Effect of bread making on formation of Maillard reaction products contributing to the overall antioxidant activity of rye bread

This paper reports the effects of flour extraction rate on antioxidant activity, early, fluorescent and coloured Maillard reaction products in rye flour, crumb, crust and bread. Extent of the reaction was determined by analyses of furosine, fluorescence compounds and browning while antioxidant properties were measured by Folin reaction, Trolox Equivalent Antioxidant Capacity (TEAC) and Oxygen Radical Antioxidant Capacity (ORAC_FL) assays. Antioxidants present in rye flours and breads scavenged peroxyl and ABTS radicals and reduced Folin-Ciocalteu reagent. Data indicated that baking favoured the formation of antioxidant compounds. In controversy, milling to obtain white rye flour negatively affected bread quality.     

Effect of germination on total phenolic compounds,total antioxidant capacity,Maillard reaction products and oxidative stress markers in canihua (Chenopodium pallidicaule)

Germination of cereals/pseudo-cereals has been suggested as an effective method to increase antioxidant compounds. However, this process could also lead to high reducing sugar levels and subsequent Maillard reaction products. The aim of this work was to determine the time course effect of canihua (Chenopodium pallidicaule) germination on: 1) antioxidant capacity, 2) extractable and non-extractable phenolic compounds content, 3) Maillard reaction products and 4) oxidative stress markers. Germination increased antioxidant capacity, phenolic compounds and Maillard reaction products, including advanced glycated end products while it decreased oxidative stress markers. All parameters exhibited a similar time course pattern with a maximum at 72 h. In addition to the increase in phenolic compounds and antioxidant capacity, canihua germination produced advanced glycated end products. The impact on human health of these compounds in germinated seeds deserves future attention.     

Phenolic compounds in raw and cooked rice (Oryza sativa L.) and their inhibitory effect on the activity of angiotensin I-converting enzyme

Whole rice has been widely studied due to the abundance of bioactive compounds in its pericarp. Some of the beneficial effects of these compounds on human health have been attributed to their antioxidant and other biological activities, such as enzyme inhibition. In this work, we evaluated the contents of total, soluble and insoluble phenolic compounds of 6 red and 10 non-pigmented genotypes of whole rice as well as their inhibitory effect on the activity of angiotensin I-converting enzyme (ACE). The effects of cooking on phenolics and their inhibitory activities were also investigated. Red genotypes showed high content of phenolics, mainly soluble compounds, at an average of 409.7 mg ferulic acid eq./100 g, whereas overall lower average levels (99.4 mg ferulic acid eq./100 g) at an approximate soluble/insoluble compound ratio of 1:1 were observed in non-pigmented rice. Pigmented rice displayed a greater inhibitory effect on ACE than non-pigmented rice. In fact, a significant correlation between the content of soluble phenolics and ACE inhibition was observed (r = 0.8985, p < 0.05). In addition to significantly reducing the levels of total phenolics and ACE inhibition, cooking altered the soluble/insoluble compound ratio, especially among red rice genotypes.     

A Multistrategic Approach in the Development of Sourdough Bread Targeted Towards Blood Pressure Reduction

Rising prevalence of hypertension is pushing food industry towards the development of innovative food products with antihypertensive effects. The aim was to study the effect of reduced sodium content and 21 % addition of wholemeal wheat sourdough (produced by Lactobacillus brevis CECT 8183 and protease) on proximate composition, γ-aminobutyric acid (GABA) and peptide content of wheat bread. Angiotensin converting enzyme I (ACE) inhibitory and antioxidant activities were also evaluated. Sodium replacement by potassium salt did not affect chemical composition and biological activities of bread. In contrast, GABA and peptides <3 kDa contents in sourdough bread (SDB) were 7 and 3 times higher, respectively, than the observed in control. ACE inhibitory and antioxidant activities of the peptide fraction?<?3 kDa from SDB was 1.7 and 2.6-3.0 times higher than control. Therefore, the combination of reduced sodium content with enriched concentrations of bioactive compounds in bread making may provide interesting perspectives for development of innovative breads towards blood pressure reduction.

     

Susceptibility of wheat gluten to enzymatic hydrolysis following deamidation with acetic acid and sensory characteristics of the resultant hydrolysates

The effect of acetic acid and hydrochloric acid (HCl) deamidation pretreatment on the susceptibility of wheat gluten to enzymatic hydrolysis by Pancreatin and sensory characteristics of the resultant hydrolysates was investigated. At two degrees of deamidation (24% and 60%, with or without moisture-heating, respectively), wheat gluten pretreated by acetic acid deamidation was more susceptible to be hydrolyzed as evaluated by the hydrolysis degree, nitrogen solubility index, titratable acid amount and free carbohydrate content of the hydrolysates. Wheat gluten pretreated by acetic acid deamidation at a degree of 24% exhibited the highest susceptibility to enzymatic hydrolysis. Moisture-heating (121 °C, 10 min) in the deamidation pretreatment decreased the susceptibility of wheat gluten to enzymatic hydrolysis and the peptide factions of ≤3000 Da in the hydrolysates due to the formation of larger molecule weight aggregates. The hydrolysates prepared from acetic acid deamidated wheat gluten showed more intense glutamate-like and sauce-scented taste and better nutritional characteristics.     

Antioxidant and antiproliferative activities of heated sterilized pepsin hydrolysate derived from half-fin anchovy (Setipinna taty)

In this paper we studied the antioxidant and antiproliferative activities of the heated pepsin hydrolysate from a marine fish half-fin anchovy (HAHp-H). Furthermore, we compared the chemical profiles including the amino acid composition, the browning intensity, the IR and UV-visible spectra, and the molecular weight distribution between the half-fin anchovy pepsin hydrolysate (HAHp) and HAHp-H. Results showed that heat sterilization on HAHp improved the 1,1-diphenyl-2-picryl-hydrazil (DPPH) radical-scavenging activity and reducing power. In addition, the antiproliferative activities were all increased for HAHp-H on DU-145 human prostate cancer cell line, 1299 human lung cancer cell line and 109 human esophagus cancer cell line. The contents of free amino acid and reducing sugar of HAHp-H were decreased (P < 0.05). However, hydrophobic amino acid residues and the browning intensity of HAHp-H were increased. FT-IR spectroscopy indicated that amide I and amide III bands of HAHp-H were slightly modified, whereas band intensity of amide II was reduced dramatically. Thermal sterilization resulted in the increased fractions of HAHp-H with molecular weight of 3000-5000 Da and below 500 Da. The enhanced antioxidant and antiproliferative activities of HAHp-H might be attributed to the Maillard reaction.     

A combined procedure to evaluate the global antioxidant response of bread

Baking is the most representative manufacturing process applied to bread, involving thermal and moisture conditions that facilitate the Maillard reaction (MR) and, at the same time, the destruction-formation of natural-labile and thermally-induced antioxidant compounds respectively. In the present paper, the use of a new approach to measure the Global Antioxidant Response (GAR) of cereal derivatives is proposed: a combination of in vitro digestion – which enables measurement of the bioaccessible fraction – and the QUENCHER, which makes it possible to determine the antioxidant activity of the insoluble fraction, since it is a simple and direct procedure for determining the total antioxidant capacity of solid products. After digestion, the results obtained by the antioxidant assays are up to 20-fold higher than those reported using the standard extraction methods. The non-extractable residue displayed significant antioxidant activity that accounted for up to 17% of the total antioxidant activity. Moreover, the GAR obtained in some of the assays developed was 10–40% higher than the antioxidant activity registered by the QUENCHER procedure in wheat bread, and the difference was even higher in wheat bran bread. Therefore, the use of the GAR approach could avoid underestimation of the antioxidant activity of cereal derivatives.     

Characteristics of enzymatic hydrolysis of thermal-treated wheat gluten

Effect of thermal treatment at 50–90 °C on wheat gluten hydrolysis by papain was evaluated in this study. Thermal treatment decreased the amount of sodium dodecyl sulfate (SDS) extractable protein. The treatments at 80 and 90 °C had a strong impact on protein extractability. Thermal treatment for 30 min resulted in a significant reduction in SDS extractable glutenin level in wheat gluten. A significant drop in free sulphydryl level was found in wheat gluten treated at 70 °C for 30 min. It indicated that cross-linking of glutenin through S–S occurred during thermal treatment. The treatments at 70–90 °C led to significant decreases in soluble and nitrogen level, while significant increases in peptide nitrogen amount in the hydrolysates from treated gluten were found. A time-dependent effect was observed for the changes in soluble forms of nitrogen and PN. Thermal treatment resulted in molecular mass distribution change according to gel permeation chromatography analysis. Thermal treatment significantly increased the amount of fractions with molecular mass beyond 10 K (67.2%) in the hydrolysates and greatly decreased the amounts of fractions with MM of 10–5 K and below 5 K in hydrolysates.     

Potential angiotensin I converting enzyme inhibitory peptides from gluten hydrolysate: Biochemical characterization and molecular docking study

The present study was carried out to characterize ACE inhibitory peptides which are released from the trypsin hydrolysate of wheat gluten protein. In silico proteolitic digestion of a high molecular weight glutenin subunit was performed. Among the resultant fragments, four peptides were selected for chemical synthesis based on the chemoinformatics studies and docking properties. The ACE inhibitory activity and kinetic parameters of the most important peptides were determined. Molecular docking simulation was also performed to predict the sites on ACE in which these peptides bind and displayed inhibition mechanisms. Two peptide sequences of IPALLKR (P4) and AQQLAAQLPAMCR (P6) showed higher ACE inhibitory activity among peptide collection. The IC₅₀ values of P6 and P4 were 43 ± 1.3 μM and 68 ± 2.8 μM, respectively. P6 peptide was proved to be a more potent ACE inhibitor than P4 peptide. Lineweaver-Burk plots revealed that P6 and P4 behaved as non-competitive and competitive ACE inhibitors, respectively. The simulations showed that P4 bound to the active site region. Conversely, P6 bound to the N-terminus entrance of substrate tunnel and obstructed the substrate access into the catalytic site. Overall, the results showed that these peptides would be considered as a model for discovering new bio-compatible ACE inhibitors.     

Effect of hydrostatic pressure and temperature on the chemical and functional properties of wheat gluten: Studies on gluten, gliadin and glutenin

The effect of hydrostatic pressure (0.1–800 MPa) in combination with various temperatures (30–80 °C) on the chemical and physical properties of wheat gluten, gliadin and glutenin was studied. Chemical changes of proteins were determined by extraction, reversed-phase high-performance liquid chromatography (HPLC), sodium dodecylsulphate (SDS) polyacrylamide gel electrophoresis (PAGE), circular dichroism (CD) spectroscopy, thiol measurement and studies on disulphide bonds. Rheological changes were measured by extension tests and dynamic stress rheometry. Treatment of gluten with low pressure (200 MPa) and temperature (30 °C) increased the proportion of the ethanol-soluble fraction (ESF) and decreased gluten strength. The enhancement of both pressure and temperature provoked a strong reduction of the ESF and the thiol content of gluten. Within gliadin types, cysteine containing α- and γ-gliadins, but not cysteine-free ω-gliadins were sensitive to pressure and were transferred to the ethanol-insoluble fraction. Disulphide peptides isolated from treated gluten confirmed that cleavage and rearrangement of disulphide bonds were involved in pressure-induced reactions. Increased pressure and temperature induced a significant strengthening of gluten, and under extreme conditions (e.g. 800 MPa, 60 °C), gluten cohesivity was lost. Isolated gliadin and glutenin reacted differently: solubility, HPLC and SDS-PAGE patterns of gliadin having a very low thiol content were not influenced by pressure and heat treatment; only conformational changes were detected by CD spectroscopy. In contrast, the properties of isolated glutenin having a relatively high thiol content were strongly affected by high pressure and temperature, similar to the effects on total gluten.     

Production of Proteases by Fusarium Species Grown on Barley Grains and in Media Containing Cereal Proteins

The production of proteases by the cereal plant pathogens Fusarium culmorum, F. graminearum and F. poae was followed through seven days of cultivation. The fungi were grown in mineral and in gluten culture media, and on autoclaved barley grains. The proteolytic activities of each sample were analysed at pH 2·2, 5·0 and 8·0 and the pH optima of the most active proteases were determined. All of the fungi grown in the gluten medium produced proteases that were active at pH levels between 6 and 10 and were most active at about pH 9·0. Fusarium poae also produced acid protease(s) with pH optima between 3.0 and 3.5 when grown in the gluten medium. No protease activity was detected in the cultures that were grown in the mineral medium, except that a small amount was formed after the glucose substrate was depleted. When grown on the barley grain medium the Fusarium species produced protease activities that were similar to the neutral and alkaline ones present in the gluten cultures, but no pH 2·2 protease activity was detected. The alkaline proteases had some characteristics that were similar to those of chymotrypsin.     

Fate of ACE-inhibitory peptides during the bread-making process: Quantification of peptides in sourdough,bread crumb,steamed bread and soda crackers

This study compared the concentration of angiotensin-converting enzyme (ACE) inhibitory peptides at different stages of the bread-making process, including kneading, proofing, and final products. Steamed bread, baked bread, and soda crackers were produced with 3–20% addition of rye malt sourdoughs to assess products differing in their thermal treatment. Eight tripeptides with known or predicted ACE-inhibitory activity were quantified by LC/MS in multiple reaction monitoring (MRM) mode. In wheat sourdough and rye-malt gluten sourdough, IPP was the predominant tripeptide at 58 and 473 μmol kg⁻¹, respectively, followed by LQP, IQP, and LPP. During the bread-making process, peptide concentrations were modified by enzymatic conversions at the dough stage and by thermal reactions during baking. The concentrations of IPP, LPP and VPP remained stable during dough preparation but decreased during thermal treatment; the concentrations of other peptides were changed at the dough stage but remained relatively stable during baking. The cumulative concentration of 8 ACE-inhibitory peptides in steamed bread and bread crumb exceeded 60 μmol kg⁻¹, while soda crackers contained less than 3 μmol kg⁻¹. The peptide levels in bread thus likely meet in vivo active concentrations.     

Influence of reducing agents on properties of thermo-molded wheat gluten bioplastics

The present work aims to study the influence of reducing agents of sodium bisulfite, sodium sulfite and thioglycolic acid on the equibiaxial extensional deformation of glycerol plasticized wheat gluten and the properties of gluten bioplastics thermo-molded at 125 °C. Moisture absorption, weight loss and water uptake, uniaxial tensile properties (Young's modulus, tensile strength, elongation at break and tensile set), and morphology observations were performed to characterize the physical properties of the thermo-molded gluten bioplastics. The results showed that reducing agents facilitated the viscous flow and restrained the elastic recovery of the plasticized gluten while not hindering the crosslinking reaction of gluten proteins during thermo-molding. On the contrary, reducing agents do not significantly influence moisture absorption, Young's modulus, tensile strength and the morphology of the gluten bioplastics thermo-molded at 125 °C. It is shown that reducing agents are highly effective for tailoring the flow viscosity of the plasticized gluten dough and the mechanical properties of thermo-molded gluten bioplastics.     

Phospholipids and wheat gluten blends: interaction and kinetics

A model system comprising of lysophosphatidylcholine (LPC) and isolated gluten were used help understand the positive effect of PL on bread-loaf volume. The kinetics of the effect of gluten on the thermal properties of LPC were determined using DSC. Blends of PL and 3, 6, and 10% gluten were heated from 0 to 70 °C at rates between 3 and 19 °C/min and cooled to 0 °C. The onset and peak temperatures and ΔH were recorded. The peak temperature was used to calculate the activation energy (E_a) and Z value. The transition for pure LPC vesicle formation was detectable by DSC in the presence of gluten. Gluten increased the activation energy of LPC during vesicle formation and disruption. The increase in gluten content from 3 to 6% and then to 10% had a slight effect on the activation energy value of LPC during vesicle disruption, whereas during formation a steady increase was noticed with higher gluten additions. Overall, the ΔH of the blends showed a decrease at higher heating rate. The change in the PL activation energy in the presence of gluten is indicative of a form of interaction.     

Talaromarins A–F: Six New Isocoumarins from Mangrove-Derived Fungus Talaromyces flavus TGGP35

Six new isocoumarin derivative talaromarins A-F (1–6), along with 17 known analogues (7–23), were isolated from the mangrove-derived fungus Talaromyces flavus (Eurotiales: Trichocomaceae) TGGP35. Their structures were identified by detailed IR, UV, 1D/2D NMR and HR-ESI-MS spectra. The absolute configurations of new compounds were determined by the modified Mosher’s method and a comparison of their CD spectra with dihydroisocoumarins described in the literature. The antioxidant, antibacterial, anti-phytopathogenic and inhibitory activity against α-glucosidase of all the isolated compounds were tested. Compounds 6–11, 17–19 and 21–22 showed similar or better antioxidant activity than the IC₅₀ values ranging from 0.009 to 0.27 mM, compared with the positive control trolox (IC₅₀ = 0.29 mM). Compounds 10, 18, 21 and 23 exhibited strong inhibitory activities against α-glucosidase with IC₅₀ values ranging from 0.10 to 0.62 mM, while the positive control acarbose had an IC₅₀ value of 0.5 mM. All compounds showed no antibacterial or anti-phytopathogenic activity at the concentrations of 50 μg/mL and 1 mg/mL, respectively. These results indicated that isocoumarins will be useful to developing antioxidants and as diabetes control agents.     

Dynamic viscoelastic, calorimetric and dielectric characteristics of wheat protein isolates

Dynamic oscillatory rheology of two wheat protein isolate (Prolite 100 and Prolite 200) doughs (≈48% moisture content, wet basis) were studied over a frequency range of 0.1–10 Hz during temperature sweep from 20 to 90 °C at a heating rate of 2 °C/min. Both doughs behaved similarly during heating; showed a threshold value and increased sharply, thereafter. Prolite 200 dough had a higher elastic modulus (G′) and lower phase angle (δ) whereas Prolite 100 showed a distinct gel point at 52.2 °C followed by significant increase up to 90 °C. Rheological data of doughs after isothermal heating at 90 °C for 15 min followed by cooling to 20 °C resulted in strong mechanical strength. However, Prolite 100 dough showed more viscoelastic characteristics with significant transformation from liquid-like to solid-like behavior after heating than Prolite 200. Thermal analysis of isolates indicated distinct endothermic peaks in wider temperature range (50–130 °C) at various moisture levels. Lower temperatures could be associated with denaturation of various fractions of proteins whereas higher temperature linked to glass transition temperature of isolates. SDS–PAGE did not show any clear distinction among protein subunits between two isolates. Dielectric measurements of isolates at frequencies from 500 to 3000 MHz and temperature range between 30 and 80 °C indicated Prolite 200 had higher dielectric constant (ε′) and loss factor (ε″) than Prolite 100. Isolates showed significant changes in dielectric properties above 50 °C indicating protein denaturation and supported rheological and calorimetric data.     

New Furan and Cyclopentenone Derivatives from the Sponge-Associated Fungus Hypocrea Koningii PF04

Two new furan derivatives, hypofurans A and B (1 and 2), and three new cyclopentenone derivatives, hypocrenones A–C (3–5), along with seven known compounds (6–12), were isolated from a marine fungus Hypocrea koningii PF04 associated with the sponge Phakellia fusca. Among them, compounds 10 and 11 were obtained for the first time as natural products. The planar structures of compounds 1–5 were elucidated by analysis of their spectroscopic data. Meanwhile, the absolute configuration of 1 was determined as 2R,3R by the comparison of the experimental and calculated electronic circular dichroism (ECD) spectra. All the isolates were evaluated for their antibacterial and antioxidant activity. Compounds 1, 10, and 12 all showed modest antibacterial activity against Staphylococcus aureus ATCC25923 (MIC, 32 μg/mL). In addition, compounds 1, 10 and 11 exhibited moderate DPPH radical scavenging capacity with IC₅₀ values of 27.4, 16.8, and 61.7 µg/mL, respectively.     

Changes in soluble carbohydrates, lipid peroxidation and antioxidant enzyme activities in the embryo during ageing in wheat grains

Soluble sugar contents and antioxidant enzyme activities were measured in the embryo of wheat (Triticum aestivum L., cv Charger) seeds throughout their storage under two conditions (45 °C and 100% relative humidity (RH), and 30 °C and 75% RH) to investigate whether grain deterioration during ageing was related to lipid peroxidation resulting in a decrease in the efficiency of the antioxidant defence system, and in changes in sugar metabolism. The half-viability period (P₅₀) was only 6 d at 45 °C and 100% RH against about 3.75 months at 30 °C and 75% RH. However, sensitivity of grains to accelerated ageing carried out at 45 °C and 100% RH increased during their pre-storage at 30 °C and 75% RH. Loss of grain viability at 45 °C and 100% RH was associated with an accumulation of H₂O₂ which was concomitant with a progressive decrease in catalase (CAT) and superoxide dismutase (SOD) activities, and with an increase in glutathione reductase (GR) activity. However, malondialdehyde content did not change, suggesting that there was no lipid peroxidation during such an ageing. In return, ageing of grains at 30 °C and 75% RH was not associated either with strong changes in CAT, SOD and GR activities or with an accumulation of H₂O₂. When there was no correlation between CAT, SOD and GR activities and seed viability, there was a linear correlation between CAT activity and seed vigour evaluated by the T₅₀ during ageing at 45 °C and 100% RH. Sugar metabolism in wheat embryo largely depended on ageing conditions. Loss of grain viability at 45 °C and 100% RH was associated with a marked decrease in sucrose (Su) and a slight increase in raffinose (Ra), and subsequently in the Ra/Su ratio. At 30 °C and 75% RH, seed ageing was associated with an increase in both sugars but with no strong increase in Su/Ra ratio. Our results suggest that ageing was associated with various mechanisms depending on the conditions of ageing, and that accelerated ageing at 45 °C and 100% RH was not the only model to consider in order to understand the mechanisms involved in seed deterioration.     

Antioxidant activity and phenolic content of chestnut (Castanea sativa) shell and eucalyptus (Eucalyptus globulus) bark extracts

Chestnut (Castanea sativa) shell and eucalyptus (Eucalyptus globulus) bark, waste products of the food and wood industries, respectively, were analysed as potential sources of antioxidant compounds. The extraction yield, the antioxidant activity and total phenols content of the extracts were greater in chestnut shell than in eucalyptus bark for most of the extraction conditions essayed. Extraction of chestnut shell with a 2.5% Na₂SO₃ aqueous solution led to the highest extraction yield, 25.6%, total phenols, 13.4 g gallic acid equivalent/100 g oven-dried shell, and FRAP antioxidant activity, 80.7 mmol ascorbic acid equivalent/100 g oven-dried shell. Extraction with methanol:water (50:50, v/v) provided the best results for eucalyptus bark. The antioxidant activity and the total phenols content of the extracts had a positive linear correlation. FTIR spectroscopy confirmed the higher content of phenolic compounds in chestnut shell extracts compared to eucalyptus bark extracts. Chestnut shell extracts were characterized by the presence of high molecular weight species whereas lower molecular weight species were predominant in eucalyptus bark extracts.     

Antioxidant properties of feruloyl glycerol derivatives

The natural plant components, 1-feruloyl-sn-glycerol (FG) and 1,3-diferuloyl-sn-glycerol (F₂G), were synthesized by the enzymatic esterification of glycerol and soybean oil mono- and diacylglycerols, respectively, with ethyl ferulate. The isolated FG and F₂G were examined for their antioxidant activities as free radical scavengers (DPPH assay) and peroxyl lipid oxidation inhibitors (TBARS assay). The H atom transfer kinetics, as monitored by DPPH free radical bleaching, of FG showed that the mono-feruloyl glycerol acted as a rapid antioxidant (50% reduction of DPPH radical < 5 min) in ethanol solutions while F₂G and ferulic acid activity rates were in the range of intermediate antioxidants (50% reduction of DPPH radical in 5-30 min). FG and F₂G showed similar activity as the control agent, ethyl ferulate, towards the inhibition of the AAPH-induced peroxyl radical oxidation of surfactant emulsified γ-linolenic acid. A slight excess of feruloyl groups was sufficient to completely suppress the formation of secondary lipid oxidation products.