Conjugation prepared by wet-Maillard reactions improves the stability and properties of lutein and lycopene loaded nanoparticles.

In this study, lutein and lycopene were encapsulated in plant protein (faba bean protein concentrate, (FPC))-carrageenan (Car) conjugates prepared by Maillard reaction in an aqueous media. The conjugation improved encapsulation yield that reached to 82.69% and 93.07%, for lycopene and lutein, respectively. The mean particle diameters for lutein loaded nanoparticles observed smaller in FPC-Car conjugates (66.60 nm) than FPC (71.49 nm). Scanning electron microscopy images showed that FPC-Car conjugates were more spherical and no fractures or fissures on the surface, revealing that wall materials provided better protection and retention for core materials. The diameter of lycopene nanoparticles coated with FPC remained constant between pH 3-4 and 7-9 but increased to 220 nm at pH 4-6. Even though the diameter of lutein nanoparticles coated with FPC remains steady between pH 5 and 9, increased to 953 nm at pH 3. The bioaccessibility of the lutein or lycopene samples encapsulated by FPC were found as higher than FPC-Car conjugates. These findings suggest that protein-polysaccharide conjugates could be used as a wall material to encapsulate lipophilic lutein and lycopene in order to improve their stability, property and bioaccessibility. As a result, FPC-Car conjugates may be an alternative for the formation of functional beverages as well as other nutraceutical products. Supplementary Information: The online version contains supplementary material available at 10.1007/s13197-024-05976-4.

Contents of ɑ-dicarbonyl compounds in commercial black tea and affected by the processing.

The species and contents of ɑ-dicarbonyls in commercial black tea were examined, along with the effects of the manufacturing process and drying temperature on the formation of ɑ-dicarbonyls. Ten ɑ-dicarbonyls were quantified in commercial and in-process black tea samples by using UPLC-MS/MS and their derived quinoxalines. The ɑ-dicarbonyls content in commercial black tea decreased significantly (p < 0.05) in the following order: 3-deoxyglucosone > glucosone > 3-deoxypentosone = threosone > galactosone ≥ methylglyoxal = glyoxal ≥ 3-deoxygalactosone = 3-deoxythreosone = diacetyl. Except for 3-deoxyglucosone and 3-deoxygalactosone, a further eight ɑ-dicarbonyls were identified in all manufacturing steps of black tea. Except for the drying step, the rolling and fermenting played important roles in the formation of ɑ-dicarbonyls. The total contents of ɑ-dicarbonyls in black tea infusion ranged from 16.48 to 75.32 µg/g based on our detected ten ɑ-dicarbonyls.

Construction of protein-, polysaccharide- and polyphenol-based conjugates as delivery systems.

Natural polymers, such as polysaccharides and proteins, have been used to prepare several delivery systems owing to their abundance, bioactivity, and biodegradability. They are usually modified or combined with small molecules to form the delivery systems needed to meet different needs in food systems. This paper reviews the interactions of proteins, polysaccharides, and polyphenols in the bulk phase and discusses the design strategies, coupling techniques, and their applications as conjugates in emulsion delivery systems, including traditional, Pickering, multilayer, and high internal-phase emulsions. Furthermore, it explores the prospects of the application of conjugates in food preservation, food development, and nanocarrier development. Currently, there are seven methods for composite delivery systems including the Maillard reaction, carbodiimide cross-linking, alkali treatment, enzymatic cross-linking, free radical induction, genipin cross-linking, and Schiff base chemical cross-linking to prepare binary and ternary conjugates of proteins, polysaccharides, and polyphenols. To design an effective target complex and its delivery system, it is helpful to understand the physicochemical properties of these biomolecules and their interactions in the bulk phase. This review summarizes the knowledge on the interaction of biological complexes in the bulk phase, preparation methods, and the preparation of stable emulsion delivery system.

Alternative Processing Options for Improving the Proteins Functionality by Maillard Conjugation.

Conjugation of the proteins with carbohydrates, occurring in the early stages of the Maillard reactions, received increased attention because of the high potential to ensure the improvement of the biological activity and functional properties of the proteins of different origins. The Maillard conjugates are conventionally formed through wet or dry heating, but the use of alternative technologies involving ultrasound, microwave, pulsed electric fields, high-pressure, or electrodynamic treatments appears to be efficient in accelerating the reaction steps and limiting the formation of toxic compounds. An overview of the mechanisms of these processing technologies, the main parameters influencing the Maillard conjugate formation, as well as their advantages and disadvantages, is provided in this paper. Different strategies employing these alternative technologies are reported in the literature: as pretreatment of the proteins, either alone or in admixture with the carbohydrates, followed by conventional heating, as a single alternative treatment step, or as a combination of heating and alternative processing. The desired functional properties of the proteins can be achieved by selecting the appropriate processing strategy and optimizing the reaction parameters. Moreover, alternative technologies can be exploited to obtain Maillard conjugates with remarkable biological activity in terms of antioxidant, antimicrobial, antihypertensive, anti-inflammatory, antimutagenic, or bifidogenic properties.

Sensory attributes and functional properties of maillard reaction products derived from the crassosotrea gigas (Ostrea rivularis gould) enzymatic hydrolysate and xylose system.

To improve the flavor of Ostrea rivularis Gould, enzymatic hydrolysis was conducted and xylose-OEH Maillard reaction products were prepared. Then, their physicochemical properties and metabolites were determined by UHPLC-MS-MS, and volatile compounds were determined by GC-MS to investigate the changes. The results showed that His, Gln, Lys, Asp, and Cys were the major amino acids consumed. After being heated at 120 °C for up to 150 min, the DPPH (2,2-Diphenyl-1-picrylhydrazyl) was 85.32 ± 1.35% and the reducing capacity was 1.28 ± 0.12. Both were the highest in the groups. Additionally, 45 volatile compounds, including 2-ethyl-5-methyl-pyrazine and 2-ethyl-3,5-dimethyl-pyrazine, and 678 compounds were identified. We also found that 18 metabolites with significant differences (VIP ≥2) were differential metabolites, which involved lipid oxides and amino acid derivatives. The content of lipids favored the regulation of Maillard products and affected the lower threshold of the flavor of aldehydes, which contributed to the flavor and antioxidant activity. These results suggested the potential of xylose-OEH MRPs as a natural antioxidant for further processing oysters.

Investigation of cocoa and cinnamon effect on acrylamide formation in cakes production using GC/MS method: A risk assessment study.

This study was conducted with the aim of investigating the effect of cinnamon and cocoa on the formation of acrylamide in cake samples and their carcinogenic and non-carcinogenic risks. The cake samples were prepared using alkaline extraction, xanthidrol derivative and micro-extraction, then injected into a gas chromatography-mass spectrometry (GC-MS) to identify acrylamide. The maximum and minimum mean concentration of acrylamide among samples was related to the cinnamon cakes (212.28 ng/g) and the cocoa cake samples (10.14 ng/g), respectively. Acrylamide concentration for unflavored samples, cinnamon cake samples and cocoa cake samples were 61.86 ng/g, 169.38-212.28 ng/g and 10.14-44.64 ng/g, respectively. Human health risk assessment based on Monte Carlo simulation (MCS) indicated that the target hazard quotient and incremental lifetime cancer due to ingestion of acrylamide formation in cake samples for adults and children were in the acceptable limits (THQ > 1 and CR > 1E-4). In conclusion, cocoa flavor was able to decrease the concentration of acrylamide in cakes. According to the results, it is necessary to measure the amount of acrylamide in consumer cakes by regulatory organizations.

Formation of Volatile Heterocyclic Compounds and Open-Chain Amides of Theanine in Model Systems with Glucose, Tea Leaves, and Tea Extract under Tea-Roasting Conditions.

Theanine is a non-proteinogenic amino acid found in the tea plant Camellia sinensis. At an elevated temperature (>90 °C), it released two major volatile compounds 1-ethyl-1,5-dihydro-2H-pyrrol-2-one and N-ethylsuccinimide. Other products were identified, including 10 pyrroles and 12 amides/imides. The formation of the two major compounds was proposed to be initiated by the deamination of theanine and through the intermediate α-keto acid. In the presence of glucose, the two major products and many other volatiles from theanine thermal degradation were accelerated and further Maillard reactions occurred. A total of 56 compounds were identified in the model system of theanine and glucose, including 12 amides/imides, 16 pyrazines, 16 pyrroles and other N-heterocycles, and 12 furans and other O-heterocycles. Although most of the reaction products were detected in tea leaves and in their aqueous extract with or without the addition of theanine under the same experiment conditions, imides and amides were considerably suppressed, left only minute amounts, or were even no longer detectable. Pyrazines and pyrroles were also shown at reduced concentrations as a result of the interaction with tea components but to a lesser extent. A total of 16 and 12 pyrazines were identified in the theanine/glucose reaction system and tea leaves/aqueous extract after roasting, respectively. The results indicated that pyrazines and other main volatiles in roasted tea leaves were formed from the Maillard reactions of the aqueous fraction of tea leaves. Theanine participated in the formation of pyrazines in tea leaves under roasting conditions.

Sensory and Chemical Characteristic of Two Insect Species: Tenebrio molitor and Zophobas morio Larvae Affected by Roasting Processes.

The volatile compounds from insects (Tenebrio molitor and Zophobas morio larvae) roasted at 160, 180, or 200 °C and fed with potato starch or blue corn flour were isolated by solid-phase microextraction (SPME), and identified by gas chromatography-mass spectrometry (GC-MS). In the tested material, 48 volatile compounds were determined. Among them, eight are pyrazines, aroma compounds that are formed in food products during thermal processing due to the Maillard reaction. Eleven of the identified compounds influenced the roast, bread, fat, and burnt aromas that are characteristic for traditional baked dishes (meat, potatoes, bread). Most of them are carbonyl compounds and pyrazines. To confirm the contribution of the most important odorants identified, their odor potential activity values (OAVs) and %OAV were calculated. The highest value was noted for isobuthylpyrazine, responsible for roast aroma (%OAV > 90% for samples roasted at lower temperatures), and 2,5-dimethylpyrazine, responsible for burnt aroma (%OAV > 20% for samples roasted at the highest temperature). According to the study, the type of feed did not significantly affect the results of the sensory analysis of roasted insects. The decisive influence was the roasting temperature. The highest scores were achieved for Tenebrio molitor larvae heat-treated at 160 °C.

[Analysis of peptides and proteins from Asini Corii Colla using nano LC-Q-Exactive-MS/MS].

This paper aims to systematically analyze the peptides and proteins from Asini Corii Colla(ACC) through shotgun proteomics. After high-pH reversed-phase fractionation, the proteins and peptides in the hydrolysate of ACC were further separated by nano LC-Q-Exactive-MS/MS under the following conditions: Thermo Scientific EASY column(100 µm×2 cm, 5 µm, C_(18)) as precolumn, Thermo Scientific EASY column(75 µm×100 mm, 3 µm, C_(18)) for solid phase extraction, gradient elution with 0.1% formic acid in water(mobile phase A) and 84% acetonitrile in water containing 0.1% formic acid(mobile phase B), and MS in positive ion mode. Based on Uniprot_Equus caballus, MS data, and literature, 2 291 peptides were identified from ACC by MaxQuant, with 255 Maillard reactions(AML, CML, CEL)-modified peptides identified for the first time. Through alignment, the peptides were found to belong to 678 equine proteins. In conclusion, the combination of nano LC-Q-Exactive-MS/MS and shotgun proteomics achieved rapid and accurate identification of the proteins and peptides in ACC, which provides the key information and new insights for further investigation of chemicals and effective substances in ACC.

Analysis of peptides and proteins from Asini Corii Colla using nano LC-Q-Exactive-MS/MS / 中国中药杂志

This paper aims to systematically analyze the peptides and proteins from Asini Corii Colla(ACC) through shotgun proteomics. After high-pH reversed-phase fractionation, the proteins and peptides in the hydrolysate of ACC were further separated by nano LC-Q-Exactive-MS/MS under the following conditions: Thermo Scientific EASY column(100 μm×2 cm, 5 μm, C_(18)) as precolumn, Thermo Scientific EASY column(75 μm×100 mm, 3 μm, C_(18)) for solid phase extraction, gradient elution with 0.1% formic acid in water(mobile phase A) and 84% acetonitrile in water containing 0.1% formic acid(mobile phase B), and MS in positive ion mode. Based on Uniprot_Equus caballus, MS data, and literature, 2 291 peptides were identified from ACC by MaxQuant, with 255 Maillard reactions(AML, CML, CEL)-modified peptides identified for the first time. Through alignment, the peptides were found to belong to 678 equine proteins. In conclusion, the combination of nano LC-Q-Exactive-MS/MS and shotgun proteomics achieved rapid and accurate identification of the proteins and peptides in ACC, which provides the key information and new insights for further investigation of chemicals and effective substances in ACC.

Introduction to the Special Issue: New Frontiers in Acrylamide Study in Foods-Formation, Analysis and Exposure Assessment.

Acrylamide is a chemical contaminant that naturally originates during the thermal processing of many foods. Since 2002, worldwide institutions with competencies in food safety have promoted activities aimed at updating knowledge for a revaluation of the risk assessment of this process contaminant. The European Food Safety Authority (EFSA) ruled in 2015 that the presence of acrylamide in foods increases the risk of developing cancer in any age group of the population. Commission Regulation (EU) 2017/2158 establishes recommended mitigation measures for the food industry and reference levels to reduce the presence of acrylamide in foods and, consequently, its harmful effects on the population. This Special Issue explores recent advances on acrylamide in foods, including a novel insight on its chemistry of formation and elimination, effective mitigation strategies, conventional and innovative monitoring techniques, risk/benefit approaches and exposure assessment, in order to enhance our understanding for this process contaminant and its dietary exposure.

Effect of Microwave Heating on the Acrylamide Formation in Foods.

Acrylamide (AA) is a neurotoxic and carcinogenic substance that has recently been discovered in food. One of the factors affecting its formation is the heat treatment method. This review discusses the microwave heating as one of the methods of thermal food processing and the influence of microwave radiation on the acrylamide formation in food. In addition, conventional and microwave heating were compared, especially the way they affect the AA formation in food. Available studies demonstrate differences in the mechanisms of microwave and conventional heating. These differences may be beneficial or detrimental depending on different processes. The published studies showed that microwave heating at a high power level can cause greater AA formation in products than conventional food heat treatment. The higher content of acrylamide in microwave-heated foods may be due to differences in its formation during microwave heating and conventional methods. At the same time, short exposure to microwaves (during blanching and thawing) at low power may even limit the formation of acrylamide during the final heat treatment. Considering the possible harmful effects of microwave heating on food quality (e.g., intensive formation of acrylamide), further research in this direction should be carried out.

Chemical and Sensory Characteristics of Soy Sauce: A Review.

Soy sauce is a fermented product, and its flavor is a complex mixture of individual senses which, in combination, create a strong palatable condiment for many Eastern and Western dishes. This Review focuses on our existing knowledge of the chemical compounds present in soy sauce and their potential relevance to the flavor profile. Taste is dominated by umami and salty sensations. Free amino acids, nucleotides, and small peptides are among the most important taste-active compounds. Aroma is characterized by caramel-like, floral, smoky, malty, and cooked potato-like odors. Aroma-active volatiles are chemically diverse including acids, alcohols, aldehydes, esters, furanones, pyrazines, and S-compounds. The origin of all compounds relates to both the raw ingredients and starter cultures used as well as the parameters applied during production. We are only just starting to help develop innovative studies where we can combine different analytical platforms and chemometric analysis to link flavor attributes to chemical composition.

Methylglyoxal-hydroimidazolones (MG-Hs) instead of Nɛ-(carboxymethyl)-l-lysine (CML) is the major advanced glycation end-product during drying process in black tea.

This study was to examine the formation of advanced glycation end-products (AGEs) in black tea during drying process at 90, 120, and 150 °C for 1 h. Nine AGEs including Nɛ-(carboxyethyl)-l-lysine (CEL), Nɛ-(carboxymethyl)-l-lysine (CML), three isomers of methylglyoxal-hydroimidazolones (MG-Hs), three isomers of glyoxal-hydroimidazolones (GO-Hs), and argpyrimidine were quantified by using HPLC-MS/MS with isotope-labelled internal standard. Results showed that each AGE during the drying process of 150 °C was significantly higher (p < 0.05) than at 90 and 120 °C, and argpyrimidine was only found in the treatment of 150 °C. MG-H1/3 was first quantified as the major AGE during drying at 120-150 °C, the content respectively reached to (39.66 ± 2.61) µg/g and (58.88 ± 1.76) µg/g after 1 h drying, where CML content only had (19.86 ± 1.02) µg/g and (23.71 ± 1.40) µg/g. This study indicated that arginine derived-AGEs are the key components of black tea AGEs.

Use of random forest methodology to link aroma profiles to volatile compounds: Application to enzymatic hydrolysis of Atlantic salmon (Salmo salar) by-products combined with Maillard reactions.

To use salmon protein hydrolysates as food ingredients and to mask the fish odor, Maillard reactions were associated with enzymatic production of hydrolysates. The study explored an original approach based on regression trees (RT) and random forest (RF) methodologies to predict hydrolysate odor profiles from volatile compounds. An experimental design with four factors: enzyme/substrate ratio, quantity of xylose, hydrolysis and cooking times was used to create a range of enzymatic hydrolysates. Twenty samples were submitted to a trained panel for sensory descriptions of odor. Hydrolysate volatile compounds were extracted by means of Headspace Solid Phase MicroExtraction (HS-SPME) and analyzed using gas chromatography/mass spectrometry (GC-MS). The results showed that RT and RF methodologies can be useful tools for predicting an entire sensory profile from volatile compounds. Four main volatile compounds made it possible to separate hydrolysates into five groups according to their specific sensory profile. 2,5-dimethylpyrazine, 1-hydroxy-2-propanone and 3-hydroxy-2-pentanone were identified as the main predictors of the roasted odor, whereas methanethiol was associated with a mud odor. These results also suggest the appropriate process conditions for obtaining a typical roasted odor.

The glycation level of milk protein strongly modulates post-prandial lysine availability in humans.

Industrial heat treatment of milk results in protein glycation. A high protein glycation level has been suggested to compromise the post-prandial rise in plasma amino acid availability following protein ingestion. In the present study, we assessed the impact of glycation level of milk protein on post-prandial plasma amino acid responses in humans. Fifteen healthy, young men (age 26 (SEM 1) years, BMI 24 (SEM 1) kg/m2) participated in this randomised cross-over study and ingested milk protein powder with protein glycation levels of 3, 20 and 50 % blocked lysine. On each trial day, arterialised blood samples were collected at regular intervals during a 6-h post-prandial period to assess plasma amino acid concentrations using ultra-performance liquid chromatography. Plasma essential amino acid (EAA) concentrations increased following milk protein ingestion, with the 20 and 50 % glycated milk proteins showing lower overall EAA responses compared with the 3 % glycated milk protein (161 (SEM 7) and 142 (SEM 7) v. 178 (SEM 9) mmol/l × 6 h, respectively; P ≤ 0·011). The lower post-prandial plasma amino acid responses were fully attributed to an attenuated post-prandial rise in circulating plasma lysine concentrations. Plasma lysine responses (incremental AUC) following ingestion of the 20 and 50 % glycated milk proteins were 35 (SEM 4) and 92 (SEM 2) % lower compared with the 3 % glycated milk protein (21·3 (SEM 1·4) and 2·8 (SEM 0·7) v. 33·3 (SEM 1·7) mmol/l × 6 h, respectively; P < 0·001). Milk protein glycation lowers post-prandial plasma lysine availability in humans. The lower post-prandial availability of lysine following ingestion of proteins with a high glycation level may compromise the anabolic properties of a protein source.

Acrylamide and Thermal-Processing Indexes in Market-Purchased Food.

Determining acrylamide (AA) content in foods using chromatographic methods is expensive and time-consuming. Therefore, there is a need to develop a simple, economical method for monitoring the content of acrylamide in foods. This study analysed whether there is a relationship between acrylamide levels with some heat-induced parameters, such as 5-hydroxymethylfurfural (HMF) and browning, in order to assess their usefulness in predicting the potential acrylamide levels in market-purchased food. Sixty plant-based food products were tested. The correlation coefficients for AA levels with L*, a* and b* values and HMF content were significant (p < 0.05) for French fries and potato chips. There was no statistically significant correlation between thermal-processing indexes (HMF and colour parameters) and acrylamide levels in commercial bread, breakfast cereals and biscuits. The results indicate that these classical thermal-processing indexes are not directly related to the acrylamide content in commercial cereal-based food and they cannot be indicators of AA level. Thus, the correlation between HMF and colour parameters with acrylamide content depends on the type of food and it is difficult to estimate the amount of AA based on these classical thermal-processing indexes of market-purchased food.

The Chemistry behind Chocolate Production.

Chocolate production is a complex process during which numerous chemical reactions occur. The most important processes, involving most of the reactions important for development of the proper chocolate flavor, are fermentation, drying and roasting of cocoa bean, and chocolate conching. During fermentation, formation of important precursors occurs, which are essential for further chemical reactions in the following processes of chocolate production. Roasting is one of the most important processes due to the occurrence of Maillard's reactions, during which aroma compounds are formed. In this paper, we have reviewed the most important chemical reactions that occur with proteins, carbohydrates, lipids, and polyphenols. Additionally, we present other components that may be naturally present or form during the production process, such as methylxanthines, aldehydes, esters, ketones, pyrazines, acids, and alcohols.

Effect of pH on the reaction between naringenin and methylglyoxal: A kinetic study.

Methylglyoxal (MGO) is a highly reactive ɑ-dicarbonyl compound that may adversely impact food quality and human health by modifying proteins. The kinetics of the reaction of naringenin with MGO was studied at pH 6-8 and 37 °C by UV-Vis spectrophotometry and reaction products were characterized by liquid chromatography-mass spectrometry (LC-MS/MS). The apparent second order rate constant (k2) increased at pH above the lowest pKa value of naringenin, indicating deprotonated naringenin as the main reactant. A Lederer-Manasse type reaction mechanism is suggested, with dehydration of the MGO-dihydrate as a rate determining step. The quantitative data obtained in the present study was used to simulate the competitive reaction between MGO and nucleophilic amino acid residues (Lys, Arg and Cys) and naringenin in milk. It is predicted that naringenin will be able to efficiently trap MGO during storage of milk, although the reversible trapping of MGO by Cys residues is initially kinetically favourable.

Formation of α-Dicarbonyls from Dairy Related Carbohydrates with and without Nα-Acetyl-l-Lysine during Incubation at 40 and 50 °C.

α-Dicarbonyls are reactive intermediates formed during Maillard reactions and carbohydrate degradation. The formation of seven α-dicarbonyls was characterized in solutions containing dairy related carbohydrates (galactose, glucose, lactose, and galacto-oligosaccharides (GOS)) during incubations at 40 and 50 °C with and without Nα-acetyl-l-lysine at pH 6.8 for up to 2 months. The concentrations of α-dicarbonyls in samples of monosaccharides with Nα-acetyl-l-lysine were found to be 3-deoxyglucosone (3-DG) > 3-deoxygalactosone (3-DGal) > glyoxal > glucosone, galactosone > methylglyoxal > diacetyl. The presence of Nα-acetyl-l-lysine resulted in up to 100-fold higher concentrations of C6 α-dicarbonyls but lesser formation of glyoxal in the monosaccharide-containing models compared to what was observed in the absence of Nα-acetyl-l-lysine. Galactose incubated with Nα-acetyl-l-lysine generated the highest concentrations of 3-DGal (up to 130 µM), glyoxal (up to 100 µM), and methylglyoxal (up to 9 µM) compared to the other carbohydrates during incubation. Surprisingly, 3-DG (1500 µM) and 3-DGal (80 µM) were formed at levels of 2 orders of magnitude higher in solutions of GOS in the absence of Nα-acetyl-l-lysine as compared to the other carbohydrates at 40 °C, while GOS generated the lowest levels of glyoxal. GOS are widely used as an ingredient in various types of foods products, and it is therefore of importance to consider the risk of generating high levels of the reactive C6 α-dicarbonyl, 3-DG, in these types of products. This study contributes to the understanding of major α-dicarbonyl formation as affected by the presence of primary amines in GOS-, lactose-, and galactose-containing solutions under moderate heating in liquid foods.