High correlation of methylglyoxal with acrylamide formation in glucose/asparagine Maillard reaction model

α-Dicarbonyl compounds were highly reactive intermediates formed in Maillard reaction (MR), and o-phenylenediamine (OPD) was widely used as a trapping agent for α-dicarbonyl compounds. Both aqueous glucose/asparagine (Glc/Asn) and glucose/asparagine/o-phenylenediamine (Glc/Asn/OPD) model systems were heated at 150 °C for up to 30 min. The α-dicarbonyl compounds formed in MR were identified by HPLC/MS in our particular model system, indicating that 3-deoxy-2-hexosulose, 2,3-butanedione and methylglyoxal (MG) were three main α-dicarbonyl compounds. In this work, MG was chosen as a representative of α-dicarbonyl compound in MR to investigate the influence on the formation of acrylamide (AA). The concentrations of AA, MG and Asn were detected during MR by HPLC method. The results indicated that the formation of AA increased with the heating time, and nearly 80% of AA formed through participation of α-dicarbonyl compounds. These results were consistent with the changes of amounts of MG. The amounts of formation and consumption of MG increased with heating time, and from 9 min of reaction, the consumed amounts of MG accounted for 73–88% on basis of total amounts of MG formed in MR, suggesting that most of MG take part in the next reaction steps. Meanwhile, the Asn concentration decreased with heating time in both models. The formation of AA and consumption of Asn were highly correlated with MG. Indeed, as MG concentration in MG/Asn model system decreased during heating at 150 °C, the concentration of AA significantly increased. The coefficient of correlation between consumed amounts of MG and the formed amounts of AA is 0.931, again demonstrating that MG does play a role in AA formation.     

Effects of o-phenylenediamine on methylglyoxal generation from monosaccharide: Comment on “correlation of methylglyoxal with acrylamide formation in fructose/asparagine Maillard reaction model system”

Methylglyoxal (MG), a reactive carbonyl compound, has recently garnered much attention because of its ability to modify proteins over time and yield advanced glycation end products (AGEs) that are thought to contribute to the development of diabetes mellitus and its complications. In a recent paper published in Food Chemistry by Yuan et al. [Yuan, Y., Zhao, G. H., Hu, X. S., Wu, J. H., Liu, J., & Chen, F. (2007a). Correlation of methylglyoxal with acrylamide formation in fructose/asparagines Maillard reaction model system. Food Chemistry, 108(3), 885–890] authors showed a high correlation between methylglyoxal formation and acrylamide formation. However, in their study, model systems of aqueous fructose/asparagines (Fru/Asn) and fructose/asparagines/o-phenylenediamine (Fru/Asn/OPD) heating at 150 °C were used. The validity of these models relies on the assumption that OPD will only serve the role of a trapping agent for MG. In this short communication, we would like to call to attention that MG can also have a strong catalytic effect in the generation of MG from fructose. Therefore, it is concluded that the concentration of MG obtained in Fru/Asn/OPD model system cannot correspond to the total amount of MG formed by Maillard reaction of Fru and Asn as claimed by Yuan et al. [Yuan, Y., Zhao, G. H., Hu, X. S., Wu, J. H., Liu, J., & Chen, F. (2007a). Correlation of methylglyoxal with acrylamide formation in fructose/asparagines Maillard reaction model system. Food Chemistry, 108(3), 885–890, Yuan, Y., Zhao, G. H., Hu X. S., Wu, J. H., Liu, J., & Chen. F. (2007b). High correlation of methylglyoxal with acrylamide formation in glucose/asparagine Maillardreaction model. European Food Research and Technology. doi:10.1007/s00217-007-0658-0].     

Impact of selected additives on acrylamide formation in asparagine/sugar Maillard model systems

The main purpose of this paper was to study the effect of selected additives, NaCl, NaHSO₃, ascorbic acid, cysteine and allicin, on acrylamide (AA) formation in asparagine/fructose (Asn/Fru) and asparagine/glucose (Asn/Glc) by microwave processing. Our results showed that NaHSO₃ and cysteine had the best reduction rate on AA formation, but the browning would be influenced by the addition of these additives. Ascorbic acid is another good inhibitor for AA formation both in Asn/Fru and Asn/Glc model systems, but the browning would be inhibited by the high concentration of ascorbic acid. Natural antioxidants are attractive candidates for the development of effective inhibitors for AA formation. In the present study, allicin effectively reduced AA formation and achieved a maximum reduction rate of > 50% for the use of allicin at a concentration of 0.0375% in Asn/Fru model system. While in Asn/Glc model system, allicin did not show good reduction rate. Through RSM study, the lowest AA content was 0.181 ??g/mL by the addition of allicin in Asn/Fru and 0.029 ??g/mL by the addition of ascorbic acid in Asn/Glc model system, respectively. The study could be regarded as a pioneer contribution on AA reduction in Maillard model system by the addition of allicin.     

Advanced glycation end products inhibitors from Alpinia zerumbet rhizomes

Advanced glycation end products (AGEs) are major factors responsible for the complication of diabetes. The present study was carried out to investigate the inhibitory activities on fructosamine adduct and α-dicarbonyl formations by hexane extracts of various parts of Alpinia zerumbet. Furthermore, we isolated two previously known compounds, namely 5,6-dehydrokawain (DK) and dihydro-5,6-dehydrokawain (DDK). 8(17),12-Labdadiene-15,16-dial (labdadiene) was isolated for the first time from the rhizome of A. zerumbet. The results showed that labdadiene (IC₅₀ = 51.06 μg/mL) had similar activity to rutin and quercetin against fructosamine adduct. The inhibition of α-dicarbonyl compounds formation by labdadiene was significantly higher than that of DK and DDK. Our results indicate that labdadiene is a potent antiglycation agent which was found to inhibit AGEs formation in three different steps in the pathway. These data indicate that labdadiene could be used to prevent glycation-associated complications in diabetes.     

Study of acrylamide mitigation in model systems and potato crisps: effect of rosmarinic acid

In the current study, rosmarinic acid (RosA) played a critical role in inhibiting acrylamide (AA) formation in Maillard system and potato chips. Compared to the control group, AA formation was markedly inhibited by RosA of 10⁻⁴ and 10⁻¹ mm in asparagine (Asn)-glucose (Glc) system, and 10⁻⁵−1.0 mm in Asn-fructose (Fru) system. The kinetic study indicated that with heating time ranging from 30 to 60 min, RosA had a significant inhibition effect on AA formation. Mechanism study showed the addition reaction between RosA and AA was the primary pathway to inhibit AA formation. In potato crisps, response surface methodology showed that frying temperature of 140.11 °C, frying time of 6.02 min and RosA concentration of 0.012 μm had the lowest AA formation. In conclusion, RosA inhibited AA formation in both the model systems and potato crisps, and its application in food industry is well expected.     

Formation of α-dicarbonyl fragments from mono- and disaccharides under caramelization and Maillard reaction conditions

Glyoxal, methylglyoxal and diacetyl were identified as reaction products from non-enzymatic browning of D-glucose (Glc), D-fructose (Fru), maltose and maltulose. The α-dicarbonyl compounds were quantified throughout the reaction. Monosaccharides formed more dicarbonyl fragments than disaccharides and Glc formed more than Fru. It is suggested that Fru tends to yield cyclic products rather than fragmentation products under the reaction conditions used. Furthermore, a mechanism for the fragmentation of disaccharides is proposed.     

Inhibitory effects of guava (Psidium guajava L.) leaf extracts and its active compounds on the glycation process of protein

Hyperglycaemia causes increased protein glycation and the formation of early glycation products and advanced glycation end products (AGEs) which are major factors responsible for the complications of diabetes. This study investigated the ability of guava leaf and compounds to inhibit glycation process in an albumin/glucose model system and compared the potency of these extracts with Polyphenon 60 which is a commercial polyphenol product extracted from green tea and with the standard antiglycation agent, aminoguanidine. The results showed that the inhibitory effects of guava leaf extracts on the formation of α-dicarbonyl compounds were over 95% at 50 μg/ml. Phenolic compounds present, namely gallic acid, catechin and quercetin exhibited over 80% inhibitory effects, but ferulic acid showed no activity. The guava leaf extracts also showed strong inhibitory effects on the production of Amadori products and AGEs from albumin in the presence of glucose. The phenolic compounds also showed strong inhibitory effects on the glycation of albumin, especially quercetin exhibited over 95% inhibitory effects at 100 μg/ml. According to the results obtained, guava leaf extracts are potent antiglycation agents, which can be of great value in the preventive glycation-associated complications in diabetes.     

Effects of sesamol, sesamin, and sesamolin extracted from roasted sesame oil on the thermal oxidation of methyl linoleate

This study investigated the effects of lignan compounds extracted from roasted sesame oil, which were sesamol, sesamin, and sesamolin, on oxidation of methyl linoleate (ML) during heating. These compounds were added at 500 or 1000 mg/kg to ML, and α-tocopherol was used as a reference antioxidant. The ML added with lignans or α-tocopherol was heated at 180 °C for 60 min. Thermal oxidation of ML was evaluated by conjugated dienoic acid (CDA) contents, p-anisidine value (PAV), and ML retention. Contents changes of lignan compounds or α-tocopherol in ML during heating were monitored by high-performance liquid chromatography. CDA contents and PAV of samples increased and ML decreased with heating time at 180 °C. Samples added with lignan compounds showed lower CDA contents and PAV but higher ML retention than samples without lignan compounds. The antioxidant activity of sesame oil lignan compounds in ML oxidation during heating tended to be higher than that of α-tocopherol. The contents of lignan compounds in samples decreased with heating time due to their degradation, but the degradation rates were lower than that of α-tocopherol. This study suggested that sesame oil lignan compounds be used as antioxidants in oil at high temperatures for deep-fat frying due to their higher effectiveness and stability than α-tocopherol.     

Characterisation of an acidic peroxidase from papaya (Carica papaya L. cv Tainung No. 2) latex and its application in the determination of micromolar hydrogen peroxide in milk

An acidic peroxidase isoform, POD-A, with a molecular mass of 69.4 kDa and an isoelectric point of 3.5 was purified from papaya latex. Using o-phenylenediamine (OPD) as a hydrogen donor (citrate–phosphate as pH buffer), the optimum pH for the function of POD-A was 4.6, and the optimum temperature was 50 °C. The peroxidase activity of POD-A toward hydrogen donors was both pH- and concentration-dependent. Under optimal conditions, POD-A catalysed the oxidation of OPD at higher rates than pyrogallol, catechol, quercetin and 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS). The chemical modification reagents N-bromosuccinimide and sodium azide significantly inhibited POD-A activity. The results of kinetic studies indicated that POD-A followed a ping-pong mechanism and had a K_m value of 2.8 mM for OPD. Using CPC silica-immobilised POD-A for the determination of micromolar H₂O₂ in milk, the lower limit of determination was 0.1 μM, and the recoveries of added H₂O₂ were 96–109%.     

Interactions between whey soybean protein (WSP) and beta-conglycinin (7S) during the formation of protein particles at elevated temperatures

In this study, the amount, size, calcium sensibility, and composition of heat-induced protein particles in the mixture of beta-conglycinin (7S) and whey soybean protein (WSP) dispersion are compared with those of 7S and WSP dispersion to investigate the interactions between WSP and 7S during heating. The addition of 7S prevents WSP from forming large protein particles which can be precipitated by centrifugation at 10,000g for 10 min. The protein in the heated mixture of 7S and WSP (7S/WSP = 1/1) coagulates at higher calcium concentrations than that in the mixture of heated 7S and heated WSP at a ratio of 1/1. This result strongly indicates that 7S and WSP interact with each other during heating and form complex protein particles which have special surface properties that are different from individual 7S and WSP protein particles. Particle size distribution analysis has also shown that 7S prevents WSP from forming larger protein particles during heating. SDS-PAGE analysis shows that lipoxygenase (LOX), beta-amylase, and lectin of WSP and the beta subunit of 7S tend to form a particulate fraction, while the KTI, alpha, and alpha′ subunits tend to form a soluble fraction. WSP, 7S, and their mixture have been heated at 60, 65, 70, 75, 80, 85, 90, and 95 °C for 10 min, and ultracentrifugation analysis shows that about 77–85% of the protein particles were formed at 65–75 °C in all three dispersions. SDS-PAGE analysis indicates that LOX and β-amylase have been denatured and that they have participated in the formation of protein particles when heated within 65–75 °C, while lectin has begun to participate in particle formation at above 85 °C. It is concluded that WSP plays an evident role in the formation of protein particles in soymilk during heating.     

cis/trans-Isomerisation of triolein,trilinolein and trilinolenin induced by heat treatment

To estimate the trans-fatty acid production of edible oils during the frying process, 1.0 g of triolein, trilinolein and trilinolenin, as representative oils, were heated at 180 °C for a defined period. The amounts of trans-fatty acids in heated triacylglycerols were quantitatively determined by gas chromatography after methylation. It was revealed that heating induced cis to trans-isomerisation of unsaturated triacylglycerols, and that trans-fatty acid amounts increased gradually, depending on the heating period. For example, trans-isomer amounts in triolein, trilinolein and trilinolenin (per gram) were 5.8 mg, 3.1 mg and 6.5 mg, respectively, after 8 h incubation at 180 °C. At that time, the contents of polar compounds contained in the heated triolein, trilinolein and trilinolenin were 22%, 27% and 31%, respectively. When triolein was heated under a N₂ stream, neither trans-isomerisation nor polar compounds were detected. The addition of α-tocopherol (1.0%) to triolein significantly prevented not only lipid oxidation but also trans-isomerisation during heating. A commercially available vegetable oil was also heated under the same conditions as these model oils. Compared with the trans-isomerisation in model oils, the degree of trans-isomerisation in the edible oil was relatively low. Tocopherols in the oil would prevent not only lipid oxidation but also isomerisation. These results suggest that the geometric isomerisation of unsaturated fatty acids during heating accompanies lipid oxidation.     

Preventive effects of guava (Psidium guajava L.) leaves and its active compounds against α-dicarbonyl compounds-induced blood coagulation

Diabetes is associated with a hypercoagulable state which may accelerate atherosclerosis, thrombosis and the diabetic microvascular complication. Endogenously produced α-dicarbonyl compounds are linked to the pathophysiology of diabetic complications. The effects of α-dicarbonyl compounds on coagulation parameters in vitro and the anticoagulant activities of aqueous extracts from guava leaves were examined. Incubation of plasma with glyoxal or methylglyoxal at 0.1 mM showed a significant decrease in thrombin clotting time (TT) (P < 0.05). However, they exhibited slight prolongation of the prothrombin time (PT) at 0.5 mM and no effect on the activated partial thromboplastin time (APTT). In order to define the action mechanism of the hypercoagulant activity, coagulation factors such as fibrinogen and antithrombin III activity were evaluated. The fibrinogen contents in plasma were decreased slightly with increasing concentrations of glyoxal and methylglyoxal. Moreover, methylglyoxal inhibited antithrombin III activity and over 80% of the activity was lost at 1.2 mM methylglyoxal. In contrast, guava leaf extracts exhibited significant inhibition of TT shortening induced by methylglyoxal. Guava leaf extracts and its active phenolic compounds including ferulic acid, gallic acid and quercetin also displayed a protective effect against methylglyoxal-induced loss of activity of antithrombin III. Thus, guava leaf extracts are a potent antiglycative agent and anticoagulant, which can be of great value in the preventive glycation-associated cardiovascular diseases in diabetes.     

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.     

Control of the Maillard reaction by ferulic acid

This study investigated how ferulic acid (FA) affects the formation of certain Maillard reaction products (MRPs), i.e., early MRPs, fluorescent and non-fluorescent advanced glycation end products (AGEs), and melanoidins in model systems. Glycation mixtures were prepared containing soy glycinin or bovine serum albumin (final concentration 10 mg/ml) and fructose (222 mM) in 0.2% KOH in the presence or absence of FA (12.95 mM) and incubated at 60 °C for 60 min. The extent of the MR was estimated by analysis of free amino groups, the incorporation of sugar into the protein backbone as well as the formation of N^?-(carboxymethyl)lysine (CML), fluorescent AGEs (λ_exc = 337 nm, λ_em = 350–550 nm) and melanoidins (absorbance at 420 nm). Formation of CML and fluorescent AGEs was reduced by nearly 90% by the addition of FA while early MRPs and melanoidins were inhibited to a lesser extent (∼10% and 28%, respectively) compared to AGE formation. A controlled formation of early MRPs was achieved by use of FA, and it is a new finding. To the best of our knowledge, for the first time the use of FA as a reliable means of obtaining novel glycoprotein preparations containing low amounts of AGEs, with the potential to be used as functional food ingredients, is proposed.     

Degradation compounds of carotenoids formed during heating of a simulated cashew apple juice

The influence of organic acid and heating treatments on carotenoid degradation on a simulated cashew apple juice was assessed by high performance liquid chromatography coupled with a photodiode array and mass spectrometry detectors. A total of nineteen carotenoids were separated in unheated simulated cashew apple juice, with all-trans-β-cryptoxanthin and all-trans-β-carotene as the major ones. As a consequence of heating, five xanthophylls disappeared, whereas two new cis isomers and five epoxide or furanoid-derivatives were formed and the levels of all cis isomers increased. In addition, 12′-apo-β-carotenal was formed at 90 °C. Two oxidation compounds (12′-apo-β-carotenal and 5,6-epoxy-β-cryptoxanthin) were formed after β-cryptoxanthin heating at 90 °C in an aqueous-based system. In all systems, the amounts of total carotenoids lost were not compensated by those formed. These facts indicated that isomerisation and oxidation to both coloured and non-coloured compounds were the main reactions occurring during heating of carotenoids in aqueous-based and juice systems.     

Acrylamide in potato crisp—the effect of raw material and processing

Reducing sugars and free amino acids were analysed in slices from three potato cultivars before and after blanching (0-3 min). The potato crisps were deep fried at 185 °C for different times (3-8.5 min), and analysed for the concentration of acrylamide (AA) and moisture. Potato cultivar and the temperature during processing were important parameters for AA formation in potato crisps. The amount increased with an increase in the processing time. Blanching before deep-frying reduced the concentration of free asparagine and reducing sugar in the raw material. We found no effect of blanching as pretreatment on the concentration of AA in the potato crisps. Any relationship was not detected between the levels of asparagine in the different cultivars, before and after blanching, and the formation of AA in the crisp products. However, it was shown that the content of reducing sugars determined the level of AA after frying.     

Changes in volatile compounds of palm sap (Arenga pinnata) during the heating process for production of palm sugar

This study was carried out to determine the changes of volatile compounds composition during palm sugar production. The samples were collected at every 30 min interval for 4 h of heating process at 150 °C from a local traditional manufacturer in Kuala Pilah, Malaysia. The analyses were performed by gas chromatography–mass spectrometry after headspace solid phase micro extraction. The results showed that N-heterocyclic chemical class possessed the highest relative percentage area (RPA) 83.69%, followed by O-heterocyclic group with RPA of 14.5%. Main volatile compounds the determined were 5-methyl-6,7-dihydro-5H-cyclopenta pyrazine and 4-hydroxy-2,5-dimethyl-3(2H) furanone which were responsible for roasty and sweet caramel-like aroma notes, respectively. The pyrazine compounds increase exponentially with heating time but furan derivatives compounds were formed at a later stage, i.e. at 180 min of heating time and above 105 °C.     

Activities of hydrocolloids as inhibitors of acrylamide formation in model systems and fried potato strips

Effects of eight hydrocolloids on acrylamide (AA) formation were compared. At 2% (w/w), pectin, alginic acid (>50% reduction) and xanthan gum (∼20%) significantly (P < 0.05) reduced acrylamide formation in chemical models. In the fried snack model, effective inhibition of acrylamide formation (∼30%) by most of the hydrocolloids was observed only when the concentration was increased to 5%. Immersing potato strips for 1 h in a 1% alginic acid solution before frying produced inhibition of acrylamide formation similar to that in a 5% solution, and immersing for 5 h led to a significantly lower AA content (∼60% versus ∼30% reduction) compared with immersing for 1 h in a 1% or 5% immersion solution. Similar phenomena were also observed for pectin. The findings suggest alginic acid and pectin are promising inhibitors of acrylamide formation, and immersion time is an important determinant for their effects against acrylamide formation in fried potato products.     

Identification and quantification of α-dicarbonyl compounds produced in different sugar-amino acid Maillard reaction model systems

A mixture of α-dicarbonyl compounds generated from Maillard reaction (MR) model systems, comprising of fructose with glycine (Fru-Gly) and lysine (Fru-Lys); glucose with glycine (Glu-Gly) and lysine (Glu-Lys); ribose with glycine (Rib-Gly) and lysine (Rib-Lys), were identified and quantified. α-Dicarbonyl compounds generated in the hexose models were predominantly glucosone and 3-deoxyglucosone (3-DG), with 3-deoxypentosone (3-DP) and pentosone being the major α-dicarbonyls produced in the pentose models. Ethyl acetate extraction of model MRPs resulted in poor recovery of 2,3-diaminonaphthalene benzoquinoxalines of glucosone, 3-DG, pentosone, 3-DP and methylglyoxal (MGO), respectively. The temporal profiles of pentosone, 3-DP, glyoxal (GO) and MGO were similar in the pentose models, with maximum concentration occurring within 5 min. These four α-dicarbonyl compounds were higher (P < 0.05) in Rib-Gly than in Rib-Lys MR systems. The quantity of α-dicarbonyl compounds was affected by the interaction among the type of sugar and amino acid and the reaction time. The type of sugar is the most important factor that affected both the quantity and quality of α-dicarbonyl compounds produced in MR mixtures.