Phenolic antioxidants, determination

FOTi M and RUBERTO G (2001) Kinetic solvent effects on phenolic antioxidants determined by spectrophosometric measiuements, JAgric Food Chem, 49, 342-8. 

Typical standard deviations for determinations of the sum of phenolic antioxidants determined using HPLC/UV-vis were 0.015 mmol/L for red wines, 0.004 mmol/L for rose and 0.050 mmol/L for white wines. 

Analysts in industry prefer in many cases to maintain consistent methods for their analyses. Recommended ASTM analytical procedures are quite well developed in the rubber and polymer industry. As an example, we mention the standard test method for determination of phenolic antioxidants and erucamide slip additives in LDPE using liquid chromatography [76]. However, the current industry standard test methods (ASTM, AOAC, IUPAC, etc.) use a large number of solvents in vast... 

ASTM D 1996-97, Standard Test Method for Determination of Phenolic Antioxidants and Erucamide Slip Additives in Low Density Polyethylene Using Liquid Chromatography (LC), Annual Book of ASTM Standards, ASTM, West Conshohocken, PA (1997), Vol. 08.01. 

C12 to C20, primarily Ci6 to ( is), used as surface lubricants in the manufacture of food-contact articles. The method, which uses ethyl palmitate (Eastman Chemicals No. 1575 Red Label) as an internal standard, has been validated at 200 ppm total FAME [185]. Other FAME standards (methyl palmitate, methyl stearate, methyl oleate, methyl linoleate and methyl linolenate) are available (Applied Science Laboratories) [116], Worked out examples of additive determinations are given in the Food Additives Analytical Manual [116], which also describes a great many of indirect food additives, such as BHA, BHT, TBHQ, l-chloro-2-propanol, DLTDP, fatty acid methyl esters, w-heptyl-p-hydroxybenzoate, propyl-gallate, sodium benzoate, sodium stearoyl-2-lactylate, sorbitol and phenolic antioxidants. EPA methods 606 and 8060 describe the CGC separation of phthalate esters (direct injection) (cf. Figure 4.2). 

A method suitable for quantification of the functional class of bis(ethanol)amine antistatics, which lack UV chromophores, consists of reaction with methyl orange [53]. Atmer 163 (alkyl-diethanol amine) has been determined as a yellow complex at 415 nm after interaction with a bromophenol/cresole mixture [64]. Hilton [65] coupled extracted phenolic antioxidants with diazotised p-nitroaniline in strongly acidic medium and carried out identification on the basis of the visible absorption spectrum in alkaline solution. The antioxidant Nonox Cl in... 

Phenolic antioxidants in rubber extracts were determined indirectly photometrically after reaction with Fe(III) salts which form a red Fe(II)-dipyridyl compound. The method was applicable to Vulkanox BKF and Vulkanox KB [52]. Similarly, aromatic amines (Vulkanox PBN, 4020, DDA, 4010 NA) were determined photometrically after coupling with Echtrotsalz GG (4-nitrobenzdiazonium fluoroborate). For qualitative analysis of vulcanisation accelerators in extracts of rubbers and elastomers colour reactions with dithio-carbamates (for Vulkacit P, ZP, L, LDA, LDB, WL), thiuram derivatives (for Vulkacit I), zinc 2-mercaptobenzthiazol (for Vulkacit ZM, DM, F, AZ, CZ, MOZ, DZ) and hexamethylene tetramine (for Vulkacit H30), were mentioned as well as PC and TLC analyses (according to DIN 53622) followed by IR identification [52]. 8-Hydroquinoline extraction of interference ions and alizarin-La3+ complexation were utilised for the spectrophotometric determination of fluorine in silica used as an antistatic agent in PE [74], Also Polygard (trisnonylphenylphosphite) in styrene-butadienes has been determined by colorimetric methods [75,76], Most procedures are fairly dated for more detailed descriptions see references [25,42,44],... 

Potentiometric titration procedures with sodium methoxide have been reported for non-sulfur-containing organotin compounds in solvent extracts of polymers, and for phenolic antioxidants with sodium isopropox-ide in pyridine medium [21]. Organotin compounds in solvent extracts of PVC can be determined by potentiometric and manual titration procedures [487,488]. 

Microcoulometric titration is used as the detection mode in some commercial sulfur-specific analysers. Sulfur in PP and waxes (range from 0.6 to 6 ppm S) were determined by means of an oxidative coulometric procedure [537]. The coulometric electrochemical array detector was used for determining a variety of synthetic phenolic antioxidants (PG, THBP, TBHQ, NDGA, BHA, OG, Ionox 100, BHT, DG) in food and oils [538],... 

Decomposition of Peroxides by Various Stabilizers. The efficiency of tert-butyl hydroperoxide decomposition in tert-butyl alcohol by various additives was determined (Table 9). Under the conditions of these experiments, the phenolic antioxidants and dilauryl thiodipropionate had little or, often, no effect on the hydroperoxide decomposition. The three zinc salts effectively inhibited peroxide decomposition. This effect might briefly inhibit the onset of substrate oxidation under weathering-test conditions, but the peroxide would decompose whenever its concentration reached a sufficient level to permit significant light... 

A wide variety of methodologies have been employed for the analysis of antioxidants in polymers and some standard methods are available. For high-density polyethylene ASTM method D5524 (ASTM International) — Determination of phenolic antioxidants in high-density polyethylene, describes a method whereby the sample is ground to a small particle size and then extracted by refluxing with cyclohexane. The cyclohexane extract is then examined by reverse-phase HPLC with UV detection. 

Sousa WR, da Rocha C, Cardoso CL, Silva DHS and Zanoni MVB. 2004. Determination of the relative contribution of phenolic antioxidants in orange juice by voltammetric methods. J Food Compos Anal 17(3) 619—633. 

Table 5.6 shows the total phenolic content (determined using the Folin-Ciocalteu assay) and antioxidant activity (ABTS radical scavenging capacity) of extracts from morama bean seed coat and cotyledon prepared with acidified mefhanol. If is clear fhaf morama bean seed coat and cotyledon have appreciable levels of fofal phenolics and antioxidant activity. These phenolics are concentrated in the seed coat. It has been reported that the morama bean cotyledon contains high levels of the amino acid tyrosine (Maruatona et ah, 2010) which is phenolic in nature and can therefore confribufe fo fhe fofal phenolic content of the cotyledon as determined with the Folin-Ciocalteu assay. 

Dr. Joe Vinson of the University of Scranton believes that there is something to the chocolate effect, and he came to Belmont to tell us about his intriguing research. Vinson has determined the total polyphenol content of various chocolates and has also found a way of measuring how effective these mixtures are in preventing the oxidation of human ldl in a test tube. In other words, he has calculated a phenol antioxidant index, which takes into account both the quantity and the quality of these desirable substances. At the symposium Vinson reported that cocoa powder and dark chocolate are the best, followed by milk chocolate. Instant cocoa mixes trail the field. Then Vinson delivered the kicker chocolate has more, and better, polyphenols than fruits or vegetables and more than red wine. A forty-gram bar of dark chocolate has as many polyphenols as a cup of that widely promoted antioxidant cocktail we call tea. But there is still the matter of chocolate s fat content. Researchers tell us, though, that at least half of it is stearic acid, which does not raise blood cholesterol. 

After benzoylation, it was possible to analyze together the food substances of varying chemical structures, such as alcohols, esters of 4-hydroxybenzoic acid, phenolic antioxidants, saccharides, and sugar alcohols. The method allowed the determination of these substances in different matrices by the same analytical procedure, using the same cleanup. The preservatives were separated on an RP-18 column. Acetonitrile-water (50 35) or acetonitrile-water-butylmethyl ether (110 35 40) were used as mobile phases. Detection was UV at 230 nm (71). 

In general, antioxidants are divided into natural and synthetic groups. Because natural antioxidants are discussed in other chapters ( The Fat-soluble Vitamins, Analysis of Phenolic Compounds, and Analysis of Organic Acids ), we deal here only with the determination of synthetic phenolic antioxidants (SPA). 

Table 9 HPLC Systems Used for the Determination of Synthetic Phenolic Antioxidants... 

BD Page. Liquid chromatographic method for the determination of nine phenolic antioxidants in butter oil collaborative study. J AOAC International 76 765-779, 1993. 

DR McCabe, IN Acworth. Determination of synthetic phenolic antioxidants in food using gradient HPLC with electrochemical array detection. Am Lab News 30(13) 18B, 18D, 16, 1998. 

AW Archer. The determination of phenolic antioxidants in edible oils and fats by high-performance liquid chromatography. Anal Chim Acta 128 235-237, 1981. 

As a chemical class, nitrones have found heavy use in studies of reactions of superoxo and alkylperoxyl radicals.120,122,123Table 8.8 lists several examples. The rate constant for the reaction of STAZN with Me2C(CN)00CH2CH(00 )Ph was determined recently, k = 7.6 x 104 M 1 s-1 in chlorobenzene and 4.8 x 105M 1 s-1 in mixed chlorobenzene/methanol (95 5, v/v).122 This reaction is sufficiently fast for STAZN to be an efficient chain-breaking antioxidant with reactivity that is within one to two orders of magnitude of the phenolic antioxidants such as tocopherols. 

Figure 2-17 Determination of Protection Factor. (A) lard, (B) lard + antioxidant. Source From J. Pokorny, Stabilization of Fats by Phenolic Antioxidants, Can. Inst. Food Sci. Technol. J., Vol. 4, pp. 68-74, 1971.

Detwiler and Markley (76) found that the smoke point varied considerably with the degree of refining, especially the removal of free fatty acids, and also with the mode of oil extraction. Yen et al. (118) found a smoke point of 191°C, which was raised several degrees by the addition of phenolic antioxidants. The flash point of soybean oil, the temperature at which vapors coming from the oil will catch fire from an ignition source, were reported as 304°C (117), 326-331°C (76), 174°C (69), 318°C (70), and 320°C (119). The low value reported by Ali et al. (69) was obtained by using a Pensky-Martens closed tester and ASTM method 093-90. The flash points of hexane-soybean oil mixtures were determined and correlated with headspace gas chromatography data (120). 

An HPLC-DAD method was developed for the separation and the determination of flavonoid and phenolic antioxidants in commercial and freshly prepared cranberry juice.Two sample preparation procedures were used with and without hydrolysis of the glycoside forms of flavonoids carried out by the addition of HCl in the step prior to solid-phase extraction (SPE). The flavonoid and phenolic compounds were then fractionated into neutral and acidic groups via a solid-phase extraction method (Sep-Pak Cig), followed by a RP HPLC separation with gradient elution with water-methanol-acetic acid and a detection at 280 and 360 nm. A comparison of the chromatograms obtained for extracts prepared with and without hydrolysis showed that flavonoids and phenolic acids exist predominantly in combined forms such as glycosides and esters. In a freshly squeezed cranberry juice, for instance, 400 mg of total flavonoids and phenolics per liter of sample was found, 56% of which were flavonoids. Quercetin was the main flavonoid in the hydrolyzed products, where it accounted for about 75% of the total flavonoids, while it was absent in the unhydrolyzed products. 

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