Influence of Hydroxycinnamic Acids on the Maillard Reaction of Arabinose and Galactose beyond Carbonyl-Trapping.

Hydroxycinnamic acids, known for their health benefits and widespread presence in plant-based food, undergo complex transformations during high-temperature processing. Recent studies revealed a high browning potential of hydroxycinnamic acids and reactive Maillard reaction intermediates, but the role of phenolic compounds in the early stage of these reactions is not unambiguously understood. Therefore, we investigated the influence of caffeic acid and ferulic acid on the nonenzymatic browning of arabinose, galactose, and/or alanine, focusing on the implications on the formation of relevant early-stage Maillard intermediates and phenol-deriving products. Contrary to previous assumptions, hydroxycinnamic acids were found to promote nonenzymatic browning instead of solely trapping reactive intermediates. This was reflected by an intense browning, which was attributed to the formation of heterogeneous phenol-containing Maillard products. Although, caffeic acid is more reactive than ferulic acid, the formation of reactive furan derivatives and of heterogeneous phenol-containing colorants was promoted in the presence of both hydroxycinnamic acids.

Contribution of Hydroxycinnamic Acids to Color Formation in Nonenzymatic Browning Reactions with Key Maillard Reaction Intermediates.

The Maillard reaction is a vital part of food processing, involving a vast number of complex reaction pathways, resulting in high-molecular-weight colorants. So far, studies have been focused on the conversion of carbohydrates and amino compounds, but the literature elaborating the contribution of phenolic compounds to the formation of the colored end-products is still rare. The aim of this study was to characterize early reactions, underlying the formation of phenol-containing melanoidins. For this purpose, binary model systems of the prominent phenolic compounds caffeic acid and ferulic acid combined with α-dicarbonyl compounds typically formed in the Maillard reaction such as glyoxal, methylglyoxal, and diacetyl were analyzed after heat treatment. High-resolution mass spectrometry revealed that decarboxylation, aromatic electrophilic substitution, and nucleophilic addition are important reaction steps that lead to colored heterogeneous oligomers. Polymerization was favored for phenolic compounds with a high electron density in the aromatic system and for α-dicarbonyl compounds carrying aldehyde functions.

Colorants and Antioxidants Deriving from Methylglyoxal and Heterocyclic Maillard Reaction Intermediates.

The Maillard reaction is well known for producing antioxidant compounds alongside colored substances. Low-molecular-weight antioxidant intermediates such as maltol (MAL) or norfuraneol (NF) are well described, but it is still unclear which of these Maillard intermediates are the precursors of antioxidant and colored melanoidins-the so-called late stage Maillard reaction products. This study aimed to provide novel insights into the correlation between browning potential and antioxidant properties of reaction products formed during the heat treatment of prominent Maillard reaction intermediates. It was achieved by the incubation of binary reaction systems composed of methylglyoxal (MGO) or NF in combination with furfural (FF), MAL, and pyrrole-2-carbaldehyde (PA) at pH 5 and 130 °C for up to 120 min. Overall, it could be shown that the formation of colored products in the binary NF reaction systems was more efficient compared to those of MGO. This was reflected in an increased browning intensity of up to 400% and a lower conversion rate of NF compared to MGO. The colorants formed by NF and FF or PA (~0.34 kDa and 10-100 kDa) were also found to exhibit higher molecular weights compared to the analogue products formed in the MGO incubations (<0.34 kDa and 10-100 kDa). The incorporation of NF into these heterogenous products with FF and PA resulted in the preservation of the initial antioxidant properties of NF (p < 0.05), whereas no antioxidant products were formed after the incubation of MGO.

Characterization of Colorants Formed by Non-Enzymatic Browning Reactions of Hydroxycinnamic Acid Derivatives.

The browning of plant-based food is commonly understood to result from the enzymatic polymerization of phenolic compounds to pigments, called melanin. However, during the thermal treatment of food, enzymes are deactivated, and non-enzymatic reactions predominate. The extent of the contribution of phenolic compounds to these non-enzymatic reactions has been speculated ("melanin-like vs. melanoidin-like"), but the literature is limited. Therefore, the aim of the present study was to investigate the heat-induced reactions of caffeic acid (CA), para-coumaric acid (CS), ferulic acid (FA), hydrocaffeic acid (HC), and 5-O-caffeoylquinic acid (CGA) under dry conditions. The model systems were characterized by color formation, reactant conversion, and antioxidant properties. Reaction products were analyzed by high-resolution mass spectrometry (HRMS) and nuclear magnetic resonance (NMR) spectroscopy. Decarboxylation could be classified as the driving force for the observed color formation and was significantly impacted by the substitution of the aromatic system. Reaction products were found to contribute to an increase in the antioxidant properties of the model systems. The oligomers described in this study could be incorporated into food melanoidins, contributing to the color and antioxidant properties observed in roasted food rich in phenolic compounds, such as coffee or cocoa.