Direct Spectroscopic Observation of Singlet Oxygen Quenching and Kinetic Studies of Physical and Chemical Singlet Oxygen Quenching Rate Constants of Synthetic Antioxidants (BHA,BHT, and TBHQ) in Methanol

Abstract: Singlet oxygen quenching by synthetic antioxidants (BHA, BHT, and TBHQ) was directly observed by spectroscopic monitoring of luminescence at 1268 nm. The luminescence data showed unambiguous evidence of singlet oxygen quenching by synthetic phenolic antioxidants with the highest activity for TBHQ, followed by BHA and BHT. The protective activities of these synthetic antioxidants on α-terpinene oxidation with chemically-induced singlet oxygen under dark further confirmed their singlet oxygen quenching abilities. Total singlet oxygen quenching rate constants (k_r + k_q) of BHA, BHT, and TBHQ were determined in a system containing α-terpinene (as a singlet oxygen trap) and methylene blue (as a sensitizer) during light irradiation, and the values were 5.14 × 10⁷, 3.41 × 10⁶, and 1.99 × 10⁸ M⁻¹s⁻¹, respectively. After the k_r value of α-terpinene was first determined, the k_r values of the synthetic antioxidants were calculated by measuring their relative reaction rates with singlet oxygen to that of α-terpinene under the identical conditions. The k_r values of the BHA, BHT, and TBHQ were 3.90 × 10⁵, 1.23 × 10⁵, and 2.93 × 10⁶, M⁻¹s⁻¹. The percent partition of chemical quenching over total singlet oxygen quenching (k_r × 100)/(k_r + k_q) for BHA, BHT, and TBHQ were 0.76%, 3.61%, and 1.47%, respectively. The results showed that the synthetic antioxidants quench singlet oxygen almost exclusively through the mechanism of physical quenching. This represents the first report on the singlet oxygen quenching mechanism of these synthetic antioxidants. Practical Application: The synthetic antioxidants, especially TBHQ, have been found to have a strong singlet oxygen quenching ability. This article also clearly showed that singlet oxygen quenching by synthetic antioxidants was mainly by the physical quenching mechanism. The results suggested that these synthetic antioxidants, especially TBHQ, could be used practically for the protection of the food components such as edible oils and vitamins against singlet oxygen induced oxidations without significant losses of antioxidant activity during storage under light.     

Evaluation of silicon intake through consumption of Takju,Soju, and wine

The protective activities of 6 different catechins on the singlet oxygen induced photooxidation of α-terpinene in methanol were studied to find out the relation between their structure and singlet oxygen quenching activity. The total singlet oxygen quenching abilities (k _r +k _q values) in the same system were also calculated by using a Stern-Volmer plot. The protective activities were in order of epigallocatechin gallate (EGCG)=epigallocatechin (EGC) > gallocatechin gallate (GCG) > epicatechin gallate (ECG) > epicatechin (EC) > catechin (C). The k _r +k _q values of EGCG and C were 1.31×10⁸ and 1.66×10⁷/M·s, respectively. The pyrogallol (B) ring structure was the most influencing factor for the k _r +k _q values. Stereospecific configuration also provided a considerable influence on the values. The G-ring structure did not show significant influence in the value for EGCG and EGC. The k _r values of the catechins were 3.23×10⁵–1.64×10⁶/M·s.     

Migration analysis,antioxidant, and mechanical characterization of polypropylene-based active food packaging films loaded with BHA,BHT, and TBHQ

Polypropylene (PP) based active composite films were prepared by adding butylated hydroxy anisole (BHA), butylated hydroxytoluene (BHT), and tertiary butylated hydroquinone (TBHQ) antioxidants using the extrusion molding process. All concentrations of BHT, 2% to 3% BHA, and 3% TBHQ significantly increased the tensile strength (TS) of the composite films compared with control films. Increasing antioxidant concentration decreased TS values for BHT films, whereas an opposite trend was observed for BHA and TBHQ films. BHA at < 2%, BHT at > 2%, and TBHQ at all added concentrations significantly reduced elongation at break (E_b) of the composite films compared to control films. Water vapor permeability (WVP) of 1% BHT film was not significantly different from control. However, other antioxidants especially at increased concentrations significantly increased WVP values. TBHQ films with 300% to 662% increase had the highest WVP and BHT films with 5% to 81% increase had the lowest WVP among composite films. All three antioxidants had a negative effect on the transparency of the films; however the effect of BHA at higher concentrations was greater. The antioxidants did not change the color attributes of the films. Films containing all antioxidants showed 2,2-diphenyl-1-picrylhydrazyl radical-scavenging activity, which increased with increase in their concentration, especially for those containing 3 wt.% BHT and TBHQ. Overall, incorporating BHA and BHT into a PP matrix improved mechanical, barrier, antioxidant properties, and film appearance and consequently were proposed for the development of antioxidant active PP films. TBHQ film is not recommended for food packaging because of its weak mechanical properties (lower E_b and TS values, higher WVP, and greater migration).     

Kinetic study on the singlet oxygen quenching activity of nordihydroguaiaretic acid (NDGA) using methylene blue sensitized photooxidation of α-terpinene

Singlet oxygen is highly reactive and can therefore induce rapid oxidation of a range of biological molecules, causing cell damages. The effects of nordihydroguaiaretic acid (NDGA) on the photochemical singlet oxygen oxidation of α-terpinene in methanol were studied. NDGA showed strong protective activity on the singlet oxygen oxidation of α-terpinene in methanol in a dose dependent manner. The protective activity of NDGA was considerably higher than that of butylated hydroxytoluene and 1,4-diazabicyclo[2.2.2]octane. Total singlet oxygen quenching rate constant (k _r +k _q ) of NDGA was determined by a steady state kinetic equation. The total singlet oxygen quenching rate constant of NDGA was 9.81×10⁷ M^?1 sec^?1. The result showed that NDGA possessed strong singlet oxygen quenching activity, indicating its potential for the protection of molecules, cells and nutrients from the highly reactive singlet oxygen. To the best of our knowledge, this is the first report on the singlet oxygen quenching rate constant of NDGA.     

Effect of BHA, BHT, TBHQ and PG on Growth and Toxigenesis of Selected Aspergilli

The antifungal effect of butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), tertiary butylhydroquinone (TBHQ) and propyl gallate (PC) alone or in combination on three toxigenic strains of aspergilli (NRRL 2999, NRRL 4123, NRRL 5835) and three nontoxigenic strains of aspergilli (NRRL 5521, NRRL 5917, NRRL 5918) was examined in a solid medium and in salami. BHT and PG (0.001,0.005,0.01,0.02g per plate) did not inhibit growth, sporulation, and toxigenesis of all six cultures. Aflatoxin production by toxigenic aspergilli (B₁, B₂, G₁ and G₂) in the presence of BHA, TBHQ, and a combination of BHA and TBHQ was reduced significantly (P < 0.05). In salami BHA, TBHQ alone or in combination at 100 ppm significantly (P < 0.05) decreased the aflatoxin production by aspergilli when compared to control samples. A combination of BHA and TBHQ showed synergistic inhibition in both studies (solid medium and salami studies).     

Kinetics of Growth and Inhibition of Listeria monocytogenes in the Presence of Antioxidant Food Additives

Listeria monocytogenes strain Scott A in Tryptose Broth was treated with 100-300 ppm butylated hydroxyanisole (BHA), 300-700 ppm butylated hydroxytoluene (BHT) and 10-30 ppm tertiary butylhydroquinone (TBHQ). Resulting growth curves were fitted using the logistic model, and growth parameters [lag period (LP), generation time (GT), and maximum growth (MG)] were calculated. BHA and BHT inhibited Listeria monocytogenes by increasing LP and GT and decreasing MG. Extent of inhibition was concentration-dependent for cultures with BHA, but not with BHT. TBHQ at 10-30 ppm increased LP but did not affect other parameters. LP increased exponentially with increased BHA or TBHQ in Listeria culture. Concentrations of additive required to increase LP by one order of magnitude were 240 ppm for BHA and 26 ppm for TBHQ.     

Antioxidant activity of lignans from fringe tree (Chionanthus virginicus L.)

Fringe tree (Chionanthus virginicus L.), a shrub of the eastern part of America, used as a raw material by pharmaceutical industries for cholagoque, diuretic, tonic and the preparation of homeopathic tinctures. The identification of lignans as major antioxidant components and determination of their antioxidant activities are of considerable interest, because of the role they play in pharmacological actions. The potential antioxidant activity of the lignans such as phillyrin, pinoresinol-β-d-glucoside (PDG) and pinoresinol di-β-d-glucoside (PDDG) from root bark of fringe tree (C. virginicus L.) were examined by different antioxidant tests including; 2,2-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) radical scavenging, 1,1-diphenyl-2-picryl-hydrazyl free radical (DPPH^•) scavenging, superoxide anion radical (O₂ ^•-) scavenging, total antioxidant activity by ferric thiocyanate method, reducing activity by Fe³⁺–Fe²⁺ transformation, hydrogen peroxide (H₂O₂) scavenging and ferrous metal (Fe⁺²) chelating activities. Phillyrin, PDG and PDDG, as antioxidants, neutralized the activities of radicals and inhibited the peroxidation reactions of linoleic acid emulsion. The total antioxidant activity was determined according to the ferric thiocyanate method. Butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), α-tocopherol and trolox, which is a water-soluble analogue of tocopherol, were used as the reference antioxidant compounds. Phillyrin, PDG and PDDG showed 67.6, 77.3 and 64.2% inhibition on lipid peroxidation of linoleic acid emulsion, respectively, at the concentration of 20 μg/mL. On the other hand, BHA, BHT, α-tocopherol and trolox exhibited 74.4, 71.2, 54.7 and 20.6% inhibition on peroxidation of linoleic acid emulsion, respectively, at the above mentioned concentration. In addition, phillyrin, PDG and PDDG were effective on DPPH^•, ABTS^•+ and O₂ ^•- scavenging, H₂O₂ scavenging, total reducing power and metal chelating effect on ferrous ions activities. Also, BHA, BHT, α-tocopherol and trolox were used as references antioxidants for these various antioxidant activities.     

Interaction of phosphatidylcholine and α-tocopherol on the oxidation of sunflower oil and content changes of phosphatidylcholine and tocopherol in the emulsion under singlet oxygen

Abstract: Interaction of phosphatidylcholine (PC) and α‐tocopherol (α‐Toc) on the oxidation of oil in the emulsion consisting of sunflower oil and water under singlet oxygen at 25 °C was studied by determining peroxide value (PV) and conjugated dienoic acid (CDA) contents. Singlet oxygen was produced by chlorophyll b under 1700 lux. Single addition of PC or α‐Toc decreased the values of peroxides and CDAs of oil in the emulsion via singlet oxygen quenching. PC and α‐Toc showed simply additive interaction in decreasing the singlet oxygen oxidation of oil in the emulsion. α‐Toc was a physical quencher of singlet oxygen in the emulsion, but PC involved chemical quenching in the antioxidant action. Chlorophyll and PC contents were decreased in the emulsion under singlet oxygen, while α‐Toc was not. α‐Toc protected chlorophyll and PC from degradation, and was a more important component than PC in the oil oxidation under singlet oxygen in the emulsion.     

Measurement of antioxidative activity in metal ion‐induced lipid peroxidation systems

This study aims to investigate the acceleration effects of various prooxidants on linoleic acid peroxidation and to assess the feasibility of applying these model systems by measuring the antioxidant activities of butylated hydroxyanisole (BHA), α‐tocopherol and rosemary extracts. According to our results, Fe²⁺ and Fe³⁺ exhibited more stimulatory effects than other prooxidants on the peroxidation of linoleic acid. An additional amount of ascorbic acid can reduce Fe³⁺ to Fe²⁺, resulting in more severe peroxidation. However, ascorbic acid displays antioxidant activity with increasing concentration. The peroxidation of linoleic acid induced by Fenton reaction is less than that induced by iron ions and was increased by addition of ascorbic acid to the system to maintain the regeneration of Fe²⁺ and the production of hydroxyl radicals. BHA shows the strongest inhibitory effects on the peroxidation of linoleic acid in all systems. The antioxidant activity of α‐tocopherol is less than that of rosemary extracts in the iron ion‐induced peroxidation systems. However, α‐tocopherol shows stronger inhibitory effects than rosemary extracts in the Fenton reaction‐induced peroxidation system at a concentration less 100 mg kg⁻¹. These systems can be useful in screening antioxidants from natural sources because of the short reaction time and clear difference between each antioxidant. © 1999 Society of Chemical Industry     

Release property and antioxidant effectiveness of tocopherol-incorporated LDPE/PP blend films

Low-density polyethylene (LDPE)/polypropylene (PP) blend films in various blending ratios containing 3000?mg?kg^?1 of tocopherol were manufactured by an extrusion process. Tocopherol release properties were characterised and correlated with antioxidant effectiveness in retarding the oxidation of linoleic acid contacting the films at 40°C. The conditions without tocopherol (control) and with instant tocopherol addition corresponding to the amount included in the films were also prepared and compared with the film-contacting solutions. The effect of tocopherol inclusion and the blending ratio on their physical properties was also examined. A wide range of tocopherol diffusivity in 6.6?×?10^?16–4.6?×?10^?14?m^2?s^?1 were obtained by blend films. As PP content increases, the diffusivity decreased sharply at the beginning and levelled off later. The slower release of tocopherol in LDPE/PP blend films corresponding to lower tocopherol diffusivity retained the higher tocopherol concentration in the linoleic acid system providing better antioxidant effectiveness of the extended induction period in oxidation. The tocopherol inclusion reduced tensile strength and transparency significantly in an affordable range with higher tensile strength given by a higher PP ratio. LDPE/PP blending can be a useful tool to modulate the release profile of tocopherol and thus the antioxidant effectiveness of the tocopherol-incorporated antioxidant packaging film.     

The effectiveness of butylated hydroxyanisole and α‐tocopherol in inhibiting oxidant‐induced chemical and structural changes of whey protein

The objective of the study was to investigate the role of butylated hydroxyanisole (BHA) and α‐tocopherol in protecting whey protein isolate (WPI) from oxidative modification. The results showed that oxidation increased protein carbonyls and decreased total sulfhydryls, and led to higher dityrosine and surface hydrophobicity (P < 0.05) than nonoxidised WPI. The presence of BHA and α‐tocopherol significantly reduced (P < 0.05) the extent of WPI oxidation, thus limiting the oxidation‐induced protein aggregates and structural changes. Therefore, BHA and α‐tocopherol may be used as potential antioxidants in WPI and WPI‐containing foods.     

Oxidative stability of purified common Kilka (Clupeonella cultiventris caspia) oil as a function of the bene kernel and hull oils

Oxidative stability of the purified common Kilka triacylglycerols (PKO) as affected by 1–8% w/w of bene kernel (BKO) and hull (BHO) oils was studied and compared with that of 100 mg kg^?1 of BHT and α‐tocopherol. Lipid oxidation was measured by monitoring peroxide value till the minute 80 (PV₈₀, meq kg^?1) and also by determining the oxidative stability index at 60 °C (OSI₆₀, h). In the Rancimat test, the OSI₆₀ of the PKO (1.66 h) was significantly increased by some of the added antioxidants, and the BKO 8% (7.98 h) had the highest antioxidant activity with no significant differences among the BHT, α‐tocopherol and the BHO 8%. Furthermore, an exponential regression curve with a good coefficient of determination (R² > 0.94) was observed between the changes in the PV₈₀ and OSI₆₀ values of the PKO.     

Antioxidative Properties and Ability of Phenolic Compounds of Myrtus communis Leaves to Counteract In Vitro LDL and Phospholipid Aqueous Dispersion Oxidation

Antioxidant activities of Myrtus communis leaf phenolic compounds (McPCs) were investigated on 2,2′‐9‐azino‐bis‐3‐ethylbenzothiazoline‐6‐sulfonic acid (ABTS⁺?) and oxygen radical absorbance capacity (ORAC) tests or on oxidation of biological models, human low‐density lipoprotein (LDL) and phospholipid aqueous dispersion (l ‐α‐phosphatidylcholine stabilized by bile salts). Two extraction techniques, microwave‐assisted (MAE) and conventional (CE), were used to isolate McPCs, producing similar results of phenolic compound content. ABTS⁺? assay showed clearly that myrtle extracts exhibited a stronger scavenging effect than butylated hydroxyanisole and α‐tocopherol, with a slight advantage for myrtle CE extract. In ORAC assay, the both McPC extracts were similarly less effective than the pure compounds as caffeic acid and myricitrin (myricetin 3‐O‐rhamnoside) but stronger than butylated hydroxytoluene. Moreover, myrtle CE and MAE extracts, and myricitrin were able to inhibit similarly the production of conjugated dienes and to prolong the lag phase (Tlag) during Cu²⁺‐induced LDL oxidation with a dose‐response effect. The cryo‐electron microscopy observations on studied phospholipid dispersion stabilized by bile salts (BS) revealed the presence of bilayer vesicles and micelles. In 2,2′‐azobis (2‐amidinopropane) hydrochloride–induced phospholipid/BS oxidation, myrtle CE and MAE extracts gave similar effects to α‐tocopherol and caffeic acid but myricitrin showed a higher protective effect than myrtle extracts. We showed also that no synergic or additive effect between α‐tocopherol and myrtle extracts or caffeic acid in α‐tocopherol–enriched phospholipid/BS dispersion, but myricitrin showed an additive effect and thus promoted the total antioxidant activity. These data showed that myrtle extract could be used as potential natural antioxidants, food stabilizers, or natural health products.     

Autoxidation of methyl linolenate. The effect of antioxidants on product distribution

Studies on autoxidation of polyunsaturated fatty acids in the presence of antioxidants have shown that there can be significant differences in the proportions and types of products produced in ‘inhibited’ autoxidations, as compared with control autoxidations, in the absence of an antioxidant. The autoxidation of methyl linolenate has been used as a model system with which to study the effects of different concentrations of both natural and synthetic antioxidants on the proportions of the various types of oxidation product formed. The antioxidants studied included α-, γ-, and δ-tocopherol, α-tocotrienol, 2,2,5,7,8-pentamethylhydroxychroman (PMHC), 2,6-di-tert-butyl-4-methylphenol (BHT), 3-tert-butyl-4-hydroxyanisole (BHA), and mono-tert-butylhydroquinone (TBHQ). In order to investigate the effect of the antioxidants, the oxidation products were analysed for the proportions of diperoxides and monohy-droperoxides present, and the monohydroperoxide class was further analysed for the proportions of cis, trans and trans, trans dienes and ‘inner’ and ‘outer’ hydroperoxides. In all cases where any significant oxidation occurred the extent of the change in product distribution caused by the antioxidant increased as the antioxidant concentration increased. In many cases the extent of methyl linolenate oxidation occurring under standard conditions (after 100 h at 40°C) also increased as the antioxidant concentration increased, but this was not so for δ-tocopherol, BHT and TBHQ. The importance of these findings in relation to food systems and to the understanding of antioxidant behaviour is discussed.     

Antioxidant properties of resveratrol: A structure–activity insight

Resveratrol, a natural product, is known to affect a broad range of intracellular mediators. In the present study, we clarified the antioxidant activity of resveratrol by employing various in vitro antioxidant assays such as DPPH?, ABTS^?+, DMPD^?+, O₂^?? and H₂O₂ scavenging activities, total antioxidant activity, reducing abilities, and Fe²⁺ chelating activities. Resveratrol inhibited 89.1% of the lipid peroxidation of linoleic acid emulsion at 30 µg/mL concentration. On the other hand, BHA, BHT, α-tocopherol, and trolox exhibited inhibitions of 83.3, 82.1, 68.1, and 81.3% against peroxidation of linoleic acid emulsion at the same concentration, respectively. In addition, resveratrol had effective DPPH?, ABTS^?+, DMPD^?+, O₂^?? and H₂O₂ scavenging activities, reducing power, and Fe²⁺ chelating activities. The present study found that resveratrol had effective in vitro antioxidant and radical scavenging activity. It can be used in pharmacological and food industry due to its antioxidant properties.Industrial relevanceAntioxidants are often added to foods to prevent the radical chain reactions of oxidation and they act by inhibiting the initiation and propagation step leading to the termination of the reaction and delay the oxidation process. At the present time, the most commonly used antioxidants are BHA, BHT, propylgallate and tert-butyl hydroquinone. Besides that BHA and BHT are restricted by legislative rules because of doubts over their toxic and carcinogenic effects. Therefore, there is a growing interest on natural and safer antioxidants in food applications, and a growing trend in consumer preferences for natural antioxidants, all of which has given more impetus to explore natural sources of antioxidants. A variety of foods and beverages of vegetable origin contain several nonflavonoid classes of phenolic compounds synthesized by plants. Among them, resveratrol has been identified as the major active compound of stilbene phytoalexins and is presumed to be beneficial for human health. Resveratrol is naturally occurring in the fruits and leaves of edible plants, peanuts, mulberries, grapes and red wine. Resveratrol is currently in the limelight all over the world due to their beneficial effects on the human body. Resveratrol can be used for minimizing or preventing lipid oxidation in pharmaceutical products, retarding the formation of toxic oxidation products, maintaining nutritional quality and prolonging the shelf life of food products and pharmaceuticals instead of BHA and BHT and other antioxidant compounds because of their safer usage.     

电分析法测定植物油中抗氧化剂研究

主要研究抗氧化剂TBHQ、BHA和BHT在玻碳电极上伏安性质,三者循环伏安图表明,三个峰形良好氧化峰分别对应:TBHQ氧化峰电位为590mV,BHA氧化峰电位为710mV,BHT氧化峰电位为1050mV,只有一个还原峰,电位为-90mV。通过试验优化电分析法测定植物油样抗氧化剂分析技术参数;借助最小偏二乘法(PLS),利用电分析法预测人工模拟试样中三种抗氧化剂含量,结果令人满意。该研究利用所开发方法测定实际油样中抗氧化剂含量,其回收率为94～104.1%;结果表明,该法同时测定植物油中两种及以上抗氧化剂是可行的,且无需提取、分离及清洗等预处理程序,应用潜力巨大。     

Effectiveness of antioxidant‐impregnated film in retarding lipid oxidation

The effectiveness of an antioxidant‐impregnated film to retard autoxidation of a packaged model product containing linoleic acid, via an evaporation/sorption mechanism, was evaluated as a function of storage time and temperature. The rate of loss of antioxidant from the package film structure was described by a first‐order expression. The first‐order rate constants were dependent on the initial concentration of antioxidant in the film. The rate of loss of 3,5‐di‐tert‐butyl‐4‐hydroxytoluene (BHT) from the package film structure was found to be much higher than the rate of loss of α‐tocopherol at both storage conditions (23 and 45 °C, 50% relative humidity) studied. A freeze‐dried model food product system was developed as the source for the autoxidation of linoleic acid in storage stability studies. The storage stability of this model food system packaged with antioxidant‐impregnated film pouches was evaluated. Hexanal as an index of oxidation from the model product system was collected by a dynamic purge and trap system and quantified by a gas chromatography/mass spectrometry procedure. The BHT‐impregnated laminate pouch showed a notable effectiveness in retarding lipid oxidation of the model product at 45 °C as a function of storage time. The control (non‐antioxidant) and α‐tocopherol‐impregnated laminate pouch structures showed no effect on retarding lipid oxidation of the model product during storage at 45 °C. Copyright © 2004 Society of Chemical Industry     

Oxidative stability of palm‐ and soybean‐based medium‐ and long‐chain triacylglycerol (MLCT) oil blends

BACKGROUND: Medium‐ and long‐chain triacylglyerols (MLCT) enzymatically esterified using Lipozyme RM IM lipase has very low oxidative stability as it does not contain any antioxidants. The aim of this work was to study the ability of various antioxidants to increase the oxidative stability of palm‐ and soybean‐based MLCT blends which assist to bring up the oxidative stability of both MLCT blends. In this study, the effectiveness of rosemary extracts, sage extracts, tert‐butylhydroquinone (TBHQ) and mixtures of tert‐butyl‐4‐hydroxyanisole (BHA) and tert‐butyl‐p‐hydroxytoluene (BHT) in protecting against oxidation of various MLCT blends was investigated. RESULTS: Blending of MLCT oil with either palm olein or soybean oil improved its smoke point values and oxidative stability. TBHQ addition to both palm‐ and soybean‐based MLCT blends increased oxidative stability. Combination of BHA and BHT showed no significant improvement (P > 0.05) in ability to protect blends from oxidation compared to natural antioxidants such as sage or rosemary extracts. CONCLUSION: Blended oils with 500 g kg^?1 MLCT and 500 g kg^?1 palm olein (MP5) were the most suitable for use at high temperature based on the fatty acid composition of the MLCT blends, which subsequently had an effect on thermal oxidative stability. In general, addition of either natural or synthetic antioxidant assisted in improving the antioxidative strength of both MLCT blends. MLCT blends with added TBHQ showed the highest thermal oxidative stability among the antioxidants used. Copyright © 2008 Society of Chemical Industry     

Influence of sn‐1,3‐lipase‐catalysed interesterification on the oxidative stability of soybean oil‐based structured lipids

The oxidative stability of structured lipids (SLs) synthesised by specific sn‐1,3‐lipase catalysed interesterification of soybean oil (SBO) with caprylic acid (CA) in a stirred batch reactor was studied. SLs contained considerable amounts of tocopherol (TOH) isomers, although they lost almost 25% of endogenous TOHs during production. The effects of the addition of different TOH homologues (α, β, γ, δ), ascorbyl palmitate (AP, 200 ppm), lecithin (Le, 1000 ppm), butylated hydroxytoluene (BHT, 100 ppm) and butylated hydroxyanisole (BHA, 100 ppm) on the oxidative stability of SLs were investigated. Induction time (IT) of SBO, determined by the Rancimat method, decreased from 8.4 to 5.8 h at 110 °C after the modification. On the other hand, purified SLs and purified SBO had the same IT due to the tocopherol reduction during silica purification. No significant difference was observed between IT of SLs and SLs plus different α‐tocopherol concentrations (50, 100, 150, 200, 300, 500 and 1000 ppm) (P > 0.05). However, the addition of Le and/or AP significantly improved oxidative stability of purified SLs and SBO. The ternary blend containing δ‐TOH, AP and Le had higher IT than ternary blends of α‐TOH, β‐TOH or γ‐TOH. Furthermore, ternary blend containing BHA, AP and Le had higher IT than ternary blends of BHT, AP and Le. In addition, there was an increase in peroxide value (PV), conjugated diene (CD) content and p‐anisidine value (AV) during oxidation of oils at 60 °C. Antioxidant mixtures of α‐TOH (50 ppm) and δ‐TOH (500 ppm) with AP and Le decreased PV, CD and AV effectively. Copyright © 2006 Society of Chemical Industry     

Determination of synthetic phenolic antioxidants in soft drinks by stir-bar sorptive extraction coupled to gas chromatography-mass spectrometry

The synthetic phenolic antioxidants butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT) and tert-butyl hydroquinone (TBHQ) were pre-concentrated by stir-bar sorptive extraction and thermally desorbed (SBSE-TD) before analysis by GC-MS. Several parameters affecting the derivatisation step and both SBSE extraction and thermal desorption were carefully optimised. When the analyses of BHA and TBHQ in their acetylated, silylated and underivatised forms were compared, the best results were obtained when the in-situ derivatisation procedure with acetic anhydride was employed. Quantification was carried out using carvacrol as the internal standard, providing quantification limits of between 0.11 and 0.15 ng ml^?1, depending on the compound. Recovery assays for samples spiked at two concentration levels, 1 and 5 ng ml^?1, provided recoveries in the 81–117% range. The proposed method was applied in the analysis canned soft drinks and the analytes were found in five of the 10 samples analysed.