Modelling of perceived sweetness in biscuits based on sensory analysis as a new tool to evaluate reformulation performance in sugar reduction studies

Food Chemistry, Volume 425, November 2023, Article Number 136490

Sugar reduction in foods is of global interest in food science and industry to limit excessive calorie intake for healthier nutrition. Therefore, a modified Weibull model-based approach is presented here to relate sweetness perception with sugar concentration for the first time. The model was tested by using sweetness perception data obtained from sensory analysis of biscuits (wholewheat flour, whey or hydrolysed pea protein, different sucrose forms, ethylvanillin, furaneol, phenylacetaldehyde) using a line scale and untrained panellists. Sweetness scores increased 56%, 59%, 41% by the addition of wholewheat flour, proteins, or aroma compounds at 17% sucrose containing biscuits, respectively. Wholewheat flour and proteins boosted Maillard reaction products imparting baked/caramel-like flavour. The Weibull model well fitted to the sweetness perception data with a sigmoidal curve and high predicting power. This approach allows to explain how much sugar reduction can be achieved to reach a targeted sweetness perception without performing further sensory analysis.
Effect of formulation on the dispersion kinetics of baby biscuits in water, milk, and fruit juice

European Food Research and Technology, Volume 249, August 2023, pages 2925–2933

Quick liquid absorption is one of baby biscuits’ most important quality criteria. A practical procedure based on liquid absorption kinetics was developed for the quality assessment of baby biscuits in this study. Biscuits made of plain flour, wholewheat flour, and vegetable puree were immersed in water, milk, and fruit juices to determine their liquid absorption rates. The data were analyzed by means of Peleg and modified Weibull models. The parameters describing physical properties such as specific volume, texture, and pore size distribution of biscuits were calculated from the model fits. High values of the scale parameter (α) of the modified Weibull model and the Peleg rate constant (k1) indicated a high rate of absorption. The initial absorption rate was related to the average pore size and followed the order: plain (395 µm) > wholewheat (334 µm) > vegetable puree biscuits (208 µm). Equilibrium absorption value was related to the total porosity of biscuits, and it was the highest for wholewheat biscuits. Liquid transfer mechanism was diffusion according to shape parameter values. The absorption behavior of biscuits in liquids was similar and explained by both models.
Optimization of reaction conditions for the design of cereal-based dietary fibers with high antioxidant capacity

Journal of the Science of Food and Agriculture, Volume 102, May 2022, pages 65026510

BACKGROUND: Bound antioxidants are distinguished by their strong potential to defend the body against oxidative stress. Cereal bran fractions contain antioxidant compounds bound to dietary fiber, but this only occurs to a limited extent. Increasing the quantity of bound antioxidant compounds using soluble phenolic compounds is thought to be a possible method for designing cereal-based dietary fibers with high antioxidant potential. Certain cereal bran samples (wheat, oat, rye, and rice) were reacted with different concentrations of beverages (green tea infusion, black tea infusion, espresso, and red wine), rich in various soluble phenolic compounds. The interactive effects of parameters (time, temperature, and pH) and the optimum conditions for the reaction were determined using response surface methodology.

RESULTS: Green tea infusion (30 g·L−1) was found to be the most effective beverage. The pH rather than the time and temperature had significant (O p < 0.0001) effects on the reaction. Neutral or slightly alkaline conditions (pH 7.0–7.9) and mild temperatures (at about 50 °C) were found to be optimum to increase the antioxidant capacity of cereal bran samples. The total antioxidant capacity of oat bran treated with green tea infusion under optimum conditions (53.3 °C, pH 7.4, 60.0 min) reached 226.42 ± 0.88 mmol Trolox equivalent·kg−1. The free amino groups in cereal bran were also found to decrease (32–95%) after treatment.

CONCLUSION: It is possible to design functional cereal-based dietary fibers, rich in bound antioxidant compounds through treatment with green tea infusion under optimum conditions.

Kinetic modeling of Maillard and caramelization reactions in sucrose-rich and low moisture foods applied for roasted nuts and seeds

Food Chemistry, Volume 395, November 2022, Article number 133583

A kinetic model was proposed by using a multiresponse kinetic modeling approach for Maillard and caramelization reactions in low moisture foods at neutral pH containing a moderate amount of amino acid and sucrose, but a restricted amount reducing sugar. The change in the amount of sucrose, protein-bound lysine, free amino acids, and certain products of Maillard reaction was monitored during roasting of sunflower seed, pumpkin seed, flaxseed, peanut, and almond at 160 and 180 °C. A slightly different model was proposed for pumpkin seed due to its difference in compositional and physicochemical characteristics as expressed by principal component analysis. Accordingly, 3-deoxyglucosone formation via sugar degradation; 5-hydroxymethylfurfural formation from 3-deoxyglucosone and only in pumpkin seeds the conversion of N-ε-fructoselysine to glyoxal and Heyns product to 1-deoxyglucosone were found to be quantitatively important. N-ε-carboxymethyllysine and N-ε-carboxyethyllysine mainly originated through oxidation of N-ε-fructoselysine and the reaction of methylglyoxal with lysine residue, respectively.

Effectiveness of asparaginase on reducing acrylamide formation in bakery products according to their dough type and properties

Food Chemistry, Volume 402, February 2023, Article number 134224

Effect of asparaginase was tested in different biscuit and cracker doughs, and wafer batter by changing processing conditions such as enzyme dosage, dough resting time and temperature, mixing speed and time, and mixing procedure of the recipe components. Acrylamide reductions achieved were 96, 80, 54% in rotary cut biscuits, crackers and wire cut cookies, respectively due to high water activity of their dough. Asparaginase did not affect surface color or spread ratio. There was a positive correlation between asparagine content and acrylamide formation except for rotary molded biscuit doughs. No significant decrease was found in rotary molded biscuits because of low water (water activity of 0.70) and high fat content. This indicated that water activity of dough is an important factor for the effectiveness of asparaginase treatment. The results suggested that water activity value exceeding 0.75 is needed in the dough to effectively reduce asparagine, so acrylamide in bakery products.

Effect of salts on the formation of acrylamide, 5-hydroxymethylfurfural and flavour compounds in a crust-like glucose/wheat flour dough system during heating

Food Chemistry, Volume 410, June 2023, Article number 135358

Among many strategies known to mitigate acrylamide formation, addition of cations, particularly calcium, is effective and can be used in bakery products. In this study, the effects of NaCl, KCl, CaCl2, MgCl2, sodium lactate, calcium lactate, and magnesium lactate on aroma and acrylamide formation were investigated in glucose/wheat flour dough systems during heating. Addition of salts inhibited Maillard reaction in favour of caramelisation, with divalent cations found to be most effective. The impact of salts on acrylamide reduction became less effective with increasing temperature. Most Strecker aldehydes and pyrazines decreased in the presence of salts, however CaCl2 and calcium lactate increased the concentration of furans, furfurals, and diketones. Calcium lactate also increased some ethyl-substituted pyrazines at high temperatures. Reduction of acrylamide with salts is associated with higher amounts of furan derivatives and decreased amounts of Strecker aldehydes and pyrazines. The mechanisms behind these changes are discussed.

Safety concerns of processed foods in terms of neo-formed contaminants and NOVA classification

Current Opinion in Food Science, Volume 47, October 2022, Article number 100876

Processing of foods is essential to supply safe and nutritious foods to the growing world population. Considering the food-processing conditions and the composition of food products, neo-formed contaminants, such as acrylamide, furan, furfural, 5-hydroxymethylfurfural, nitrosamines, heterocyclic amines, and so on, are known to be formed in highly consumed foods. NOVA classifies foods into four groups as unprocessed/minimally processed foods, processed culinary ingredients, processed, and ultraprocessed foods. This review aims to stress how the NOVA food-classification system is ambiguous in terms of food safety because thermal-process contaminants might also occur in minimally processed foods or might be prevented in so-called ultraprocessed foods by using industrial food processes or processing aids.

Interactions of epicatechin and cysteine with certain other dicarbonyl scavengers during their reaction with methylglyoxal under simulated physiological conditions

Food Chemistry, Volume 369, February 2022, Article number 130884

This study aimed at investigating the effects of interactions between dietary dicarbonyl scavengers coexisting in human plasma on the overall methylglyoxal scavenging potential. Apart from being the most effective dicarbonyl scavengers, epicatechin or cysteine, which can be easily oxidized by other compounds, was reacted with methylglyoxal in the presence of certain other dicarbonyl scavengers under simulated physiological conditions (pH 7.4, 37 °C). Methylglyoxal was monitored kinetically in the presence of the individual scavengers or in their combinations with epicatechin or cysteine. The observed and estimated reaction rate constants were calculated for each combination. As the observed rate constant for the reaction between cysteine and epicatechin was found to be significantly greater (p < 0.05) than the estimated rate constant, the results suggest synergism occurred in this combination. Epicatechin was found to interact antagonistically with scavengers that stimulate its oxidation such as creatine, quercetin, and gallic acid during methylglyoxal scavenging.

Effect of food combinations and their co-digestion on total antioxidant capacity under simulated gastrointestinal conditions

Current Research in Food Science, Volume 5, February 2022, Pages 414-422

This study aims to investigate the antioxidant interactions between mostly co-consumed foods in daily diet. Total antioxidant capacities of individual and the binary combinations of certain food samples from different groups including fruits, vegetables, grain sources, dairy and meat products were measured. The types of interactions (synergism, antagonism, and additive) between food samples were determined by a statistical comparison between estimated and measured total antioxidant capacity. The results revealed an antagonism in the combinations of milk with the fruits or green tea extract while a clear synergism was reported in the combination of fruits with breakfast cereal, whole wheat bread, or yoghurt. The selected foods were also subjected to in vitro digestion protocol. Slightly alkaline conditions were found to significantly (p < 0.05) increase the total antioxidant capacity of foods. Synergism was observed during the digestion of the combinations of milk with fruits or tea extracts. Hydroxyl radical scavenging capacity was also determined in the bioaccessible fractions of foods. Green tea extract was found to be the most efficient scavenger (936.48 ± 16.64 mmol TE.kg−1).

Formation of Bioactive Tyrosine Derivatives during Sprouting and Fermenting of Selected Whole Grains

Journal of Agricultural and Food Chemistry, Volume 69, Issue 42, October 2021, Pages 12517–12526

Sprouting is a popular method in cereal processing because sprouted grains are accepted to have high nutritional value. The increased proteolytic activity by sprouting increases the free amino acids in grains. It was hypothesized that an increased amount of tyrosine can be utilized by microorganisms during fermentation to form higher amounts of bioactive tyrosine derivatives. Sprouting increased the tyrosine and tyramine contents considerably, but increases and decreases in l-3,4-dihydroxyphenylalanine (l-DOPA) and dopamine were specific to the cereal. More tyramine, l-DOPA, and dopamine formation was observed during sourdough fermentation than that in yeast fermentation. As a result of the combined application of sprouting (48 h at 20 °C) and sourdough fermentation (36 h at 30 °C), the amounts of dopamine, l-DOPA, and tyramine found in rye were 27, 50, and 136 mg/kg, respectively. Cereal products rich in dopamine and l-DOPA can thus be produced as functional food ingredients with their positive effects on human health and mood.

Effects of sprouting and fermentation on free asparagine and reducing sugars in wheat, einkorn, oat, rye, barley, and buckwheat and on acrylamide and 5-Hydroxymethylfurfural formation during heating

Journal of Agricultural and Food Chemistry, Volume 69, Issue 32, August 2021, Pages 9419–9433

Usage of sprouted grains is an increasing trend in thermally processed foods. Sprouting alters the composition of sugars and amino acids, which are Maillard reaction precursors. Free asparagine, total free amino acids, and sugars were monitored during sprouting and yeast and sourdough fermentations. Acrylamide and 5-hydroxymethylfurfural (HMF) were analyzed in heated samples. The asparagine concentration decreased up to 40% after 24–36 h of sprouting, except for buckwheat, and then increased to the initial concentration after 48 h and several folds after 72 h. The increased amount of reducing sugars after sprouting caused higher acrylamide and HMF formation even if the asparagine concentration was lower. Acrylamide and HMF formation decreased after fermentation of sprouted wholemeal because sugars and asparagine were consumed by yeast. A pH drop of 3 units by sourdough fermentation decreased acrylamide formation but increased HMF formation. Results indicated that sprouted cereal products should be produced under controlled conditions to be used in heated foods.

Formation of amino acid derivatives in white and red wines during fermentation: Effects of non-Saccharomyces yeasts and Oenococcus oeni

Food Chemistry, Volume 343, 1 May 2021, Article number 128415

This study aimed to investigate the effect of commercial non-Saccharomyces yeasts and Oenococcus oeni on the formation of amino acid derivatives, some of which have neuroactive properties, during fermentation in laboratory-scale processing of white and red wines. Changes in the content of amino acid derivatives during fermentation of large-scale white and red wines were also evaluated. The highest kynurenic, picolinic, and quinolinic acid concentrations were observed in white wine fermented with Torulaspora delbrueckii, Kluyveromyces thermotolerans and Saccharomyces cerevisiae simultaneously. No changes in the content of picolinic and kynurenic acid were observed during large-scale white wine fermentation. Tryptophan ethyl ester concentration in all wines increased significantly during alcoholic fermentation. Natural and O. oeni malolactic fermentation did not alter the content of picolinic acid, a neuroprotective compound, in red wine. The decrease in the content of tyramine, phenylethylamine, and dopamine in laboratory-scale white wines was observed during alcoholic fermentation.

Effects of fermentation time and shooting period on amino acid derivatives and free amino acid profiles of tea

LWT, Volume 137, February 2021, Article number 110481

This study aimed to investigate the effect of oxidation on free amino acids and their derivatives in tea. Oolong tea samples, oxidized for 0, 10, 30, and 60 min, green tea, and black tea were produced from the same batch of fresh tea leaves. Effects of shooting periods on free amino acids and their derivatives were also evaluated in this study. Free amino acids and their derivatives were extracted with water and analyzed by LC-MS/MS. It was observed that total amino acid content of teas in the first shooting period (16231 ± 241 μg/g-31391 ± 2034 μg/g) was higher than the second (9635 ± 379 μg/g-11665 ± 426 μg/g) and third (13937 ± 360 μg/g-17661 ± 1359 μg/g) shooting periods. Content of most amino acids including gamma aminobutyric acid (GABA) in black and oolong teas were higher than those of green tea. However, theanine contents of black and oolong teas were lower than that of green tea. Kynurenine, kynurenic acid, quinolinic acid, dopamine, tyramine, phenylethylamine and tryptamine were found in all tea samples. Kynurenic acid content was the highest (1 ± 0.1 μg/g-3±0.4 μg/g) in green, oolong and black tea samples. Concentrations of kynurenine, kynurenic acid, quinolinic acid, and dopamine were mostly found to be higher in green tea than black tea.

Neuroactive compounds in foods: Occurrence, mechanism and potential health effects

Food Research International, Volume 128, February 2020, Article number 108744

Neuroactive compounds are synthesized by certain plants and microorganisms by undertaking different tasks, especially as a stress response. Most common neuroactive compounds in foods are gamma-aminobutyric acid (GABA), serotonin, melatonin, kynurenine, kynurenic acid, dopamine, norepinephrine, histamine, tryptamine, tyramine and β-phenylethylamine. Fermented foods contain some of these compounds, which can affect human health and mood. Moreover, food processing such as roasting and malting alter amount and profile of neuroactive compounds in foods. In addition to plant-origin and microbially-formed neuroactive compounds in foods, these substances are also formed by gut microbiota, which is the most attractive subject to assess the interaction between gut microbiota and mental health. The discovery of microbiota-gut-brain axis calls for the investigation of the effects of diet on the formation of neuroactive compounds in the gut. Furthermore, probiotics and prebiotics are indispensable elements for the understanding of the food-mood relationship. The focus of this comprehensive review is to investigate the neuroactive compounds found naturally in foods or formed during fermentation. Their formation pathways in humans, plants and microorganisms, potential health effects, effects of diet on the formation of microbial metabolites including neuroactive compounds in the gut are discussed throughout this review. Furthermore, the importance of gut-brain axis, probiotics and prebiotics are discussed.

Physiological relevance of food antioxidants

Advances in Food and Nutrition Research, Volume 93, 2020, Pages 205-250

Dietary antioxidants are associated with prevention of oxidative stress related chronic diseases including certain types of cancer, cardiovascular diseases, diabetes, and neurodegenerative diseases. In recent years, there has been a growing interest in extending the knowledge on their physiological effects in human body. There are numbers of epidemiological, clinical, meta-analysis, and in vitro studies to explain formation mechanisms of each chronic diseases as well as the potential effects of dietary antioxidants on these diseases and gut health. Comprehensive studies for food antioxidants’ journey from dietary intake to target tissues/organs deserve a serious consideration to have a clear understanding on the physiological effects of dietary antioxidants. Therefore, absorption and metabolism of dietary antioxidants, and the factors affecting their absorption, such as solubility of antioxidants, food matrix, and interaction between antioxidants have been evaluated in several research articles. This chapter provides an overview about potential health effects of dietary antioxidants considering with their absorption and metabolism in human body.

Potential reactions of thermal process contaminants during digestion 

Trends in Food Science and Technology, Volume 106, December 2020, Pages 198-208

Background: Thermal process contaminants, which exert carcinogenic or mutagenic effects on human health, are generated in foods during common thermal processing such as frying, baking, and roasting. Heterocyclic aromatic amines, acrylamide, 5-hydroxymethyl-2-furfural, α-dicarbonyl compounds, advanced glycation end products, chloropropanols and related esters, and lipid oxidation products are the most important examples for thermal process contaminants in thermally processed foods. The presence of varying amounts of thermal process contaminants in widely consumed foods daily is considered as a major concern by public authorities worldwide. Therefore, efforts to reduce the amount of these substances in heat-treated foods have gained importance. Scope and approach: Many thermal process contaminants may react with other food components in the digestive tract because of certain functional groups in their structures. Here, we overview these reactions that may potentially take place in the gastrointestinal system during a daily diet. Considering their adverse health effects, understanding better the reactions of thermal process contaminants under gastrointestinal conditions is important for a realistic risk assessment. Key findings and conclusions: During digestion, certain process contaminants are formed from their precursors. On the other hand, some are eliminated as a result of reactions with amino or sulfhydryl compounds released in the digestive tract. Reviewed data indicate that the levels of process contaminants in foods do not reflect the exact amount that human is exposed to. This suggests that potential elimination and formation reactions of process contaminants during digestion should be taken into consideration to accurately estimate their bioavailabilities.

5-Hydroxymethylfurfural accumulation plays a critical role on acrylamide formation in coffee during roasting as confirmed by multiresponse kinetic modelling

Food Chemistry, Volume 318, 15 July 2020, Article number 126467

This study aims to investigate in depth the mechanism of acrylamide formation in coffee during roasting. For this purpose, a comprehensive kinetic model including the elementary steps for acrylamide formation was proposed. The changes in sucrose, reducing sugars, free amino acids, asparagine, acrylamide, 3-deoxyglucosone, methylglyoxal, glyoxal, and 5-hydroxymethylfurfural were monitored in coffee during roasting at 200, 220 and 240 °C. Dominant pathways of complex reactions leading to acrylamide were unravelled by means of multiresponse kinetic modelling approach. The results of the model indicated that sucrose degrades into glucose and a reactive fructofuranosyl cation. Interestingly, glucose takes part mostly in the formation of intermediates, glyoxal and especially 3-deoxyglucosone rather than acrylamide formation. On the other hand, fructofuranosyl cation contributed mostly to the formation of 5-hydroxymethylfurfural which was found to be the most important intermediate precursor of acrylamide formed in coffee during roasting.

Investigation of the methylglyoxal scavenging kinetics of different food matrices under simulated intestinal conditions

European Food Research and Technology, Volume 246, Issue 12, December 2020, Pages 2461-2470

This study aimed to evaluate the potential roles of different foods to scavenge exogenous dicarbonyl compounds under simulated gastrointestinal conditions. Four food groups having different arginine, creatine, thiol, and flavonoid contents were subjected to simulated gastric and intestinal conditions together with methylglyoxal. In comparison to control, foods from group 1 (chicken, beef and egg), group 2 (walnut, hazelnut, and kidney bean) and group 3 (broccoli, onion, garlic, and cauliflower) caused a significant (p < 0.05) decrease in the concentration of methylglyoxal under gastric conditions. Egg was found as the most efficient methylglyoxal scavenger food under gastric conditions. Changes in the concentration of methylglyoxal were monitored kinetically during the intestinal phase. All foods caused significant (p < 0.05) decreases in the concentration of methylglyoxal under intestinal conditions. Chicken, beef, and broccoli were found to scavenge more than 80% of methylglyoxal during 2 h of intestinal digestion. The reaction of methylglyoxal with scavenging compounds in foods was evaluated using an irreversible bimolecular reaction model. Reaction rate constants and initial reaction rates were calculated for each food. The highest reaction rate constant was estimated as 26.6 ± 1.38 L/mol min for egg, while the highest initial reaction rate was 3.6 ± 0.42 mM/min for chicken. Foods were ranked according to their methylglyoxal scavenging rates under intestinal conditions and their scavenging potential was associated with their scavenging content.

Effects of different cooking methods on methylglyoxal scavenging potential of meat under simulated gastrointestinal conditions

LWT, Volume 132, October 2020, Article number 109833

This study aimed at investigating the effects of different cooking methods on methylglyoxal scavenging potential of cooked meats under simulated gastrointestinal conditions. Grilling and sous vide cooking were chosen as representative cooking techniques for high temperature short time and low temperature long time heating, respectively. Beef and chicken meat were grilled and sous vide cooked at different degrees of doneness. The samples were subjected to simulated gastric and intestinal digestion with methylglyoxal. Significant reductions (p < 0.05) exceeding 50% in the amounts of methylglyoxal were determined in the presence of meat samples under intestinal conditions. Comparing to raw meat, grilling and mincing were found to decrease significantly (p < 0.05) methylglyoxal scavenging potential of beef samples. However, no difference (p > 0.05) was observed in methylglyoxal scavenging potential of beef and chicken meats after sous vide cooking. Among the compositional factors (thiol groups, free amino groups, creatine, arginine, and lysine), creatine was found as the most significant methylglyoxal scavenger in raw and grilled beef under intestinal conditions.

A new procedure to measure cysteine equivalent methylglyoxal scavenging activity (CEMSA) of foods under simulated physiological conditions

Journal of Functional Foods, Volume 63, December 2019, Article number 103575

This study aims at investigating dicarbonyl scavenging potential of foods under simulated physiological conditions using a kinetic approach. Bioaccessible fractions obtained after gastrointestinal digestion were reacted with methylglyoxal for 24 h (pH 7.4, 37 °C). The changes in the percentage of methylglyoxal inhibition with time were plotted for food samples and cysteine. The area under the curves were used to calculate the cysteine equivalent methylglyoxal scavenging activity (CEMSA) of foods. Among foods, nuts, meat, egg, cheese, strawberry, broccoli, garlic, and onion were found to have CEMSA values higher than 15 mmol cysteine equivalent per kg. The CEMSA values were highly correlated with total thiol and amino groups for all foods except fruits. The foods were classified as “rapidly reacting & high capacity”, “slowly reacting & high capacity”, and “slowly reacting & low capacity” based on their MGO inhibition percentage and rate.

Multiresponse kinetic modelling of 5-hydroxymethylfurfural and acrylamide formation in sesame (Sesamum indicum L.) seeds during roasting

European Food Research and Technology, Volume 246, Issue 12, December 2020, Pages 2399-2410

This study aims to investigate the formation mechanism of 5-hydroxymethylfurfural and acrylamide in sesame seeds during roasting. Sesame seeds were roasted at 180, 200, and 220 °C for different time intervals, and changes in the concentration of sucrose, free amino acids, asparagine, 3-deoxyglucosone, 5-hydroxymethylfurfural, and acrylamide were monitored. Multiresponse kinetic modelling was used to develop a reaction model including possible ways of 5-hydroxymethylfurfural and acrylamide formation. According to this, sucrose degraded into glucose and fructofuranosyl cation under dry conditions and high temperatures during sesame roasting. The results of the kinetic model indicated that glucose mostly degraded to 3-deoxyglucosone formation and 5-hydroxymethylfurfural formation was mostly originated from fructofuranosyl cation. Additionally, acrylamide formation through the reaction of asparagine with 5-hydroxymethylfurfural was kinetically important than its reaction with glucose or 3-deoxyglucosone. Multiresponse kinetic modelling provided understanding the roles of intermediates giving rise to the formation of acrylamide and 5-hydroxymethylfurfural in roasted sesame seeds.

Multiresponse kinetic modelling of α-dicarbonyl compounds formation in fruit juices during storage

Food Chemistry, Volume 320, 1 August 2020, Article number 126620

This study aims to investigate the formation of α-dicarbonyl compounds in fruit juices and nectars during storage using multi-response kinetic modeling approach. Changes in the concentrations of sugars, amino acids, α-dicarbonyl compounds (glucosone, 3-deoxyglucosone, threosone, methylglyoxal, glyoxal) and 5-hydroxymethylfurfural in apple juice, orange juice and peach nectar were monitored during storage. The concentrations of free amino acids showed no statistically significant change during storage. This suggested that sugar degradation reactions were found responsible for α-dicarbonyl compound formation. In apple and orange juices, the reaction rate constant of glucosone formation was found higher than that of 3-deoxyglucosone formation. Contrary, in peach nectar, 3-deoxyglucosone formation was the dominant. The contribution of fructose dehydration through fructofuranosyl cation on the formation of 5-hydroxymethylfurfural was significantly higher (p < 0.05) than 3-deoxyglucosone dehydration. The use of multi-response kinetic modeling provided better understanding the most possible pathway of sugar degradation reactions in fruit juices.

Modulation of gastrointestinal digestion of ß-lactoglobulin and micellar casein following binding by (-)-epigallocatechin-3-gallate (EGCG) and green tea flavanols

Food and Function, Volume 11, Issue 7, July 2020, Pages 6038-6053

The effect of binding of flavonoids, (-)-epigallocatechin-3-gallate (EGCG) and green tea extract (GTE), to beta-lactoglobulin (ß-Lg) and micellar casein (micellar casein isolate, MCI) on protein digestibility was investigated. ß-Lg resisted digestion by pepsin, but in the presence of EGCG the digestion of ß-Lg was enhanced. Binding of EGCG to ß-Lg was identified by nitro blue tetrazolium (NBT) staining and found, by isothermal titration calorimetry, to be an enthalpy-driven exothermic process, with a binding constant of 19?950 L mol-1. Binding promoted a more rapid digestion of ß-Lg during simulated upper duodenal digestion. NBT staining indicated a loss of binding of EGCG to ß-Lg during combined gastric and distal small intestinal digestion and correlated with the cleavage of ß-Lg. However, increased ß-Lg heteromer formation and reduced ß-Lg monomer digestibility were observed for the ß-Lg-GTE complex. MCI was more digestible than ß-Lg during pepsin digestion, but reduced digestibility was observed for both MCI-EGCG and MCI-GTE complexes, with loss of binding during intestinal digestion. The free radical scavenging capacity (FRSC) of EGCG remained stable for the ß-Lg-EGCG complex throughout the gastric and intestinal phases of digestion, but this was significantly lowered for the MCI-EGCG complex. These results indicated that polyphenols bind to milk proteins modulating the in vitro digestibility and FRSC of ß-Lg and MCI as a result of the formation of complexes.

Effects of fermentation and heat treatments on bound-ferulic acid content and total antioxidant capacity of bread crust-like systems made of different whole grain flours

Journal of Cereal Science, Volume 93, May 2020, Article number 102978

In this study, bread crust-like systems were prepared by heating (5, 15 and 30 min at 200 °C) freeze-dried fermented doughs obtained using different cereal grains. The flours of whole wheat, refined wheat, whole einkorn, whole rye, whole oat and whole maize were used. The effects of fermentation and heating on bound ferulic acid concentration and total antioxidant capacity were determined. Besides, high molecular weight fractions, containing also melanoidins formed in bread crust-like systems during heating were analyzed for their bound ferulic acid content and total antioxidant capacity. Increasing heating time at 200 °C also increased the amounts of high molecular weight fractions in the bread crust-like systems for all cereals. The total antioxidant capacity of bread crust-like samples increased significantly with heating time (p < 0.05). However, the opposite was true for the high molecular weight fractions of bread crust-like samples. Mean bound ferulic acid concentrations of different cereal flours were found to range between 78.3 mg/kg (for refined wheat) and 667.7 mg/kg (for whole einkorn). Heating had no significant effect on bound ferulic acid contents of bread crust-like systems. For all cereals, the highest concentrations of bound ferulic acid were detected in the high molecular weight fractions of bread crust-like systems heated at 200 °C for 5 min. However, bound ferulic acid concentrations significantly decreased in high molecular weight fractions as heating time increased (p < 0.05).

Lactose hydrolysis and protein fortification pose an increased risk for the formation of Maillard reaction products in UHT treated milk products

Journal of Food Composition and Analysis, 2019, 84, UNSP 103308

This study aimed to survey the content of Maillard reaction products in different UHT-treated milk products and to assess how formation of these products and lysine blockage is affected by the composition. For this purpose, different commercial UHT milks including milk (whole, semi-skimmed and skimmed), lactose-hydrolyzed, protein-fortified, lactose-hydrolyzed protein fortified and follow-on infant milks were analyzed. Among the Maillard reaction products, dicarbonyl compounds, 5-hydroxymethylfurfural, furosine, N-epsilon-carboxymethyllysine and N-epsilon-carboxyethyllysine were monitored. The results showed that fortification of UHT milks with protein and carbohydrates as well as hydrolysis of lactose promoted the Maillard reaction. Among the dicarbonyl compounds, 3-deoxyglucosone formation, which was the dominant dicarbonyl compound in milks, varied between 3.12-12.67 mg/L, 13.45-21.98 mg/L and 4.59-40.38 mg/L in lactose hydrolyzed, lactose-hydrolyzed protein fortified and follow-on infant milks whereas it was 0.22-0.40 mg/L in milks, respectively. Similarly, 5-hydroxymethylfurfural could not be detected in milks, whereas mean 5-hydroxymethylfurfural concentration was found to be 56.3 mg/L and 31.5 mg/L in protein-fortified milks and lactose-hydrolyzed protein-fortified milks, respectively. Accordingly, % blocked lysine, furosine, N-epsilon-carboxymethyllysine and N-epsilon-carboxyethyllysine content of different UHT milks were found to be significantly higher than milks (p < 0.05). This is the first study reporting the Maillard reaction products in protein-fortified and infant milks.

Kinetic evaluation of the formation of tryptophan derivatives in the kynurenine pathway during wort fermentation using Saccharomyces pastorianus and Saccharomyces cerevisiae 

Food Chemistry, 2019, 297, UNSP 124975

This study aimed to evaluate the formation of tryptophan derivatives in the kynurenine pathway during wort fermentation using a multi-response kinetic model and an empirical modified logistic model. Saccharomyces cerevisiae NCYC 88 (ale yeast) and S. pastorianus NCYC 203 (lager yeast) were used to understand the effect of fermentation type on tryptophan derivatives. According to the modified logistic model, tryptophan concentration was critical for the maximum production rate of kynurenic acid, a neuroprotective compound. The results indicated that utilization of tryptophan and kynurenic acid formation were faster in wort fermented with S. cerevisiae than with S. pastorianus. The reaction rate constants implied that the kynurenic acid formation stage was minor compared to other enzymatic reactions leading to NAD(+) synthesis. Multi-response kinetic modeling of kynurenine pathway provided insights into tryptophan derivative formation, which can facilitate improved beer fermentation processing.

Investigations on the Maillard Reaction in Sesame (Sesamum indicum L.) Seeds Induced by Roasting

Journal of Agricultural and Food Chemistry, 2019, 67(17), 4923-4930

This study investigated the formation of Maillard reaction products in sesame seeds under different roasting conditions. Sesame seeds were roasted at 150, 180, 200, and 220 degrees C for 10 min, and thermal process contaminants including 5hydroxymethylfurfural, acrylamide, furan, and dicarbonyl compounds (1-deoxyglucosone, 3-deoxyglucosone, methylglyoxal, and diacetyl) together with glycation markers namely N-epsilon-fructosyllysine, N-epsilon-carboxymethyllysine, and N-epsilon-carboxyethyllysine, were monitored. Roasting induced the formation of 5-hydroxymethylfurfural, acrylamide, and dicarbonyl compounds, except furan, significantly (p < 0.05). 5-Hydroxymethylfurfural and acrylamide content of roasted sesame seeds were found to vary as 3-40 mg/kg and 135-633 mu g/kg, respectively. Dicarbonyl compounds were in the following order: methylglyoxal > 3-deoxyglucosone > 1-deoxyglucosone > diacetyl. On the other hand, N-epsilon-fructosyllysine concentration decreased while the roasting temperature increased; however, N-epsilon-carboxymethyllysine and N-epsilon-carboxyethyllysine formation was induced under those conditions. This is the first study reporting the formation of thermal process contaminants and glycation markers in sesame seeds through Maillard reaction during roasting.

Interactions of dietary fiber bound antioxidants with hydroxycinnamic and hydroxybenzoic acids in aqueous and liposome media

Food Chemistry, 2019, 278, 294-304

The interactions between dietary fiber (DF)-bound antioxidants and free antioxidants, with different substitution patterns of -OH and -OCH3 groups on their aromatic rings has been investigated. The activity and efficiency of these interactions were examined with a structural approach. Whole wheat (WW) DF-bound antioxidants and 21 hydroxycinnamic acid/hydroxybenzoic acids (HCA/HBA) were used in the experimental studies. Studies were performed in liposome and aqueous media by monitoring lipid oxidation and scavenging of DPPH radical in the presence of WW-bound antioxidants and HCA/HBA derivatives. Predominantly synergistic interactions were observed in aqueous medium, while both synergistic and antagonistic interactions were seen in liposome medium. Concentrations of HCA/HBA and WW-bound antioxidants in mixtures and their 2-way interactions made significant effect on lipid oxidation and radical scavenging reactions, with some exceptions. HCA/HBA derivatives with 3,4 -dihydroxyphenyl substitution acted as strong antioxidants in liposome medium, while the number of -OH groups affected antioxidant activity in aqueous medium.

Investigations on the effect of broccoli and wine sulphur compounds on glyoxal scavenging under simulated physiological conditions 

Journal of Functional Foods, 2019, 55, 220-228

This study aimed to investigate the glyoxal (GO) scavenging effect of broccoli and wine sulphur compounds in model systems under physiological conditions. The model systems composed of GO and different sulphur compounds both in pure forms and food extracts were subjected to simulated physiological conditions (37 degrees C & 7.4 pH, 2 h). The results revealed that some of these sulphur sources could scavenging GO under these conditions. From the pure sulphur compounds tested, potassium metabisulphite and cysteine was found as the most effective. Wine scavenged 18.01 +/- 2.83% of GO (10 mu mole) whereas potassium metabisulphite addition (7 mu mole) to wine caused additional 20.81% scavenge. In addition, the results indicated that 11.70 +/- 7.07% and 54.48 +/- 6.38% of GO was scavenged by bioaccessible raw and steamed broccoli, respectively. High-resolution mass spectrometry scan analysis confirmed that it was attributed to the addition of GO to both amino acids and sulforaphane (SF)-amino acid adducts under physiological conditions.

Behaviour of Trolox with macromolecule-bound antioxidants in aqueous medium: Inhibition of auto-regeneration mechanism

Food Chemistry, 2018, 243, 428-434

This work aimed at investigating the behaviour of Trolox, vitamin E analogue, in presence of macromolecule-bound antioxidants in aqueous radical medium. Three main groups of macromolecule-bound antioxidants were assayed: dietary fiber (DF), protein and lipid-bound antioxidants, represented by whole wheat, soybean and olive oil products, respectively. Experimental studies were carried out in aqueous ABTS (2,2′-azinobis(3-ethyl-benzothiazoline-6-sulfonic acid)) radical medium. Trolox and macromolecule-bound antioxidants were added to radical separately and together in different concentrations. Antioxidant capacities were determined using QUENCHER procedure. pH of radical media was altered for DF and protein-bound antioxidant studies to examine its effect. Chemometric tools were used for experimental design and multivariate data analysis. Results revealed antagonistic interactions for Trolox with all macromolecule-bound antioxidants. The reason behind this antagonism was investigated through oxidation reactions of Trolox via mass spectrometry analysis. Consequently, a proof was obtained for inhibitory effect of bound-antioxidants on auto-regeneration reactions of Trolox.

Determination of tryptophan derivatives in kynurenine pathway in fermented foods using liquid chromatography tandem mass spectrometry

Food Chemistry, 2018, 243, 420-427

This study aimed to develop an analytical method for the determination of tryptophan and its derivatives in kynurenine pathway using tandem mass spectrometry in various fermented food products (bread, beer, red wine, white cheese, yoghurt, kefir and cocoa powder). The method entails an aqueous extraction and reversed phase chromatographic separation using pentafluorophenyl (PFP) column. It allowed quantitation of low ppb levels of tryptophan and its derivatives in different fermented food matrices. It was found that beer samples were found to contain kynurenine within the range of 28.7 +/- 0.7 mu g/L and 86.3 +/- 0.5 mu g/L. Moreover, dairy products (yoghurt, white cheese and kefir) contained kynurenine ranging from 30.3 to 763.8 +/- g/kg d.w. Though bread samples analyzed did not contain kynurenic acid, beer and red wine samples as yeast-fermented foods were found to contain kynurenic acid. Among foods analyzed, cacao powder had the highest amounts of kynurenic acid (4486.2 +/- 165.6 mu g/kg d.w), which is a neuroprotective compound.

Investigation and kinetic evaluation of the reactions of hydroxymethylfurfural with amino and thiol groups of amino acids

Food Chemistry, 2018, 240, 354-360

In this study, reactions of hydroxymethylfurfural (HMF) with selected amino acids (arginine, cysteine and lysine) were investigated in HMF-amino acid (high moisture) and Coffee-amino acid (low moisture) model systems at 5, 25 and 50 degrees C. The results revealed that HMF reacted efficiently and effectively with amino acids in both high and low moisture model systems. High-resolution mass spectrometry (HRMS) analyses of the reaction mixtures confirmed the formations of Michael adduct and Schiff base of HMF with amino acids. Calculated pseudo-first order reaction rate constants were in the following order; k(Cysteine) > k(Arginine) > k(Lysine) for high moisture model systems. Comparing to these rate constants, the kCysteine decreased whereas, kArginine and kLysine increased under the low moisture conditions of Coffee-amino acid model systems. The temperature dependence of the rate constants was found to obey the Arrhenius law in a temperature range of 5-50 degrees C under both low and high moisture conditions.

Interactions between macromolecule-bound antioxidants and Trolox during liposome autoxidation: A multivariate approach

Food Chemistry, 2017, 237, 989-996

The interactions between free and macromolecule-bound antioxidants were investigated in order to evaluate their combined effects on the antioxidant environment. Dietary fiber (DF), protein and lipid-bound antioxidants, obtained from whole wheat, soybean and olive oil products, respectively and Trolox were used for this purpose. Experimental studies were carried out in autoxidizing liposome medium by monitoring the development of fluorescent products formed by lipid oxidation. Chemometric methods were used both at experimental design and multivariate data analysis stages. Comparison of the simple addition effects of Trolox and bound antioxidants with measured values on lipid oxidation revealed synergetic interactions for DF and refined olive oil-bound antioxidants, and antagonistic interactions for protein and extra virgin olive oil-bound antioxidants with Trolox. A generalized version of logistic function was successfully used for modelling the oxidation curve of liposomes. Principal component analysis revealed two separate phases of liposome autoxidation.

Formation and elimination reactions of 5-hydroxymethylfurfural during in vitro digestion of biscuits

Food Research International, 2017, 99, 308-314

This study investigated the possible formation and elimination reactions of 5-hydroxymethylfurfural (HMF) with amino and sulfhydryl groups in commercial biscuits during simulated in vitro gastrointestinal digestion. At the end of gastric phase, significant increase was observed in HMF contents of biscuits (p < 0.05). By high-resolution mass spectrometry (HRMS) analysis, it was confirmed that sugar dehydration products such as 3-deoxyglucosone and 3,4-dideoxyglucosone accumulated in biscuits during baking were converted to HMF under gastric conditions. However, reactions of HMF with amino acids proceeded with the progress of digestion. HRMS analysis in both HMF-amino acid model systems and in biscuits confirmed that formed HMF reacted with amino and sulfhydryl groups through Michael type addition. In addition, formation of Schiff base during intestinal phases led to a significant decrease in the concentrations of HMF (p < 0.05).

Formation of tyramine in yoghurt during fermentation – Interaction between yoghurt starter bacteria and Lactobacillus plantarum

Food Research International, 2017, 97, 288-295

This study aimed to investigate the formation of tyramine during yoghurt fermentation with the focus on interaction between Streptococcus thermophilus RSKK 04082, Lactobacillus delbrueckii subsp. bulgaricus DSM 20081 and Lactobacillus plantarwn RSKK 02030. These microorganisms were used in the yoghurt fermentation as single strains or mixed cultures containing double or triple strains. The interactions between microorganisms have been also revealed by determining total free amino acids and the pH of the medium together with the microbial count of the strains. It was observed that L. delbrueckii subsp. bulgaricus DSM 20081 did not produce tyramine while S. thermophilus RSKK 04082 and L. plantar RSKK 02030 could produce tyramine depending on the fermentation conditions. Synergistic interactions between S. thermophilus RSKK 04082 and L. delbrueckii subsp. bulgaricus DSM 20081 and, between L. delbrueckii subsp. bulgaricus DSM 20081 and L. plantarum RSKK 02030 were found in terms of tyramine production. It was observed in this study that L. delbrueckii subsp. bulgaricus DSM 20081 had indirect effect on accumulation of tyramine in the yoghurts.

Antioxidants Bound to an Insoluble Food Matrix: Their Analysis, Regeneration Behavior, and Physiological Importance

Comprehensive Reviews in Food Science and Food Safety, 2017, 16(3), 382-399

Dietary antioxidants play an important role in human health by counteracting oxidative stress and preventing chronic diseases. Most common dietary antioxidants in foods are vitamins, carotenoids, phenolic compounds, sulfurcontaining compounds, and neoformed antioxidants. Antioxidants may be present in free soluble or bound insoluble forms in foods. Antioxidants bound to insoluble food matrices have gained the spotlight because they exert their antioxidant effects much longer than free soluble ones. A direct procedure called QUENCHER has been shown to accurately measure the antioxidant capacity of antioxidants bound to insoluble matrices. This procedure overcomes the drawbacks of extraction-dependent classical assays leading to underestimation of the total antioxidant capacity (TAC) of foods. This review focuses on antioxidants that are found naturally in foods or are formed in foods during processing specifically the antioxidants bound to the insoluble food matrices. The literature gap on the importance of bound antioxidants, their physiological relevance, and methods for measurement of their antioxidant capacity will be filled by this comprehensive review. In particular, chemical properties and health effects of food antioxidants, measurement of the TAC of foods by the QUENCHER method, digestion behavior of bound insoluble antioxidants, and their interactions with free soluble antioxidants are discussed throughout this review.

Maillard reaction and caramelization during hazelnut roasting: A multiresponse kinetic study

Food Chemistry, 2017, 221, 1911-1922

A comprehensive kinetic model indicating the elementary steps of Maillard reaction and caramelization during hazelnut roasting was proposed based on a multi-response kinetic modeling approach. Changes in the concentrations of sucrose, fructose, glucose, amino acids, 3-deoxyglucosone, 1-deoxyglucosone, 3,4-dideoxyglucosone, glyoxal, methylglyoxal, dimethylglyoxal, and 5-hydroxymethylfurfural were examined in hazelnuts during roasting at 150, 160 and 170 degrees C for 15, 30, 60, 90, and 120 min. The results suggested that 1,2-enolization was important in the interconversion of glucose and fructose, 5-hydroxymethylfurfural formation mainly proceeded via fructofuranosyl cation dehydration rather than 3-deoxglucosone, glucose contributed more than fructose and fructofuranosyl cation to the early stage of the Maillard reaction. Methylglyoxal and dimethylglyoxal were mainly formed from 1-deoxyglucosone with high reaction rate constants while glyoxal formed through glucose degradation. a-Dicarbonyl compounds could have a role in the formation of melanoidins. The temperature dependence of the reactions was complicated and could not be explained by the Arrhenius equation.

Monitoring protein glycation by electrospray ionization (ESI) quadrupole time-of-flight (Q-TOF) mass spectrometer

Food Chemistry, 2017, 217, 65-73

In this study electrospray ionization quadrupole time-of-flight (ESI-Q-TOF) mass spectrometry was used to investigate protein glycation. The glycated species of cytochrome C, lysozyme, and beta-casein formed during glycation with d-glucose were identified and monitored in binary systems heated at 70 degrees C under dry and aqueous conditions. Cytochrome C had multiple charges in non-glycated state, primarily changing from +13 to +17 positive charges, whereas beta-casein had charge states up to +30. Upon heating with glucose at 70 degrees C in aqueous state, attachment of one glucose molecule onto proteins was observed in each charge state. However, heating in dry state caused much more glucose attachment, leading to the formation of multiple glycoforms of proteins. By using ESI-QTOF-MS technique, formation of glycated cytochrome C containing up to 12 glucose moieties were observed, while glycated species containing 6 and 8 glucose moieties were observed for lysozyme and beta-casein, respectively in various heating conditions.

Extending the shelf-life of pomegranate arils with chitosan-ascorbic acid coating

LWT – Food Science and Technology, 2017, 76, 172-180

The aim of this study was to evaluate the mixture of chitosan and ascorbic acid as an edible coating to extend the shelf-life of pomegranate arils. Pomegranate arils coated with varying concentrations of chitosan and ascorbic acid were stored at 5 +/- 1 degrees C for 28 days. Physical, chemical, microbiological and sensory quality attributes of the arils were determined during storage. There were no significant differences in the contents of anthocyanins, organic acids and sugars for coated and control (uncoated) samples during storage. Chitosan-ascorbic coating helped keeping the visual quality of arils during storage as confirmed by their surface color measurement. Chitosan-ascorbic coating inhibited bacterial and fungal growth on arils. Furthermore, the chitosan-ascorbic acid solution inhibited the mesophilic aerobic bacteria immediately after coating and coated arils presented no growth during storage. The bacterial and fungal growth were analyzed by using the Gompertz model to estimate the microbiological shelf-life of samples. The results revealed that chitosan-ascorbic coating can prolong the lag time of microorganisms and extend the shelf-life of arils up to 21 days during storage at 5 degrees C. Sensory scores (color, taste, aroma) were also higher in chitosan-ascorbic acid coated arils that were quite acceptable even after 25 days of refrigerated storage.

Multiresponse kinetic modelling of Maillard reaction and caramelisation in a heated glucose/wheat flour system

Food Chemistry, 2016, 211, 892-902

The study describes the kinetics of the formation and degradation of alpha-dicarbonyl compounds in glucose/wheat flour system heated under low moisture conditions. Changes in the concentrations of glucose, fructose, individual free amino acids, lysine and arginine residues, glucosone, 1-deoxyglucosone, 3-deoxyglucosone, 3,4-dideoxyglucosone, 5-hydroxymethyl-2-furfural, glyoxal, methylglyoxal and diacetyl concentrations were determined to form a multiresponse kinetic model for isomerisation and degradation reactions of glucose. Degradation of Amadori product mainly produced 1-deoxyglucosone. Formation of 3-deoxyglucosone proceeded directly from glucose and also Amadori product degradation. Glyoxal formation was predominant from glucosone while methylglyoxal and diacetyl originated from 1-deoxyglucosone. Formation of 5-hydroxymethyl-2-furfural from fructose was found to be a key step. Multi-response kinetic modelling of Maillard reaction and caramelisation simultaneously indicated quantitatively predominant parallel and consecutive pathways and rate limiting steps by estimating the reaction rate constants.

Effect of alkalization on the Maillard reaction products formed in cocoa during roasting

Food Research International, 2016, 89, 930-936

Cocoa beans are used in vast variety of food products whether as raw or after alkaline treatment. In this study, cocoa beans were treated with sodium carbonate or water and then roasted together with non-treated cocoa beans. To understand the effect of alkalization on Maillard reaction during cocoa roasting, changes in the concentrations of certain Maillard reaction compounds were determined. Additionally, changes in the concentrations of sugars and modification of lysine were also monitored. Alkaline treatment favored the degradation of sugars in cocoa together with roasting. The concentration of a-dicarbonyl compounds was higher in alkaline treated cocoa compared to water-immersed and non-treated cocoa. Roasting process substantially decreased the concentrations of 3-deoxyglucosone (3-DG), glucosone, glyoxal and diacetyl in alkaline treated cocoa. The concentrations of methylglyoxal and 5-hydroxymethylfurfural (HMF) increased in cocoa samples after roasting although this increase was less in alkaline treated cocoa compared to the other treatments. Most of the lysine was modified within 30 min and fructoselysine, measured as furosine, gradually degraded independent of the treatments, but depending on temperature. N-s-Carboxymethyllysine (CML) was doubled in alkaline treated cocoa although it did not change depending on the roasting.

Effect of sodium chloride on α-dicarbonyl compound and 5-hydroxymethyl-2-furfural formations from glucose under caramelization conditions: A multiresponse kinetic modeling approach

Journal of Agricultural and Food Chemistry, 2016, 64, 6333-6342

This study aimed to investigate the kinetics of α-dicarbonyl compound formation in glucose and glucose–sodium chloride mixture during heating under caramelization conditions. Changes in the concentrations of glucose, fructose, glucosone, 1-deoxyglucosone, 3-deoxyglucosone, 3,4-dideoxyglucosone, 5-hydroxymethyl-2-furfural (HMF), glyoxal, methylglyoxal, and diacetyl were determined. A comprehensive reaction network was built, and the multiresponse model was compared to the experimentally observed data. Interconversion between glucose and fructose became 2.5 times faster in the presence of NaCl at 180 and 200 °C. The effect of NaCl on the rate constants of α-dicarbonyl compound formation varied across the precursor and the compound itself and temperature. A decrease in rate constants of 3-deoxyglucosone and 1-deoxyglucosone formations by the presence of NaCl was observed. HMF formation was revealed to be mainly via isomerization to fructose and dehydration over cyclic intermediates, and the rate constants increase 4-fold in the presence of NaCl.

Effect of chitosan on the formation of acrylamide and hydroxymethylfurfural in model, biscuit and crust systems

Food & Function, 2016, 7, 3431-3436

Chitosan has been popular as a natural food preservative due to its antibacterial and antifungal activities. It may be used in thermally processed foods such as bread to delay staling and improve the microbial stability during the shelf-life. However, the thermal process could lead to the formation of harmful compounds in bakery products through chemical reactions, in which chitosan could take part. Therefore, this study aims to investigate the effect of chitosan on the formation of acrylamide and hydroxymethylfurfural (HMF) in different model systems. Addition of acid to the asparagine–glucose model system decreased the initial rate of acrylamide formation to approx. 4-times. The chitosan included model system contained higher acrylamide than the asparagine–glucose–acid model but still lower than the asparagine–glucose model system. The HMF content was decreased in the presence of acid due to acid-catalyzed degradation. Additionally, HMF is a potent carbonyl source and utilized in the Maillard reaction. In biscuit samples, addition of acid or chitosan solution to the dough did not significantly affect the acrylamide formation (p > 0.05), however addition of acid increased the formed HMF. In crust samples, acrylamide formation was decreased by acid, while chitosan showed no additional decrease. No interaction was found between HMF and chitosan. The results suggest that the effect of chitosan should be carefully evaluated apart from the effect of acid, in which chitosan was solubilized.

Investigations on the reactions of α-dicarbonyl compounds with amino acids and proteins during in vitro digestion of biscuits

Food & Function, 2016, 7, 2544-2550

This study investigated the interactions of reactive α-dicarbonyl compounds, particularly methylglyoxal (MGO) and 3-deoxyglucosone (3-DG), in commercial biscuits during gastrointestinal digestion. An in vitro multi-step enzymatic digestion system simulating gastric, duodenal and colon phases was used. MGO and 3-DG concentrations decreased with the progress of digestion. Model systems composed of MGO and lysine, cysteine or ovalbumin and model biscuits containing lysine, cysteine or ovalbumin were subjected to in vitro digestion. The results revealed that disappearance in dicarbonyl contents was due to interactions of reactive dicarbonyl compounds with the accumulating amino acids during digestive process. By a high resolution mass spectrometry analysis in model systems and biscuits, the formation of adducts of dicarbonyl compounds with amino or sulfhydryl groups of amino acids was confirmed.

Bioactive compounds in different hazelnut varieties and their skins

Journal of Food Composition and Analysis, 2015, 43, 203-208

Bioactive profiles of hazelnut skins belonging to fourteen hazelnut varieties were identified. Concentration of phenolic compounds, flavonoids and phenolic acids in soluble free, conjugated soluble and insoluble bound fractions together with their total concentrations were presented. In addition, tocopherol content and total antioxidant capacity of hazelnuts and their skins were revealed. Concentration of total phenolic compounds ranged between 51.9 and 203.1 mg gallic acid equivalent/g of skin among varieties, which is in accordance with the total antioxidant capacity. Total flavonoid content was almost 60% of the total phenolic compounds. Flavonoids and phenolic acids were found to be concentrated mostly in the conjugated soluble fraction. Tocopherol contents of hazelnut skins ranged from 226 to 593 mu g/g, and alpha-tocopherol was the most abundant. Total antioxidant capacity was between 309 and 1375 mu mol Trolox equivalent/g of hazelnut skins, which is more than 100 times higher than for hazelnuts without the skins.

Synergism between soluble and dietary fiber bound antioxidants

Journal of Agricultural and Food Chemistry, 2015, 63, 2338-2345

This study investigates the synergism between antioxidants bound to dietary fibers (DF) of grains and soluble antioxidants of highly consumed beverages or their pure antioxidants. The interaction between insoluble fractions of grains containing bound antioxidants and soluble antioxidants was investigated using (i) a liposome-based system by measuring the lag phase before the onset of oxidation and (ii) an ESR-based system by measuring the reduction percentage of Fremy’s salt radical. In both procedures, antioxidant capacities of DF-bound and soluble antioxidants were measured as well as their combinations, which were prepared at different ratios. The simple addition effects of DF-bound and soluble antioxidants were compared with measured values. The results revealed a clear synergism for almost all combinations in both liposome- and ESR-based systems. The synergism observed in DF-bound−soluble antioxidant system paints a promising picture considering the role of fiber in human gastrointestinal (GI) tract health.

Mechanism of the interaction between insoluble wheat bran and polyphenols leading to increased antioxidant capacity

Food Research International 2015, 69, 189-193

This study aimed to provide an in-depth investigation of the interaction between insoluble wheat bran and polyphenols. Treatment with tannic acid, but not gallic acid, increased the bound antioxidant capacity of insoluble wheat bran depending on its aqueous concentration (p < 0.05). Among the beverages tested (white and red wines, black and green tea infusions), treatment with green tea infusion caused the highest increase in the total antioxidant capacity. Temperature, time, air and pH were found to significantly affect the reaction between insoluble wheat bran and polyphenols. The bound antioxidant capacity of insoluble bran increased to above 100 mmol TE.kg(-1) after treatment with green tea infusion at optimum conditions (50 degrees C, pH 9.0, no airflow). Concentration of free amino groups available in wheat bran significantly decreased (59.5%) after the treatment The results suggested that polyphenols are oxidized to quinones under alkaline conditions further bound to free amino groups available on the surface of wheat bran.

Effects of hydrophobic and ionic interactions on glycation of casein during Maillard reaction

Journal of Agricultural and Food Chemistry, 2014, 62, 11289-11295

This study aimed to investigate the effects of hydrophobic and ionic interactions on glycation of native and high-shear treated casein during heating. Casein–epicatechin and casein–calcium complexes were formed and glycated with glucose at different temperatures ranging from 70 to 150 °C in solution and dry states. Furosine, acid derivative of N-ε-fructoselysine (FL), and N-ε-carboxymethyl lysine (CML) were measured as indicators of early and advanced glycation, respectively. CML concentrations of casein–epicatechin and casein–calcium complexes heated in solution were significantly lower as compared to the control (p < 0.05). For instance, 182 ± 9.78 μg/g of CML formed in the control, while CML concentrations were 136 ± 10.7 and 101 ± 7.37 μg/g in casein–epicatechin and casein–calcium complexes, respectively, heated at 150 °C in the solution state. Treatment by high shear microfluidization further decreased the CML formed during heating at 70 °C in dry state. The results suggest that interactions with epicatechin molecule and calcium ion could be a useful strategy to limit advanced glycation of casein under certain conditions.

Investigation of the reactions of acrylamide during in vitro multistep enzymatic digestion of thermally processed foods

Food & Function, 2015, 6, 109-114

This study aimed to investigate the fate of acrylamide in thermally processed foods after ingestion. An in vitro multistep enzymatic digestion system simulating gastric, duodenal and colon phases was used to understand the fate of acrylamide in bakery and fried potato products. Acrylamide levels gradually decreased through gastric, duodenal and colon phases during in vitro digestion of biscuits. At the end of digestion, acrylamide reduction ranged between 49.2% and 73.4% in biscuits. Binary model systems composed of acrylamide and amino acids were used to understand the mechanism of acrylamide reduction. High-resolution mass spectrometry (HRMS) analyses confirmed Michael type addition of amino acids to acrylamide during digestion. Contrary to bakery products, acrylamide levels increased significantly during gastric digestion of fried potatoes. The Schiff base formed between reducing sugars and asparagine disappeared rapidly meanwhile acrylamide level increased during the gastric phase. This suggests that intermediates like the Schiff base accumulated in potatoes during frying are potential precursors of acrylamide under gastric conditions.

Mitigation of acrylamide and hydroxymethylfurfural in biscuits using a combined partial conventional baking and vacuum post-baking process: Preliminary study at the lab scale

Innovative Food Science & Emerging Technologies, 2014, 26, 265-270

A combined conventional and vacuum process was introduced as a new baking technology to mitigate acrylamide and 5-hydroxymethylfurfural (HMF) in biscuits in this study. Firstly, these processes were compared for acrylamide and HMF formations, drying rate, and browning development at different temperatures. Acrylamide concentrations in biscuits attained during vacuum baking were significantly lower than those attained during conventional baking at all temperatures studied (p < 0.05). Besides, there was no HMF formation in biscuits during vacuum baking. Comparing to conventional baking, heating under lower pressure provided lower time-temperature profile with slightly accelerated evaporation of water in dough. However, development of surface browning was lacking in vacuum baked biscuits. Secondly, combinations of conventional and vacuum processes were used to produce biscuits. The dough that was partially baked at 220 degrees C for 2-4 min under conventional conditions was post-baked under vacuum for accelerated drying at 180 degrees C and 500 mbar for 4-6 min until the desired final moisture content was attained. Doing so, exposure of biscuits to higher temperatures for longer time, which was essential to facilitate the chemical reactions leading to thermal process contaminants, was prevented. The combined process formed no acrylamide or HMF (<LOQ) in biscuits. It was considered as a promising alternative to produce safer biscuits for targeted consumers like infants.

Industrial relevance: The study has been performed in the course of the FP7 project PROMETHEUS that aimed to develop new or alternative technologies for the mitigation of thermal processing contaminants in foods. Mitigation of thermal processing contaminants, especially acrylamide in heated foods has been an intensive area of research in the last decade. It was confirmed repeatedly by many researchers that increasing processing temperature also increases the formation rates of those undesired compounds. Therefore, one approach to mitigate them is to lower temperature during processing. However, this is not viable practically, because lowering temperature requires longer time to achieve desired final moisture contents in the final product. The approach presented in this manuscript takes the advantage of faster drying of biscuits during heating under vacuum. Using the combination of conventional par-baking with vacuum post-baking seems to produce safer biscuits than the conventional counterparts in terms of their acrylamide and HMF contents. At industrial level vacuum application has been used in bread processing for cooling purposes. In that case, breads are cooled rapidly after baking in semi-continuous vacuum chambers. As implementation of vacuum application into the process has already been practiced, it is likely that partially baked biscuits could be post-baked for short times in semi-continuous vacuum chambers maintained at specified conditions. To the best of our knowledge, such combined baking process has not been investigated to date for the mitigation of thermal processing contaminants in biscuits. So, it is believed that the results of present manuscript would be interesting for bakery industry dealing with the above-mentioned safety problem, but also for the readers of this journal.

Investigation of alpha-dicarbonyl compounds in baby foods by high-performance liquid chromatography coupled with electrospray ionization mass spectrometry

Journal of Agricultural and Food Chemistry, 2014, 62, 7714-7720

Baby foods are exposed to elevated temperatures during processing treatments such as sterilization or spray drying. These treatments decompose sugars leading to the formation of a-dicarbonyl compounds that are of importance since they have been associated with several metabolic disorders. In this study, an analytical method based on high-performance liquid chromatography coupled with electrospray ionization mass spectrometry (HPLC-ESI-MS) was used to determine a-dicarbonyl compounds in baby foods. The method entailed aqueous extraction of a-dicarbonyl compounds from the samples and derivatization with o-phenylenediamine prior to chromatographic analysis. The results indicated that major degradation product was 3-deoxyglucosone in the samples including cereal-based infant formula, canned fruit and vegetable puree. Its concentration ranged between 3.9 and 827.1 mg/kg in infant formula and between 26.7 and 92.3 mg/kg in fruit puree samples. The concentrations of glucosone, 1-deoxyglucosone, 5-hydroxymethy1-2-furfural, furfural, glyoxal, methylglyoxal, and dimethylglyoxal levels were rather low.

Formation of monochloropropane-1,2-diol and its esters in biscuits during baking

Journal of Agricultural and Food Chemistry, 2014, 62, 7297-7301

The formation of free monochloropropane-1,2-diol (3-MCPD and 2-MCPD) and its esters (bound-MCPD) was investigated in biscuits baked with various time and temperature combinations. The effect of salt as a source of chloride on the formation of these processing contaminants was also determined. Kinetic examination of the data indicated that an increasing baking temperature led to an increase in the reaction rate constants for 3-MCPD, 2-MCPD, and bound-MCPD. The activation energies of formation of 3-MCPD and 2-MCPD were found to be 29 kJ mol(-1). Eliminating salt from the recipe decreased 3-MCPD and 2-MCPD formation rate constants in biscuits by 57.5 and 85.4%, respectively. In addition, there was no formation of bound-MCPD in biscuits during baking without salt. Therefore, lowering the thermal load or limiting the chloride concentration should be considered a means of reducing or eliminating the formation of these contaminants in biscuits. Different refined oils were also used in the recipe to test their effect on the occurrence of free MCPD and its esters in biscuits. Besides the baking process, the results also confirmed the role of refined oil in the final concentration of these contaminants in biscuits.

Mitigation of acrylamide and hydroxymethyl furfural in instant coffee by yeast fermentation

Food Research International 2014, 61, 252-256

Acrylamide being known as carcinogenic and hydroxymethyl furfural (HMF) being known as cytotoxic compounds are heat induced process contaminants found in instant coffee. Today’s instant coffee production method involves roasting of coffee beans, grinding, flavor and aroma separation, extraction, concentration, and drying steps. During roasting, acrylamide and HMF are formed in varying amounts depending upon the degree of heat treatment as a result of the Maillard reaction. This study was conducted in order to reduce the concentrations of acrylamide and HMF in instant coffee. Instant coffee (20%, w/v) was mixed with sucrose (0-10, w/v) and baker’s yeast (Saccharomyces cerevisiae, 1-2%, w/v) in a tightly closed glass vessel. The mixture was fermented at 30 degrees C for 48 h. The kinetics of acrylamide and HMF degradation was investigated. HMF and acrylamide contents were reduced exponentially at varying rates, depending upon fermentation medium and time. After 24 h, HMF concentration was decreased by 61.2%, 75.7%, 93.6% and 99.2% in the fermentation media containing none, 1%, 5%, and 10% of sucrose, respectively. After 48 h, acrylamide concentration was decreased by about 70%. These results revealed that yeast fermentation is promising for the mitigation of HMF and acrylamide in instant coffee. (C) 2013 Elsevier Ltd. All rights reserved.

Hazelnut skin powder: A new brown colored functional ingredient

Food Research International 2014, 65, 291-297

Hazelnut skin arises as a by-product in the roasting process of hazelnuts. This study aimed to investigate the potential of its utilization as a brown colored functional ingredient. Chemical composition analyses revealed that hazelnut skin is a very rich source of dietary fibers (67.7%) and phenolic compounds (233 mg GAE/g). Its oil fraction (14.5%) was found to contain very high amounts of tocopherols (2.77 mu g/g) and oleic acid (75.2%). After defatting, coarse and fine hazelnut skin powders were obtained by low and high shear homogenization. High shear homogenization was performed at different pressures (10, 20 and 30 ksi) for different pass cycles (1, 3, 5 and 10). The powder samples were analyzed for particle size distribution, color, individual phenolic compounds, total phenolic content, and total antioxidant capacity. A desirable low micron particle size for the hazelnut skin for incorporation into food formulations was achieved by means of high shear homogenization, meanwhile there was no significant change in phenolic composition and antioxidant capacity.

Formation of melatonin and its isomer during bread dough fermentation and effect of baking

Journal of Agricultural and Food Chemistry, 2013, 62, 2900-2905

Melatonin is produced mainly by the pineal gland in vertebrates. Also, melatonin and its isomer are found in foods. Investigating the formation of melatonin and its isomer is of importance during bread dough fermentation and its degradation during baking since bread is widely consumed in high amounts. Formation of melatonin was not significant during dough fermentation. The melatonin isomer content of nonfermented dough was found to be 4.02 ng/g and increased up to 16.71 ng/g during fermentation. Lower amounts of isomer in crumb and crust than dough showed that the thermal process caused a remarkable degree of degradation in melatonin isomer. At the end of the 180 mm fermentation Trp decreased by 58%. The results revealed for the first time the formation of a melatonin isomer in bread dough during yeast fermentation.

Kinetics of furan formation from ascorbic acid during heating under reducing and oxidizing conditions

Journal of Agricultural and Food Chemistry, 2013, 61 (42), pp 10191–10196

This study aimed to investigate the effect of oxidizing and reducing agents on the formation of furan through ascorbic acid (AA) degradation during heating at elevated temperatures (≥100 °C) under low moisture conditions. To obtain these conditions, oxidizing agent, ferric chloride (Fe), or reducing agent, cysteine (Cys), was added to reaction medium. Kinetic constants, estimated by multiresponse modeling, stated that adding Fe significantly increased furan formation rate constant, namely 369-fold higher than that of control model at 100 °C. Rate-limiting step of furan formation was found as the reversible reaction step between intermediate (Int) and diketogluconic acid (DKG). Additionally, Fe decreased activation energy of AA dehydration and furan formation steps by 28.6% and 60.9%, respectively. Results of this study are important for heated foods, fortified by ferric ions and vitamins, which targets specific consumers, e.g. infant formulations.