Effect of storage on non‐enzymatic browning of liquid infant milk formulae

Furfural, hydroxymethylfurfural (HMF), furosine, lactulose, ascorbic acid and absorbance at 284 and 420 nm (A₂₈₄ and A₄₂₀) were all determined in two types of liquid infant formula prepared with different processing protocols. These browning indicators were used to assess the effects of storage and modified atmosphere on the shelf‐life of infant formulae. The study was carried out at 20 and 55 °C for 15, 30 and 90 days. At 20 °C, slight browning was observed and could be evaluated by furosine, furfural and total HMF indicators. At 55 °C, formula type A (pasteurised, spray‐dried and reconstituted) showed more browning in nitrogen storage conditions than did type B. Furfural, HMF, lactulose, A₂₈₄ and A₄₂₀ are useful indicators to control the extent of browning reactions in adverse storage conditions. © 2002 Society of Chemical Industry     

Characterization of the Maillard reaction in bread crisps

Maillard reaction (MR) is one of the main chemical event occurring during baking. To study the reaction in bakery products, a dry model system is more useful than an aqueous one. In this work, the effects of formulation and processing conditions in a crisp bread system were investigated to test the effects of different additives on both the overall reaction and the formation of MR products such as 5-hydroxymethyl-2-furaldehyde (HMF) and acrylamide. Cylindrical dough made up of flour, water and yeast was baked at 180 °C for 35 min and the slices were toasted at different times/temperatures combinations. Browning and water content were monitored along with the kinetic of formation of chemical indicators such as HMF and acrylamide also calculating rate constants and activation energy. These parameters were also monitored in systems added with glycine and asparaginase. During toasting water content follows an exponential trend, being the rate of water loss faster in the initial stage of toasting and at higher temperature. Browning was more intense when toasting at higher temperature and a linear correlations between browning (ΔL*, ΔE*), HMF and acrylamide concentration were observed when toasting at 180 °C. HMF and acrylamide content increased with the toasting time and temperature. Their concentrations were strongly dependent on the water content of the final product, and both the addition of glycine and asparaginase are effective in reducing acrylamide content. The addition of glycine enhanced the browning of toasted bread, and slightly increased HMF content at any toasting temperature. The system characterized in this work represents a suitable tool to study the development of the MR in dry systems.     

Effect of storage on nonenzymatic browning reactions in carob pekmez

Carob pekmez was stored at 5, 25, 35 and 45 °C for studying the reaction kinetics of nonenzymatic browning reactions. Hydroxymethylfurfural (HMF) formation, browning index (A₄₂₀) and CIE (International Commission on Illumination) colour parameters were analysed to evaluate nonenzymatic browning reactions. HMF formation and A₄₂₀ values increased linearly with the storage time and temperature and both followed zero‐order reaction. No fitting model was found for the changes in visual CIE parameters. The dependence of rate constant of nonenzymatic reactions on temperature was represented by an Arrhenius equation and the activation values were found as 114.87 kJ mol^?1 and 86.62 kJ mol^?1 for HMF formation and A₄₂₀ values, respectively. The excellent linear correlations (r = 0.728–0.99) among colour parameters, browning index and HMF were found.     

Acrylamide–asparagine relationship in baked/toasted wheat and rye breads

Acrylamide in baked and toasted wheat and rye bread was studied in relation to levels of asparagine in flour, dough, bread and toasts. Asparagine was consumed during bread preparation resulting in reduced acrylamide content in the products. In wheat bread, 12% of the asparagine initially present in the flour (0.14 g kg^?1) remained after yeast fermentation and baking; for rye bread, 82% of asparagine remained after sourdough fermentation and baking. Asparagine present in untoasted wheat bread had totally reacted after hard toasting. Toasted wheat and rye bread slices contained 11–161 and 27–205 µg kg^?1 acrylamide, respectively, compared to untoasted wheat and rye bread with <5 and 7–23 µg kg^?1 acrylamide, respectively. The dietary intake of acrylamide from bread (untoasted) of 2 µg day^?1 is relatively low; however, acrylamide exposure from bread increases several fold for people eating toasted bread.     

Furosine is a useful indicator in pre‐baked breads

There is increasing demand for pre‐baked bread. Bakers can meet consumer requirements for breads of specific flavour and colour by pre‐baking an amount of bread in the morning and completing the baking process in the afternoon. This type of product is of special interest to sandwich bars, restaurants and large communities. In order to obtain an indicator of utility to monitor the processing of pre‐baked bread, the browning indicators furosine, hydroxymethylfurfural (HMF) and glucosylisomaltol were analysed in two independent assays of bread pre‐baked at 175 °C for between 5 and 30 min. No furosine was detected in raw or fermented dough. In the pre‐baking stage, furosine increased from 1.5‐ to 5‐fold between 5 and 30 min. The furosine values obtained in the two independent experiments were similar. HMF and glucosylisomaltol were only detected after 15 min, which is the time period commonly used for processing by the industry. Thus, among these indicators, furosine is the only one with utility for monitoring the pre‐baking process. On the other hand, a study of the baking of pre‐baked bread at 220 °C showed that HMF and glucosylisomaltol can be used to monitor the latter process. Copyright © 2004 Society of Chemical Industry     

Combined use of HMF and furosine to assess fresh honey quality

BACKGROUND: The quality of honey can be affected by practices such as adulteration, inadequate storage or the application of severe heat treatments. Because hydroxymehylfurfural (HMF) is an indicator of honey freshness and furosine (ε‐2‐furoylmethyl lysine) has proved to be a useful chemical indicator of the progress of the Maillard reaction in foods, the aim of this work was to assess their usefulness as indicators of fresh honey quality. The effect of heat treatment, storage and adulteration with different types of syrups on HMF and furosine content has been studied. RESULTS: In fresh honey, HMF and furosine values ranged from 0.9 to 14.6 mg kg^?1 of product and from 3.06 to 12.06 g kg^?1 of protein, respectively. Heating of honey samples with different pH (3.76 and 5.14) produced slight increases in HMF content and negligible changes were detected in furosine values. The storage of fresh honey for 2 years caused a high increase in the HMF level, reaching values above EU limits. However, furosine showed a different behavior depending on the type of honey sample. Adulteration assays using different syrups produced an increase in HMF and a decrease of furosine values by dilution effect. HMF content of adulterated honey samples with syrup of known origin did not exceed EU limits. CONCLUSION: These results show the influence of long periods of storage or adulteration, using different percentages of corn or invert sugar syrups, on HMF and furosine content of fresh honey. This seems to indicate that the combination of HMF and furosine may be useful for evaluating the quality of fresh honey. Copyright © 2009 Society of Chemical Industry     

Occurrence of patulin and 5-hydroxymethylfurfural in apple sour,which is a traditional product of Kastamonu,Turkey

Apple sour is a traditional product of Kastamonu, Turkey. It is consumed by spreading on bread or drinking after diluting with water. The aim of this study was to determine patulin (PAT) and 5-hydroxymethylfurfural (HMF) in apple sour. This study is the first to evaluate the occurrence of PAT and HMF in apple sour. The samples were extracted with ethyl acetate using liquid-liquid extraction technique. PAT and HMF were determined by HPLC with UV detection. PAT was detected in all samples, and the PAT level in 94.9% of samples was found to be equal or greater than the legal limit for juice concentrates. The mean value for PAT was found to be 284 ± 307 μg kg^?1. PAT levels in 13 of 39 samples were in the range of 100 ≤ x < 200 μg kg^?1, two samples were in the range of 0 ≤ x < 50 μg kg ?1 and two samples were in the range of 1000 ≤ x < 1500 μg kg¹. HMF levels of all samples were above the legal limit for solid molasses. The mean value for HMF was found to be 16215 ± 13317 mg kg^?1. HMF levels of 10 of 39 samples were determined to be in the range of 10000 ≤ x < 20000 mg kg^?1, eight samples were in the range of 20000 ≤ x < 30000 mg kg^?1 and only three samples were in the range of 100 ≤ x < 1000 mg kg^?1. There was a significant and inverse relationship between HMF and pH of the samples. These results indicate that consumption of apple sour is a considerable risk in terms of HMF and PAT toxicity.     

Effect of flour type on Maillard reaction and acrylamide formation during toasting of bread crisp model systems and mitigation strategies

Maillard reaction along with caramelisation are the main chemical reactions occurring in bakery products. They are referred to as non enzymatic browning. In this work, the effect of flour type (wheat, rye and whole-wheat flours) and process conditions were investigated by using a bread crisp model system made up of flour, water and yeast. The bread was toasted at different temperature for different times. In a second set of experiments several additives (glycine, 0.1% on flour; asparaginase, 2000 U kg⁻¹ of flour and an antioxidant extract from green tea) were added to the basic formulations in order to test their ability in reducing the formation of potentially harmful Maillard reaction compounds such as HMF and acrylamide. Browning development and water content along with antioxidant activity were also monitored.Rye model systems produced more HMF and acrylamide at all temperature tested, while wholewheat systems produced less HMF, but more acrylamide than wheat one. The addition of glycine was effective in reducing acrylamide formation, and it increased browning development, antioxidant activity and HMF formation. Asparaginase reduced acrylamide formation up to 88% and had no effect on browning development and antioxidant activity. The addition of exogenous antioxidant compounds from green tea did not produce clear effect on acrylamide formation, thus it was not useful as mitigation strategy in bakery products, likely because of the low fat content.     

Maillard Reaction in Microwave Cooking: Comparison of Early Maillard Products in Conventionally and Microwave-Heated Milk

The impact of microwave cooking on the formation of early Maillard products was investigated and compared with the effect of conventional cooking, using milk as a test system. Experiments were carried out at controlled temperatures of 80°C and 90°C, respectively, at holding times up to 420min. Furosine, hydroxymethylfurfural (HMF) and lactulose, which are all established indicators to estimate heat damage, were determined. The concentrations of all the heating indicators increased with increasing heating time. For example in the 90°C test series the furosine values rose from 34mglitre⁻¹ (0·5h) to 94mglitre⁻¹ (2h holding time) in the milk heated by microwaves and from 35mglitre⁻¹ (0·5h) to 96mg litre⁻¹ (2h) in the conventionally heated milk. None of the reaction products showed significant differences as between the microwave heating and conventional cooking methods.     

Quality of bread made from ozonated wheat (Triticum aestivum L.) flour

BACKGROUND: Ozone gas could be used as a fumigant during grain and flour storage. Experiments were conducted to determine the effects of exposure to ozone and the effects of blending ozone‐treated flour with control flour on flour functionality and bread‐making quality. RESULTS: Ozone treatment oxidized lipids, increased brightness and reduced the yellow hue of flour, and increased peak viscosity and setback viscosity of flour. Bread made from flour treated with ozone at 1500 mg kg^?1 for 4.5 min and bread made from flour blended with 100 g kg^?1 ozonated flour had good crust color and a whiter crumb and had more crumb cells, which resulted in a greater specific volume of the bread when compared with control flour. Flour functionality declined as ozone exposure increased beyond 9 min and as the concentration of ozonated flour increased beyond 200 g kg^?1. CONCLUSION: Bread made from flour exposed to ozone for 4.5 min or flour that contained 100 g kg^?1 fully ozonated flour had greater specific loaf volume and whiter crumb compared to bread made with control flour. Exposure of flour to ozone for longer times (9–45 min) and higher blends (200–1000 g kg^?1) deteriorated quality of bread. Copyright © 2011 Society of Chemical Industry     

Usefulness of some Maillard reaction indicators for monitoring the heat damage of whey powder under conditions applicable to spray drying

The Maillard reaction (MR) rate was observed according to available lysine loss, furosine, hydroxymethylfurfural (HMF), furfural, and brown colour during the heating of freeze-dried nano-filtered whey at 60, 75, and 90 °C and water activities of 0.11, 0.33, 0.43, and 0.73. The physical state of lactose was measured and associated with MR rate. The values obtained for available lysine, furosine, HMF and browning index ranged between, respectively, 11.3 and 1.63 (g 100 g⁻¹ protein), 0.44 and 11.1 (g 100 g⁻¹ protein), not detected and 57.7 (mg 100 g⁻¹ protein) and 0.0104 and 0.1707. The greatest heat damage occurred with low moisture content and high temperature. The MR rate was influenced by the physical state of lactose, heating temperature and the moisture content of the whey. This occurred to a greater extent during the initial and intermediate stages of the MR as opposed to during the formation of coloured compounds.     

Effect of flaxseed and wheat flour blends on dough rheology and bread quality

The rheological and baking properties of flaxseed/wheat composite flours were studied. Flaxseed flour was used to replace 50, 100, 150 and 200 g kg^?1 of wheat flour in bread. Farinographic studies showed that water absorption, dough development time and mixing tolerance index increased as the amount of flaxseed flour increased, while dough stability decreased at 100, 150 and 200 g kg^?1 of flaxseed flour substitution. The extensographic energy of dough also decreased at 150 and 200 g kg^?1 flaxseed levels. The addition of increasing amounts of flaxseed flour caused a decrease in extensibility. Doughs containing 100, 150 and 200 g kg^?1 flaxseed flour showed resistance to extension comparable to that of control dough. The specific volume of flaxseed flour breads was similar to that of control bread. Crust L, a, b values of breads with flaxseed flour were lower than those of control bread. Breads with flaxseed flour gave lower crumb L and b values and higher a values than control bread. The sensory properties showed that an acceptable bread could be produced using flaxseed flour up to a level of 200 g kg^?1. Copyright © 2007 Society of Chemical Industry     

O-dihydroxyphenoloxidase action on natural polyhydric phenolics and enzymic browning of edible yams

Ten cultivars of five edible yam species were examined for o-dihydroxyphenoloxidase (o-DPOase) activity against yam extracts containing phenolic compounds, and for their propensity to brown when cut slices are exposed to air. (+)-Catechin levels in Dioscorea cayenensis (260 mg kg^?1) and D. bulbifera (240 mg kg^?1) were similar to those in D. dumetorum (270 mg kg^?1), but the latter contained less o-DPOase and showed less tendency to browning. D. alata contained more (+)-catechin than other yams, and one cultivar with a higher (+)-catechin content (660 mg kg^?1) showed more browning than another cultivar containing 430 mg kg^?1 (+)-catechin. Five cultivars of D. rotundata showed less tendency to brown, and had lower (+)-catechin content (90–190 mg kg^?1) than the other yams examined, but showed marked variation in o-DPOase activity. o-DPOase activity, assayed by recording the rate of oxygen consumption, varied between 75 units (1 unit=μmol O₂ consumed min^?1 100 g^?1 fresh yam tissue) in D. dumetorum and 2380 units in one D. rotundata cultivar when a crude extract of phenolic compounds diluted to contain 10 mM (+)-catechin was used as substrate and from 60 to 3480 units for these same two enzyme extracts when assayed using crude extracts of phenolic compounds (also adjusted to contain 10 mM (+)-catechin) prepared from the same yam as the enzyme extract. However, in general, the o-DPOase activities recorded using the D. alata extract showed little correlation with the activity when the phenolic extract was prepared from the same yam as the enzyme extract. Incubation of crude extracts containing phenolics with crude extracts of o-DPOase at 20°C for 24 h resulted in a decrease in the quantity of (+)-catechin estimated by h.p.l.c. Cyanidin released by hydrolysis with HCl under mild conditions was also measured. The level in D. alata was sufficiently high to account for ‘pinking’ when this species is boiled. It is concluded that the o-DPOase-catalysed oxidation of (+)-catechin is largely responsible for the browning of yams. The possible influence of other factors, including the reducing agent ascorbic acid in moderating the rate and extent of browning observed, is discussed.     

Indicators of non-enzymatic browning in the evaluation of heat damage of ingredient proteins used in manufactured infant formulas

Twelve infant formula ingredients of animal origin (caseinates, whey proteins and hydrolysates of casein and of whey proteins) and three of vegetable origin (soybean proteins) were analyzed. Furosine, hydroxymethylfurfural (HMF) and pyrraline were studied as indicators of thermal damage and available lysine as nutritional indicator, determined by HPLC in phase reverse and UV detector. The objectives were to evaluate heat damage to ingredients used in commercial infant formulas by measuring non-enzymatic browning indicators and to determine the nutritional value of these ingredients by available lysine determination. Very high furosine values were detected in whey proteins, ranging from 354 to 1,435 mg/100 g of protein. Lower furosine values were found in the remaining ingredients, ranging from 1.36 mg/100 g in hydrolyzed casein to 60.5 mg/100 g in sodium caseinate. Available lysine content ranged from 1.85 g/100 g of protein in hydrolyzed casein to 7.91 g/100 g in calcium caseinate. HMF was detected in whey protein samples between 0.16 and 2.47 mg/100 g of protein. Pyrraline was only detected in one sample of whey proteins at 41 mg/100 g of protein. Similar ingredients from different manufacturers show varied heat damage and nutritional values     

Kinetics of colour development in aqueous fructose systems at high temperatures

Non‐enzymatic browning was studied in aqueous model systems containing fructose and aspartic acid, glutamic acid or asparagine at three different soluble solid concentrations (150, 300 and 450 g kg⁻¹), which were heat treated for different times at four temperatures (85, 90, 95 and 100 °C). Various indicators were used to evaluate the extent of the Maillard reaction: spectrophotometric measurements at 280 and 420 nm (A₂₈₀ and A₄₂₀) and CIE (Commission Internationale de l'Eclairage) parameters L* (lightness), a* (redness), b* (yellowness) and ΔE* (colour difference, which is expressed as [(Δa*)² + (Δb*)² + (ΔL*)²]^1/2). The pH and the formol index were also determined. The indicator for colourless intermediate formation, A₂₈₀, showed that the kinetic constant values increased with increasing heat treatment temperature, while the influence of soluble solid concentration was not clear. After a short induction period the data were well described by assuming zero‐order kinetics. Glutamic acid turned out to be the most reactive amino acid, while asparagine was the least reactive. With reference to brown pigment formation, A₄₂₀ and ΔE*, glutamic acid was the least reactive amino acid. In all the experiments assayed, except for glutamic solutions with fructose concentrations of 150 and 300 g kg⁻¹, the data were best correlated with combined kinetics. © 2000 Society of Chemical Industry     

Presence of furosine in honeys

Nineteen commercial samples (with a shelf‐life of 2 years) and two artisanal samples (freshly collected and stored for 1 year respectively) of Spanish honeys were analysed for pH, protein content and furosine content. Most of the samples had pH values and protein contents within the limits reported in the literature. The presence of furosine was confirmed by comparison of its retention time with that of a furosine standard and by HPLC–MS. The level of furosine in the samples studied ranged from 4.32 to 13.62 g kg^?1 protein. The lowest furosine value was observed in the freshly collected artisanal sample. Heat treatment under severe conditions (90 °C for up to 135 min) increased the furosine content from 4.43 to 14.38 g kg^?1 protein. The results show that furosine seems to be a promising indicator to detect overheating during honey manufacture. © 2001 Society of Chemical Industry     

Effects of toasting procedures on the levels of polycyclic aromatic hydrocarbons in toasted bread

Some polycyclic aromatic hydrocarbons (PAHs), particularly those with a high molecular weight, have been classified as probably carcinogens to humans by the International Agency for Research on Cancer (IARC). The significance of the determination of PAHs is reflected by the special attention of the European Union, which is paying to regulate the maximum allowed levels of PAHs in foodstuffs such as smoked foods. Like other thermally processed foodstuffs, toasted bread can contain these carcinogenic chemicals, not only due to a contamination at source but also during toasting. In order to check PAHs generated from toasting in sandwich bread, several treatment conditions were evaluated: direct toasting (flame-toasting, coal-grilling or gas oven-toasting) or indirect toasting (electric oven-toasting). PAHs were extracted by solid–liquid extraction (SLE) and determined by liquid chromatography with fluorescence detection (LC-FD). Based on the results, the used toasted technique would strongly affect in PAH levels in the final product. No samples obtained by electric oven and toaster were polluted; otherwise the samples toasted by charcoal and flame grilling presented very important levels. Up to 350 μg/kg of total PAHs were detected in toasted samples by wood flame. Differences between different ways of toasting could be ascribed to deposition of PAHs from smoke. Finally, several commercial toasted samples of bread were tested to determine PAHs. Overall, the PAH levels were very low. Benzo[a]pyrene ranged from no detectable to 0.23 μg/kg.     

Occurrence of furosine and hydroxymethylfurfural as markers of thermal damage in dehydrated vegetables

The presence of furosine and hydroxymethylfurfural (HMF) as markers of thermal damage in commercial dehydrated vegetables has been studied. Furosine was measured in all the analysed samples whereas HMF was detected only in garlic, onion, and tomato groups and some other individual vegetables. Furosine, as indicator of the first steps of the Maillard reaction, ranged from 1.12 to 923 mg/100 g protein (depending on the vegetable species and thermal treatment applied) and was well correlated with the browning development in not severely heat-treated samples. In addition, the results seem to indicate that reducing sugars play an important role in the formation of furosine in some vegetable species but not HMF at the conditions used for the dehydration process. The findings of this study show the usefulness of furosine as a quality indicator for sensitive control of the dehydration process in vegetables.     

Proximate composition and functional properties of African breadfruit kernel and flour blends

African breadfruit seeds (ABS) were toasted at 80 and 120°C for varied period of times. The effects of the toasting temperature and time on selected functional properties of the seed flours were determined. Flour blends were prepared from the toasted ABS and wheat flours. The chemical composition and functional properties of the blends were determined. Toasting increased the water absorption capacity (WAC) of ABS flours with increased toasting time at both toasting temperatures. The oil absorption capacity (OAC) on the other hand, increased up to 20 min of seed toasting at both 80 and 120°C and thereafter decreased. At both 80 and 120°C, the foaming capacity (FC) of the seeds decreased with increased toasting time, with greater decreased at 120°C. The protein, fat, ash and crude fibre contents of the flour blends increased while carbohydrate and moisture contents decreased with increased levels of toasted African breadfruit flour (TABF) in the blends. The TABF showed significantly higher (P<0.05) WAC, OAC, FC and emulsion activity (EA) than wheat flour (WF). These properties increased with increased amounts of TABF in the blends. All the flour blends exhibited a least gelation concentration of 8% (W/V). The bulk density (g/cm³) and wettability values of flour blends varied from 0.74 to 0.84 and 19 to 31, respectively. Heating increased the swelling capacity of the flour blends.     

Reduction in hydroxymethylfurfural content in ‘churros’, a Spanish fried dough,by vacuum frying

This work explores the advantages of vacuum frying of ‘churros’, a Spanish dough pastry, compared to standard deep‐fat frying. Oil uptake, texture change, colour development, nonenzymatic browning and hydroxymethylfurfural (HMF) concentration were analysed at different frying conditions. The results obtained during vacuum frying at 100, 120 and 140 °C and 21 kPa were compared with those obtained at atmospheric pressure at 140 and 180 °C. For the same final water content, the vacuum fried ‘churros’ showed no significant differences in the fat uptake compared to those fried at atmospheric pressure (P > 0.05). However, the vacuum fried dough had a much crunchier texture. The evolution of the CIELab a* coordinate and the browning measurement at 280 nm show that vacuum frying is able to slow down the development of browning tones. Furthermore, products can be obtained with an HMF content <1 mg kg^?1 of dry dough.