Effect of standard phenolic compounds and olive oil phenolic extracts on acrylamide formation in an emulsion system

In this work the effect of standard phenolic compounds such as trolox, phenolic acids (ferulic, gallic, protocatechuic and caffeic acid) and secoiridoids, extracted from virgin olive oil (VOO), on acrylamide formation in an emulsion system was investigated. The emulsion system was heated in an oil bath at different temperatures and for different periods of time. At 105 and 115 °C the generated amounts of acrylamide were negligible during the monitoring time. At 125 °C addition of standard phenolic compounds reduced acrylamide formation which was more pronounced at initial time of heating (20 min) reaching up to 70%. Protocatechuic and gallic acid were more effective than trolox, caffeic and ferulic acid in acrylamide reduction at the final time intervals of heating (30–60 min). On the contrary, addition of VOO extract in the emulsion system resulted in a remarkable increase of acrylamide level, which was ascribed to secoiridoids’ structure containing aldehydic groups.     

Phenolic profiles and antioxidant activities of commercial beers

The phenolic profiles and corresponding antioxidant activities of 34 commercial beers in Chinese markets were evaluated. Results found remarkable variations in total and individual phenolic contents as well as antioxidant activity across beer brands. Gallic and ferulic acids were the dominant phenolic compounds identified in the tested beer samples and both of them accounted for >50% of the total phenolic compounds. Results from Pearson correlation analysis suggested that five antioxidant activity assays positively correlated well (p < 0.01) with each other and showed significant positive correlations (p < 0.05) with (+)-catechin, protocatechuic, and caffeic acids contents. Stepwise linear regression further demonstrated that different phenolic components responsible for beer antioxidant activity were dependent on the method used, and that ferulic acid, syringic acid, (+)-catechin, caffeic acid, protocatechuic acid and (−)-epicatechin together made 55.0–88.1% of contribution to the antioxidant activity of beer.     

阿魏酸与咖啡酸对丙烯酰胺形成及消减的影响

探讨阿魏酸与咖啡酸在美拉德模拟体系中对丙烯酰胺形成和消减的影响。结果表明:在天冬酰胺/葡萄糖模拟反应体系中,阿魏酸与咖啡酸的添加量为250 mmol/L和25mmol/L时可抑制丙烯酰胺的形成,而二者浓度低于2.5mmol/L时则促进丙烯酰胺的形成。将阿魏酸与咖啡酸分别与丙烯酰胺单独高温处理,发现2种酚酸对丙烯酰胺都具有消减效果,但效果不明显,因此判定阿魏酸与咖啡酸对美拉德模拟体系中丙烯酰胺含量的影响主要作用于丙烯酰胺的形成阶段。另外,酸性条件下,醌型酚酸比酚型酚酸对丙烯酰胺的消减作用更大,而在中性条件下,酚型酚酸的消减作用更强。     

Model studies on the role of 5-hydroxymethyl-2-furfural in acrylamide formation from asparagine

This study aimed to investigate the mechanism of acrylamide formation during heating asparagine (ASN) at elevated temperatures with glucose (GLC), and 5-hydroxymethyl-2-furfural (HMF). The results revealed that HMF rapidly reacted with ASN, leading to acrylamide formation. The ASN-HMF model system generated acrylamide more efficiently than the ASN-GLC model system during heating at 180 °C. A significantly higher amount of 3-aminopropionamide (3-APA) was formed in the ASN-HMF model system than in the ASN-GLC model system within 5 min at 180 °C. The amount of 3-APA decreased after 5 min of heating in both model systems while the amount of acrylamide continued to increase in the ASN-HMF model system. In-depth high resolution mass spectrometry analyses of reaction products formed in the model systems together with the kinetic data suggested that HMF is a potent carbonyl accelerating acrylamide formation during heating. 3-APA was found as one of the key intermediates leading to acrylamide formation.     

Studies on oxidative stabilisation of lard by natural antioxidants recovered from olive-oil mill wastewater

Free phenolic compounds was extracted by ethyl acetate from olive oil mill wastewater. Extraction yield was 50 mg of total phenol on 100 g of wastewaters. Phenolic compounds recovered, determined by HPLC, were hydroxytyrosol (as major compound) and tyrosol, caffeic acid and ferulic acid (as minor compounds). For determination of antioxidant effects by Rancimat, phenolic extract, dissolved in distilled water, was added in different lard samples in quantity ranged between 50 and 350 mg kg⁻¹. Antioxidant effectiveness was measured also at low temperature.     

Impact of oregano and virgin olive oil phenolic compounds on acrylamide content in a model system and fresh potatoes

In this study the effect of olive oil and oregano phenolic compounds on antioxidant activity (AOA) and acrylamide formation in a model system and fresh potatoes was evaluated. The addition of oregano phenolic extract in the model system resulted in an increase of AOA and in a reduction of acrylamide content, up to 49%, after heating. On the contrary, addition of olive oil extract resulted in AOA reduction and a concentration-dependent effect on acrylamide formation was observed with a reduction up to 15% (p < 0.05) followed by an increase up to 48%. The same trend, in acrylamide formation, was observed in fresh potatoes but to a lower extent. Finally, addition of tyrosol, oleuropein and p-hydroxyphenylacetic acid in the model system resulted in acrylamide reduction up to 50%. The discrepancy in acrylamide formation, caused by phenolic compounds, is ascribed to their structure and related to their terminal functional hydroxyl and aldehydic groups.     

Antioxidant activity of phenolic fractions in olive mill wastewater

Olive mill wastewater (OMW) contains a substantial amount of valuable antioxidant phenols that can be recovered for industrial application as food additives and pharmaceuticals. The present study was aimed at extracting different phenolic OMW fractions, and determining their antioxidant potential. Five different OMW fractions were obtained using fractionation techniques, their antioxidant potential determined by DPPH, ORAC and a β-carotene bleaching test. The total phenol level ranged between 115 and 170 mg/l. The phenolic compounds present in individual fractions were identified using the HPLC–PAD method, where the main compounds were hydroxytyrosol, tyrosol, caffeic acid, vanillic acid, verbascoside, oleuropein, ferulic acid, and p-coumaric acid. The five OMW fractions showed different antioxidant levels depending on the test used. DPPH test showed that the fraction of alkyl aromatic alcohols (AAAs) was the best with EC₅₀ of 20 mg/l and the pure hydroxytyrosol with 2 mg/l. ORAC test showed that AAA and semi hydrolysed total phenol (s-TP) fractions were significantly better than Trolox when compared to 20 mg/l of Trolox.     

Antioxidant phenolic compounds loss during the fermentation of Chétoui olives

Evolution of phenolic compounds was studied during spontaneous and controlled fermentations of “Chétoui” cultivar olives at three degree of ripeness. Both spontaneous and controlled fermentations led to an important loss of total phenolic compounds with a reduction rate of 32–58%. Consequently, the antioxidant activity decreased by 50–72%. After fermentations, hydroxytyrosol and caffeic acid concentrations increased, whilst protocatechuic acid, ferulic acid and oleuropein concentrations decreased. The hydroxytyrosol concentration in black olives increased from 165 mg/100 g dry weight to 312 and 380 mg/100 g dry weight, respectively, after spontaneous and controlled fermentation. The oleuropein concentration in green olives decreased from 266 mg/100 g dry weight to 30.7 and 16.1 mg/100 g dry weight, respectively, after spontaneous and controlled fermentation. During olive fermentation, phenolic loss is essentially due to the diffusion of these compounds into the brine; the main phenolic compound identified and quantified in the different brines was hydroxytyrosol. To preserve antioxidant quality of table olives it is necessary to use a controlled process to minimise phenolic compound loss.     

Determination of phenolic acids in coffee by micellar electrokinetic chromatography

A seven-minute micellar electrokinetic chromatography analytical procedure capable of resolving the five principal phenolic acids in coffee, including the isomers of 5-caffeoylquinic acid (5-CQA), 4-CQA and 3-CQA, caffeic acid and ferulic acid is reported. The electrophoretic conditions consisted of an SDS (70 mM)-phosphate (17.6 mM)-methanol (5% v/v) buffer system, pH 2.5, 22.1 °C, −17 kV and detection at 325 nm. The Joule effect and the possible interactions between the buffer components and temperature with respect to peak quality, resolution and selectivity were assessed in the concentration range of 25–900 μg/mL. Performance evaluation of the system used a 3^3–7 factorial design at the 95% confidence level. The lowest correlation coefficient for linearity was 0.99888 for the 4-CQA. Limits of detection and quantification were 0.98 and 4 μg/mL. The method was tested with both green and roasted coffee beans using four systems of extraction.     

Antioxidant activities of Sideritis congesta Davis et Huber-Morath and Sideritis arguta Boiss et Heldr: Identification of free flavonoids and cinnamic acid derivatives

Different solvent extracts of endemic Sideritis (Labiatae) species, Sideritis congesta Davis et Huber-Morath and Sideritis arguta Boiss et Heldr, were analyzed for free flavonoids (quercetin, apigenin, myricetin and kaempferol) and cinnamic acid derivatives (rosmarinic acid, ferulic acid, caffeic acid, p-coumaric acid and chlorogenic acid) using HPLC-DAD. All the phenolics were quantified in acid-hydrolyzed extracts, except rosmarinic acid, chlorogenic acid and myricetin which were quantified in raw samples. Antioxidant activities of extracts of these two plants and many of their components in pure form were evaluated based on DPPH^. and ABTS^.+ assays. In general, S. arguta extracts displayed higher antioxidant activity than S. congesta extracts possibly due to their richness in antioxidant components of strong activity. Acetone extract of S. arguta, with its strikingly high TEAC value of 3.2 mM trolox and low IC₅₀ value of 38.3 ??g/mL showed the highest antioxidant potency among all extracts. ??-tocopherol, the positive control, displayed IC₅₀ and TEAC values of 33.8 ??g/mL and 2.9 mM trolox, respectively. No direct correlation was found between antioxidant activities and total phenolic contents of the plant extracts studied.     

Effect of hydroxycinnamic acids on lipid oxidation and protein changes as well as water holding capacity in frozen minced horse mackerel white muscle

The antioxidant effectiveness of different hydroxycinnamic acids for inhibiting the formation of off-flavours associated to rancidity in minced frozen horse mackerel white muscle stored at −10 and −18 °C was studied. The influence of lipid oxidation on protein aggregation, protein denaturation and water holding capacity was also determined. Caffeic acid, o-coumaric acid and ferulic acid were the antioxidants tested. The order of antioxidant effectiveness was caffeic acid > ferulic acid > o-coumaric acid accordingly with previous results obtained in chilled horse mackerel. A strong dependence of antioxidant effectiveness to the ratio lipid/antioxidant concentration was observed. There was no evidence to suggest that antioxidants reduce protein aggregation or water holding capacity changes. Protein aggregation was not accompanied by gross protein denaturation, as monitored by differential scanning calorimetry. No evidence was found for a link between extent of lipid oxidation and degree of protein aggregation or water holding capacity changes.     

Changes in phenolic composition and antioxidant activity of white wine during bottle storage: Accelerated browning test versus bottle storage

Polyphenol content, antioxidant activity, reducing power, colour and changes during storage over nine months in bottles and after accelerated browning were studied in selected Hellenic varietal white wines. The following phenolic compounds were identified in the wines: Caftaric, coutaric, fertaric, ferulic, caffeic, p-coumaric and gallic acids, (+)-catechin and (−)-epicatechin. The results showed that the contents of most of the phenols diminished with time, with the exception of caffeic, ferulic and p-coumaric acids. Antioxidant activity increased with storage whereas reducing power remained significantly unaffected. Accelerated browning did not significantly alter the concentrations of tartaric acid esters but it increased the concentrations of the hydroxycinnamic and gallic acids. (+)-Catechin concentration was not affected while (−)-epicatechin decreased. Antioxidant activity did not show any significant change but reducing power was reduced after the end of the browning test. As for the absorbance at 420 nm, it remained unchanged during storage, but it was significantly increased after accelerated browning.     

Phenylalanine ammonia lyase (PAL) enzyme activity and antioxidant properties of some cyanobacteria isolates

In the present study, six cyanobacteria isolates were evaluated for the PAL enzyme activity, and their methanol extracts were assessed for the total phenolic amount and other antioxidant parameters. Synechocystis sp. BASO444 and Synechocystis sp. BASO673 isolates with high levels of total phenols (66.0 ± 1.2 μg/mg, 78.1 ± 1.8 μg/mg, respectively) also showed high levels of PAL activities (20.5 ± 3.1 U/mg protein, 17.2 ± 2.3 U/mg protein, respectively) and strong antioxidant activities. To understand the effect of l-phenylalanine (l-phe) on the PAL activity, total phenolic amount, and phenolic constituents, isolates were evaluated with 100 mg/l l-phe. While PAL activities exhibited no significant change with l-phe addition, total phenolic amount of the isolates significantly increased. HPLC analysis revealed gallic acid, trans-cinnamic acid, p-coumaric acid, and ferulic acid as the main compounds. Results suggested that the two isolate mights be an important source for the l-phe inducible phenolic compounds.     

Retardation of myoglobin and haemoglobin-mediated lipid oxidation in washed bighead carp by phenolic compounds

Antioxidative activities of phenolic compounds (caffeic acid, gallic acid and tannic acid; 200 ppm) in washed mince (pH 6), with added myoglobin (Mb) and haemoglobin (Hb), from bighead carp (Hypophthalmichthys nobilis), during 9 days of iced storage, were studied. Tannic acid exhibited the preventive effect on discolouration of washed mince containing Mb or Hb during storage (P < 0.05). High peroxide value (PV) was found and large amount of, thiobarbituric acid-reactive substances (TBARS) and hexanal were formed in washed mince containing haem proteins, especially Hb. As determined by apo Streptococcal haem-associated protein, Hb had the lower haem affinity than Mb. Phenolic compounds, especially caffeic acid and gallic acid, could lower lipid oxidation induced by Mb or Hb throughout storage (P < 0.05). Prevention of haem release, as well as inhibition of lipid oxidation induced by haem proteins with selected phenolic compounds, should be an alternative means in lowering discolouration and lipid oxidation in fish muscle.     

Effect of phenolic compounds on the properties of porcine plasma protein-based film

Properties of porcine plasma protein-based film incorporated with tannic acid, caffeic acid and ferulic acid at different concentrations (1–3% (w/w) of protein content) were studied. Film-forming solution (FFS) containing 3% protein (w/v) and 70% glycerol (w/w of protein content) was preheated at 70 °C for 30 min and adjusted pH to 10 followed by the addition of phenols and film casting. Tensile strength (TS) of resulting film increased by 123.3, 194.3 and 19.5% and elongation at break (EAB) increased by 71.1, 86.3 and 10.2%, respectively, compared with the control film, when tannic acid, caffeic acid and ferulic acid at a level of 3% was added. The use of all phenolic compounds slightly increased water vapor permeability (WVP) of resulting films (p < 0.05). The increases in a^∗- and b^∗-values of films were observed as the higher concentrations of tannic acid and caffeic acid were used. This was associated with the lowered transparency of resulting films. FFS containing 3% caffeic acid with prior oxygenation, especially with pH 10, yielded the film with increased TS but lowered EAB (p < 0.05). Oxygenation of FFS was associated with the lower L^∗-value and higher a^∗-value of resulting films. Therefore, phenolic compounds could be used as natural cross-linkers which affected the properties of porcine plasma protein-based film differently.     

The hydroxycinnamic acid content of barley and brewers’ spent grain (BSG) and the potential to incorporate phenolic extracts of BSG as antioxidants into fruit beverages

The hydroxycinnamic acid (HA) content of starting barley for brewers’ spent grains (BSG), whole BSG and phenolic extracts from BSG was measured using high performance liquid chromatography (HPLC) and correlated with antioxidant potential. The effect of BSG phenolic extracts on antioxidant activity of fruit beverages was also assessed (using the total phenolic content (TPC), 2,2-diphenyl-1-picrylhydrazyl (DPPH) and ferric reducing antioxidant power (FRAP) assays). The concentration of HA present in barley extract and BSG was in the order of ferulic acid (FA), p-coumaric acid (p-CA) derivatives, FA derivatives, p-CA, caffeic acid (CA) and CA derivatives. Results suggested that brewing and roasting decreased the HA content. Antioxidant activity was significantly (P < 0.05) correlated with caffeic acid (R² = 0.8309) and total HA (R² = 0.3942) concentrations. Addition of extracts to fruit beverages resulted in a significant (P < 0.05) increase in antioxidant activity of cranberry juice, measured by the FRAP assay. In vitro digestion significantly (P < 0.05) reduced TPC, DPPH and FRAP activity of the fruit beverages.     

Phenolics and antioxidant properties of bayberry (Myrica rubra Sieb. et Zucc.) pomace

Five cultivars of Myrica rubra, Biqi, Wandao, Dongkui, Dingao, and Zaodamei, were collected to analyze the phenolic compounds and evaluate the antioxidant properties of bayberry pomaces. The main anthocyanin was cyanidin-3-o-glucoside (3073.3–6219.2 mg/kg dry weight (DW)) and the main flavonol was quercetin-3-o-glucoside (296.2–907.9 mg/kg dry weight). Quercetin and myricetin were also found in the bayberry pomaces, and quercetin deoxyhexoside and myricetin deoxyhexoside were tentatively identified. The dominant phenolic acids were gallic acid (102.9–241.7 mg/kg dry weight) and protocatechuic acid (29.5–57.2 mg/kg dry weight). Other phenolic acids such as p-hydroxybenzoic, vanillic, caffeic, p-coumaric, and ferulic acids were also present in the bayberry pomaces, whereas, chlorogenic acid was only detected in Dongkui (1.58 mg/kg dry weight). The antioxidant activity of Wandao was the strongest of the five cultivars, whereas the activity of Dongkui was the weakest, and a significant positive relationship was observed between antioxidant activity and total phenolic content or total anthocyanins.     

Changes of phenolic acids and antioxidant activities during potherb mustard (Brassica juncea, Coss.) pickling

Phenolic acids in potherb mustard (Brassica juncea, Coss.) were determined and the effects of pickling methods on the contents of total free phenolic acids, total phenolic acids, total phenolics, and antioxidant activities were investigated. Gallic acid, protocatechuic acid, p-hydroxybenzoic acid, vanillic acid, caffeic acid, p-coumaric acid, ferulic acid, and sinapic acid were identified in the present study. The contents of total free phenolic acids, total phenolic acids and total phenolics in fresh potherb mustard were 84.8 ± 0.58 μg/g dry weight (DW), 539 ± 1.36 μg/g DW, and 7.95 ± 0.28 mg/g DW, respectively. The total free phenolic acids increased during the pickling processes, but the total phenolic acids, total phenolics, and antioxidant activities decreased. However, after 5 weeks of fermentation, all the pickling methods retained over 70% of total phenolic contents and above 65% of antioxidant capacities. The results indicated that pickling processes were relatively good methods for the preservation of phenolic acids and antioxidants for potherb mustard.     

The analysis of phenolic constituents in glabrous canaryseed groats

Nineteen glabrous canaryseed samples, comprising brown- and yellow-coloured seeds, were investigated to determine the nature of phenolic constituents present. Total phenolic content (TPC) was determined, using the Folin–Ciocalteau assay. Flavonoid and phenolic acid compositions were determined, using high performance liquid chromatographic and mass spectrometric (LC–MS/MS) techniques. TPC ranged from 174 to 209 mg/100 g for canaryseed wholemeal samples. The canaryseed bran contained twice as much TPC as the wholemeal. The brown- and yellow-coloured whole canaryseeds exhibited the same flavonoid profiles. LC–MS/MS analysis showed that the canaryseed acetone extract was rich in flavonoid glycosides, with the bran being mainly composed of O-pentosyl isovitexin and the flour having a compound at m/z 468. No proanthocyanidins were detected in the 19 samples. Ferulic acid was the dominant phenolic acid, followed by caffeic and p-coumaric acids. The wholemeal obtained from the brown-coloured group had significantly higher contents of ferulic (>196 mg/kg) and caffeic (>96 mg/kg) acids in comparison to the yellow-coloured canaryseed group. The latter had ferulic and caffeic acids at levels less than 165 and 78 mg/kg, respectively, with one exception which had relatively higher levels (190 and 94 mg/kg). Whilst canaryseed flour contained significantly very low levels of ferulic acid (22–34 mg/kg), the bran was enriched in ferulic (593–766 mg/kg), caffeic (304–452 mg/kg) and p-coumaric (119–142 mg/kg) acids.     

Investigations into acrylamide precursors in sterilized table olives: Evidence of a peptic fraction being responsible for acrylamide formation

Formation of acrylamide from commercial model peptides containing protein-bound aspartic acid, alanine and methionine, respectively, at 200 °C and different times in the absence of any carbonyl sources, was demonstrated by HPLC–MS/MS analyses. Further experiments using a more complex model system based on olive water, i.e., the aqueous fraction of olive pulp from untreated and lye-treated green olives, were performed. After partial fractionation of olive water by solid-phase extraction, only peptides/proteins containing fractions, being devoid of free asparagine, generated significant amounts of acrylamide during less harsh heat treatment (121 °C for 30 min). In contrast, acrylamide was not detected after heating the same fraction under identical thermal conditions when previously subjected to acid hydrolysis. Consistently, significant amounts of acrylamide were released after heating the albuminous precipitate resulting from acetone precipitation of olive water. These results strongly support the role of peptides/proteins as precursors of acrylamide formation in sterilized olives.