoacrylic acid and its esters by organohydridesilanes

The C=C bond in -cyanoacrylic acid is readily hydrogenated by organohydridesilanes in the absence of catalyst. The hydrogenation of -cyanoacrylate esters requires the presence of acid.A. N. Nesmeyanov Institute of Organometallic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 7, pp. 1655–1657, July, 1992.     

Preparation and characterization of zein/chitosan complex for encapsulation of α-tocopherol, and its in vitro controlled release study

Chitosan (CS) nanoparticles coated with zein has been newly demonstrated as a promising encapsulation and delivery system for hydrophilic nutrient with enhanced bioactivities in our previous study. In this study, a hydrophobic nutrient, α-tocopherol (TOC), was successfully encapsulated into zein/CS complex. The fabrication parameters, including zein concentration, zein/CS weight ratio, and TOC loading percentage, were systematically investigated. The physicochemical and structural analysis showed that the electrostatic interactions and hydrogen bonds were major forces responsible for complex formation. The scanning electron microscopy study revealed the spherical nature with smooth surface of complex. TOC encapsulation was also evidenced by differential scanning calorimetry. The particle size and zeta potential of the complex varied from 200 to 800 nm and +22.8 to +40.9 mV, respectively. The kinetic release profile of the TOC showed burst effect followed by slow release. Compared with zein nanoparticles, zein/CS complex provided better protection of TOC release against gastrointestinal conditions, due to CS coatings. Zein/CS complex is believed to be a promising delivery system for supplementation or treatment of hydrophobic nutrients or drugs.     

Kinetic and mechanism of oxidation of thiocarbohydrazide and its metal complex by acid bromate in aqueous and partial aqueous media

The kinetics of oxidation of thiocarbohydrazide in the free and zinc(Ⅱ)-bound states byacid bromate have been studied in aqueous and water-acetic acid(1:1,V/V)media under varyingconditions,both in the absence and presence of added bromide ion.The rates of oxidations show firstorder kinetics in[bromate]in all the cases,but exhibit different kinetic behaviour in[substrate]and[H~+].Oxidation of TCH in aqueous medium shows zero order in[TCH]and nearly second order in[H~+],while oxidation in aqueous acetic acid shows two ranges in[H~+].The rate shows first and fractionalorder kinetics in[TCH]in the first and second acid ranges.Kinetics observed in the presence of Br~-are similar to those observed for oxidation of TCH in second acid range.In addition,the reactionshows fractional order in[Br~-].Oxidation of TCH in Zn(Ⅱ)-bound state exhibits first order kinetics in[substrate]and second order in[H~+].Increase in ionic strength of the medium decreases the rate in allthe cases.Increase in acetic acid composition of the solvent increases the rate.Mechanisms consistentwith the observed results have been considered and the rate laws deduced.The rate limiting steps havebeen identified and the coefficients of these steps have been calculated at different temperatures.Therelated activation parameters have also been computed.The validity of the deduced rate laws has alsobeen tested by recalculating the rate constants from them as[TCH]and[H~+]are varied.