Effects of dough formula and baking conditions on acrylamide and hydroxymethylfurfural formation in cookies

The effects of dough formula and baking conditions on the formations of acrylamide and hydroxymethylfurfural (HMF) were studied in a cookie model system. Increasing the sugar concentration in the dough formula increased acrylamide formation during baking at 205 °C for 11 min. The effect of sugar on acrylamide formation was more pronounced for glucose than for sucrose, expectedly. Addition of citric acid into dough formula comprising sucrose increased the susceptibility of acrylamide formation, while it decreased acrylamide formation in the dough formula comprising glucose. Decreasing the pH of dough formula increased the tendency to surface browning and the formation of hydroxymethylfurfural in cookies during baking. The results suggest that a cookie with acceptable texture and colour, but having less than 150 ng/g of acrylamide, can be manufactured by lowering the baking temperature and avoiding reducing sugars in the recipe.     

Comparison of the effects of sucrose and hexose on furfural formation and browning in cookies baked at different temperatures

The influence of the type of sugar and baking temperature on sugar degradation, hydroxymethylfurfural (HMF) formation and browning was studied in model cookies. The baking process was characterised by the temperature in the cookie and the water content and activity. A reference browning was selected to compare the differently processed cookies. The accumulation of HMF was modelled at three temperatures for three formulas (sucrose (S-CK), glucose (G-CK) or fructose (F-CK)). HMF started to accumulate at a_w between 0.5 and 0.7 depending on the temperature and followed a first order kinetic, highly dependent on the baking temperature and type of sugar. Cookies baked at 200 °C accumulated 10–100 times less HMF than those baked at higher temperatures. Below 250 °C, S-CK produced less HMF than G- or F-CK, but the inverse was observed at 300 °C.     

A generic procedure to monitor Maillard-derived fluorescent compounds in cookies by flow-injection analysis

Flow-injection analysis is proposed for routine measurement of Maillard-derived fluorescent compounds (FC) in cookies as a marker of the extent of baking. In addition, procedure was applied to investigate the formation of free and total (bound to protein free) FC in cookie-resembling models and in commercial wheat-based cookies as well. FC accounts for the overall fluorescence response of Maillard-derived fluorescent compounds (bound or not to protein) formed during baking but not for a single compound. Free and total FC values increased exponentially during baking at 200, 210 and 220 °C and an induction period of 10 min was observed for free FC. In the complex scenario of the progress of the Maillard reaction (MR) during baking, formation of FC (347/415, ext/emm) was not the limiting step for browning development at the advanced stage of the reaction. Furthermore, the formation of Maillard-derived fluorescent compounds and browning during baking were a consequence of parallel reactions apart from the classical MR scheme of consecutive reactions. Total/free FC ratio was dependent on the baking conditions applied and ratio was significantly decreased at severe baking conditions. Total/free FC ratio could be used as a reference marker for monitoring the process and to identify potential over-processing situations during baking. In addition, fluorescent residues were originally bound to protein because total/free FC ratio decreased drastically as increased the temperature and time of the process. Levels of total FC were nearly 20-fold of free FC in commercial samples. Values of FC were positively correlated with acrylamide, a Maillard-derived food processing contaminant.     

Baking kinetics of muffins in convection and steam assisted hybrid ovens (baking kinetics of muffin…)

Effects of oven type and baking temperature on acrylamide concentration, surface browning, temperature profiles and drying rates of muffins were investigated. Muffins were baked in convection and steam assisted hybrid ovens at 145, 160 and 175 °C for different baking times. For all oven types, the acrylamide concentration of muffins increased with increasing baking time and temperature (p < 0.05). The formation was considered as the first order reaction kinetics except for the lowest baking temperature at natural convection and steam assisted hybrid ovens. The reaction rate constant, k was found to be in the range of 0.027–0.078 (min⁻¹). For the forced convection oven, the effect of baking temperature on acrylamide concentration followed the Arrhenius type of equation; with activation energy of 36.35 kJ/mol. The minimum drying rate was observed by the steam assisted hybrid oven, at all conditions. Steam assisted baking resulted in lower acrylamide concentration at all baking temperatures, while providing the average moisture content not significantly different.     

Mitigation of acrylamide formation in cookies by using Maillard reaction products as recipe modifier in a combined partial conventional baking and radio frequency post-baking process

This study aimed to mitigate acrylamide formation in cookies by lowering thermal energy input along with certain recipe modifications. Lowering temperature required longer cooking times as expected in order to achieve desired final moisture content. To shorten cooking time, conventional baking was combined with radio frequency post-baking process. Lack of development of surface browning in cookies during lower-temperature baking could be overcome by adding the Maillard reaction products (MRP) into dough. The MRP used to modify dough was prepared by heating a binary mixture of arginine and glucose at 100?°C for 6?h or by overbaking thin dough-layered disks. In comparison with control cookie baked at 205?°C for 11?min, combined conventional baking (205?°C for 8?min) and radio frequency post-drying process (45?s) decreased acrylamide formation in biscuits by up to 50?%. The use of Maillard reaction products to improve the visual acceptability of cookies to the consumer may have applications in food industry.     

Reduction of acrylamide formation in potato slices during frying

Reduction of acrylamide formation in potato chips was investigated in relation to frying temperature and three treatments before frying. Potato slices (Tivoli variety, diameter: 37 mm, width: 2.2 mm) were fried at 150°C, 170°C and 190°C until reaching moisture contents of ∼1.7 g water/100 g (total basis). Prior to frying, potato slices were treated in one of the following ways: (i) soaked in distilled water for 0 min (control), 40 min and 90 min; (ii) blanched in hot water at six different time-temperature combinations (50°C for 30 and 70 min; 70°C for 8 and 40 min; 90°C for 2 and 9 min); (iii) immersed in citric acid solutions of different concentrations (10 and 20 g/l) for half an hour. Glucose and asparagine concentration was determined in potato slices before frying, whereas acrylamide content was determined in the resultant fried potato chips. Glucose content decreased in ∼32% in potato slices soaked 90 min in distilled water. Soaked slices showed on average a reduction of acrylamide formation of 27%, 38% and 20% at 150°C, 170°C and 190°C, respectively, when they were compared against the control. Blanching reduced on average 76% and 68% of the glucose and asparagine content compared to the control. Potato slices blanched at 50°C for 70 min surprisingly had a very low acrylamide content (28 μm/kg) even when they were fried at 190°C. Potato immersion in citric acid solutions of 10 and 20 g/l reduced acrylamide formation by almost 70% for slices fried at 150°C. For the three pre-treatments studied, acrylamide formation increased dramatically as the frying temperature increased from 150°C to 190°C.     

The effect of asparaginase on acrylamide formation in French fries

Acrylamide formation in French fries was investigated in relation to blanching and asparaginase soaking treatments before final frying. Par-fried potatoes of Bintje variety were prepared by cutting strips (0.8 × 0.8 × 5 cm) which were blanched at 75 °C for 10 min. Unblanched strips were used as the control. Control or blanched strips were then dried at 85 °C for 10 min and immediately partially fried at 175 °C for 1 min. Finally, frozen par-fried potatoes were fried at 175 °C for 3 min to obtain French fries. Pre-drying of raw or blanched potato strips did not generate acrylamide formation as expected. Partial frying of pre-dried control potato strips generated 370 μg/kg of acrylamide and the final frying determined French fries with 2075 μg/kg of acrylamide. When control potato strips were treated with a 10000 ASNU/l asparaginase solution at 40 °C for 20 min, the acrylamide formation in French fries was reduced by 30%. When blanched potato strips were treated in the same way, the produced French fries have 60% less acrylamide content than blanched strips without the enzyme treatment. Soaking of blanched potato strips (75 °C, 10 min) in an 10000 ASNU/l asparaginase solution at 40 °C for 20 min is an effective way to reduce acrylamide formation after frying by reducing the amount of one of its important precursors such as asparagine.     

Antioxidant activity of cookies and its relationship with heat-processing contaminants: a risk/benefit approach

Formation of both health promoting and potential harmful substances (acrylamide and hydroxymethylfurfural) has been associated to the extent of the Maillard reaction. The effects of recipe compositions in terms of leavening agent (ammonium and sodium bicarbonates) and sugars (sucrose and glucose), and baking conditions (temperature and time) on the antioxidant activity (AOA) in cookies were studied. The cookies were baked at different temperatures (180–220 °C) for different times (10–25 min). AOA was measured by the ferric reducing power (FRAP), 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), 2,2,-diphenyl-1-picrylhydrazyl (DPPH) coloured radicals, and oxygen radical absorbance capacity (ORAC-fluorescein) in automated plate-reader assays. Net AOA varied regarding the assay applied, whereas higher AOA was always obtained for the ABTS assay and lower for DPPH assay, and ranging from 2 to 200 μmol Trolox/g sample. At higher temperature and baking times, higher AOA in cookies regardless of the formulation was recorded. Glucose enhances formation of compounds with higher AOA compounds as compared with sucrose recipes. Ammonium bicarbonate clearly promotes the formation of AOA for sucrose recipes but this effect is not observed in glucose recipes and varied with the AOA procedure applied. A risk/benefit index, based on the concomitant formation of neo-formed contaminants and substances with AOA (potentially health-promoting substances) is presented, and its application for recipe comparison is discussed. Risk/benefit index rapidly increased with increased temperature and time of baking.     

An instrumented oven for the monitoring of thermal reactions during the baking of sponge cake

An electric convective oven was conceived and equipped to allow monitoring thermal reactions during the baking of sponge cake. High total heat fluxes of between 6000 and 9000 W m⁻² were recorded under baking temperatures of 140-200 °C. The mapping of thermal conditions indicated satisfactory thermal homogeneity, with average temperature variations of 5 °C and maximum relative variations of the convective heat transfer coefficient of 15% on the thermal domain investigated. Internal heat and mass transfers, the extent of thermal reactions within the sponge cake and repeatability of the baking operation were all characterized by experimental measurements. Some of the main operating variables were monitored in the cake (core and surface temperatures, moisture content, levels of chemical reactants and products) and others in the baking atmosphere (temperature, humidity and concentrations of volatile compounds). Specific non-disruptive sampling devices were designed to extract data from cakes and the oven atmosphere in order to follow the kinetics of thermal reactions during the baking operation. Three phases could be identified during baking, corresponding to the relative importance of conductive and evaporative internal heat transfer regimes and to macroscopic changes in the cake structure with formation of a crust. The progress of thermal reactions was monitored with satisfactory precision in both the cake and the baking vapors: relative standard deviations of 2% and 8.7% were obtained respectively for the water content and hydroxymethylfurfural (HMF) content of three replicates during a baking operation.     

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

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

Influence of the amount of steaming during baking on the kinetic of heating and on selected quality attributes of bread

The effect of the amount of steam injection on selected bread characteristics were investigated using a deck oven (1 m² internal surface). Baking was done at 200 °C for 20 min with steaming of 100, 200, 300, 400 and 500 ml. The temperature at center of the bread and the CO₂ concentration in the oven have been measured during baking. Specific volume, moisture loss and crust crumb ratio were measured after baking.The heating rate between 35 and 55 °C was considered to compare the steaming conditions. For low steaming (100 and 200 ml), the heating rate was significantly higher (p < 0.05) than those at higher steaming (400-500 ml). The heating rate at 300 ml was between the 100-200 and 400-500 ml groups. This difference was attributed to the condensation of steam on the loaf for higher steaming, which in turns slows down the heating rate. The largest bread volume was obtained either for low or high steaming. However, tearing of the crust was observed for low steaming. The crust-crumb ratio was increasing with decreasing amount of steaming. The amount of CO₂ released during baking was higher for the highest amount of steaming; however, this result was not statistically different except between 100 and 500 ml. This could be attributed to a slower heating rate which in turns favors the secondary production of CO₂ during baking until thermal inactivation of CO₂.     

Characterizing the cellular structure of bread crumb and crust as affected by heating rate using X-ray microtomography

The effect of two baking conditions 240 °C and 220 °C (corresponding to heating rates 7.39 and 6.11 °C/min respectively) on the cellular structure of bread was investigated using X-ray microtomography. A comparison between helium pycnometry and X-ray microtomography was carried out and confirmed the quality of analysis in 3-D. Porosity profiles were determined in the interface crust/crumb and showed higher porosity and lower density of the upper crust when increasing heating rate and baking with steaming. The porosity profile of the whole slice bread showed differences between breads baked at 220 °C and 240 °C; that can be explained by the non uniformity in local expansion during baking resulting in different areas of variable density. Higher density was found in the bottom of the slice due to compression forces during baking. However, the upper zone of the slice was more porous, in relation with the expansion. These differences influence the texture and led to different kinetics of staling. Results of tortuosity confirm that the relative path length is shorter along the height related to the expansion of the bread during baking. Additionally, the relative path length through the pores is shorter when baking at 240 °C than when baking at 220 °C, in relation with porosity.     

Analysis and formation of trans fatty acids in hydrogenated soybean oil during heating

Hydrogenated oil has been widely used for production of shortenings or margarine, however, the presence of trans fatty acids may be detrimental to human health. The objectives of this study were to develop an improved method for analysis of trans fatty acids and evaluate their formation in both unhydrogenated and hydrogenated soybean oil during heating at 160, 180 and 200 °C for varied length of time. Results showed that among the four columns tested, an Agilent HP-88 column (100 × 0.25 mm I.D., 0.2-μm film thickness) could resolve eight trans fatty acids and nine cis fatty acids simultaneously within 31 min with injector temperature 240 °C, detector temperature 250 °C, and column temperature 170 °C in the beginning, maintained for 24 min, increased to 220 °C at 7.5 °C/min, 230 °C at 10 °C/min, and maintained for 5 min. The contents of both cis and trans fatty acids showed a decreased trend for the increase of heating time or temperature. No trans fatty acid formation was observed even after extensive heating of unhydrogenated and hydrogenated soybean oil for 24 h. This phenomenon demonstrated that trans fatty acids can only be formed under severe conditions.     

Kinetics of formation of acrylamide and Schiff base intermediates from asparagine and glucose

From the concentration of glucose and asparagine as reactants and of acrylamide as product each determined by LC–MS during reaction in an acetonitrile/water (68:32) model system at pH 7.6 (0.04 M phosphate buffer) and from the relative concentration of the Schiff base intermediate, the decarboxylated Schiff base intermediate, the Amadori product and aminopropionamide determined in the same reaction mixtures at 120 °C, 140 °C, 160 °C and 180 °C for up to 16 min, the energy of activation for formation of the Schiff base intermediate was found to have the value 50 ± 2 kJ mol⁻¹, while the apparent activation energy for formation of acrylamide was 64.4 ± 0.6 kJ mol⁻¹, for formation of the decarboxylated Schiff base intermediate 92 ± 2 kJ mol⁻¹, and for formation of the Amadori compound 59 ± 4 kJ mol⁻¹, respectively. At high temperature conditions, formation of the Schiff base is accordingly rate determining, while at lower temperatures, decarboxylation becomes rate determining. Aminopropionamide was only detected at reaction times at which acrylamide formation already is significant in favor of, a reaction path including direct formation of acrylamide from the decarboxylated Schiff base, rather than including dissociation of ammonia from aminopropionamide.     

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

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

Thermal inactivation of Salmonella spp. during conching

Although chocolate is a microbiologically stable product it has been described as a vehicle for Salmonella spp. Because of the low water activity (a_w) and the high fat content of chocolate Salmonella spp. shows an increased heat resistance, even during the thermal process of chocolate making. The aim of this study was to evaluate the thermal inactivation of Salmonella spp. during conching in various masses of chocolate and cocoa butter at different temperatures (50-90 °C). The effect of thermal treatment on Salmonella spp. was determined with the MPN (Most-Probable-Number) method. Results of thermal treatment showed approximate D-values for cocoa butter from D_50°C = 245 min to D_60°C = 306 min, for cocoa liquor from D_50°C = 999 min to D_90°C = 26 min and for dark chocolate of D_50°C = 1574 min. z-values were found to be z = 20 °C in cocoa liquor and z = 14 °C in dark chocolate. This study demonstrates that the conching process alone does not ensure the inactivation of Salmonella spp. in different chocolate masses and that an additional decontamination step at the beginning of the process as well as an HACCP concept is necessary during chocolate production to guarantee the absence of Salmonella spp. in chocolates and related products.     

Study on formation of acrylamide in asparagine–sugar microwave heating systems using UPLC-MS/MS analytical method

Microwave heating can be regarded as a possible way to produce a considerable amount of acrylamide. The present study investigated the formation of acrylamide in asparagine–glucose, asparagine–fructose and asparagine–sucrose microwave heating systems by the response surface methodology (RSM) and the orthogonal array methodology (OAM). The acrylamide content was rapidly quantified by a validated ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) method. Results of RSM study indicated that in the asparagine–glucose system, the acrylamide content increased in the combined condition of high temperature accompanying with short heating time (>190 °C, <20 min) or low temperature accompanying with long heating time (<180 °C, >30 min). In the asparagine–fructose system, the similar conclusion was made in the combined condition of high temperature accompanying with short heating time (>175 °C, <20 min) or low temperature accompanying with long heating time (<170 °C, >25 min). In the asparagine–sucrose system, the amount of acrylamide enhanced with the increase of both heating temperature and heating time. The fitted mathematic models were successfully applied to the quantification of acrylamide formation when the heating temperature and heating time fell into the ranges of 120–240 °C and 5–35 min simultaneously. OAM study showed that acrylamide is readily formed via heating binary precursors 5 min at 180 °C in the asparagine–glucose and asparagine–fructose systems. However, acrylamide is readily generated when the binary precursors are heated 15 min at 180 °C in the asparagine–sucrose system.     

Acrylamide kinetic in plantain during heating process: Precursors and effect of water activity

Almost two thirds of plantain world production is processed by means of deep frying which place it in the same occurrence as potatoes-based food in some tropical regions (Latin America, Central Africa and Southeast Asia). Asparagine content and effect of water activity on acrylamide kinetic in a plantain matrix was surprisingly investigated for the first time. Asparagine content was analyzed in ten edible Musa L., and “Cooking bananas” were found (maximum of 70 mg/100 g db) to be less concentrated than “dessert bananas” (maximum of 321 mg/100 g db). Moreover, asparagine content decreased by 75% after 11 days of post-harvest ripening. Acrylamide formation/elimination kinetics were determined in plantain paste at three different initial water activity values (0.972, 0.904, and 0.430) measured at 25 °C and heated at high temperatures (140-200 °C) in a closed reactor. Acrylamide in plantain was formed at the same magnitude as for potatoes, rye and wheat-based products (max ~ 0.9 ppm, wb). Kinetic parameter estimation was performed using a single response modeling. The reaction kinetic and the estimated kinetic parameters revealed an increase in acrylamide formation and elimination reaction rates with decreasing water activity. The corresponding activation energies of the rate constants remained unaffected.     

Effect of Steam Baking on Acrylamide Formation and Browning Kinetics of Cookies

Abstract: Effects of baking method and temperature on surface browning and acrylamide concentration of cookies were investigated. Cookies were baked in natural and forced convection and steam‐assisted hybrid ovens at 165, 180, and 195 °C and at different times. For all oven types, the acrlyamide concentration and surface color of cookies increased with increasing baking temperature. Significant correlation was observed between acrylamide formation and browning index, BI, which was calculated from Hunter L, a, and b color values, and it showed that the BI may be considered as a reliable indicator of acrylamide concentration in cookies. Acrylamide formation and browning index in cookies were considered as the first‐order reaction kinetics and the reaction rate constants, k, were in the range of 0.023 to 0.077 (min^?1) and 0.019 to 0.063 (min^?1), respectively. The effect of baking temperature on surface color and acrylamide concentration followed the Arrhenius type of equation, with activation energies for acrylamide concentration as 6.87 to 27.84 kJ/mol; for BI value as 19.54 to 35.36 kJ/mol, for all oven types. Steam‐assisted baking resulted in lower acrylamide concentration at 165 °C baking temperature and lower surface color for all temperatures. Steam‐assisted baking is recommended as a healthy way of cooking providing the reduction of harmful compounds such as acrylamide for bakery goods, at a minimal level, while keeping the physical quality. Practical Application: The kinetics of acrylamide formation and browning of cookies will possibly allow definition of optimum baking temperatures and times at convectional and steam‐assisted baking ovens. The kinetic model can be used by developing baking programs that can automatically control especially a new home‐scale steam‐assisted hybrid oven producing healthy products, for the use of domestic consumers.     

The formation of potentially harmful compounds in churros, a Spanish fried-dough pastry,as influenced by deep frying conditions

Colour, moisture, hydroxymethylfurfural (HMF) and acrylamide (AA) were investigated in traditional Spanish churros. Samples were deep-fried in sunflower oil at lab-scale temperatures of 180, 190 and 200 °C and for frying times of 2, 3, 5 and 7 min. Fresh made churros were also obtained from local producers. HMF ranged from 1.2 ± 0.02 to 221.4 ± 2.02 mg/kg for lab-scale experiments and an average of 74.3 ± 47.5 mg/kg was recorded in commercial samples. AA ranged from below the limit of quantitation to 90 ± 0.6 μg/kg for lab-scale experiments and an average of 46 ± 24.5 μg/kg was measured in commercial samples. Temperatures between 185 and 200 °C are commonly used to obtain churros with an acceptable palatability and a crispy surface. However, HMF and AA levels increased nearly two-fold from 190 to 200 °C at the same frying times, indicating that a more precise control of frying temperatures is required to minimize their formation.