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.

Lotus rhizome is an important aquatic vegetable, but the blackening of lotus rhizome epidermis (LRE) seriously affects its appearance and quality, which makes lotus rhizome products unmarketable. In this study, the effects of polyphenols and iron on the LRE color were studied to explore the possible mechanism of LRE blackening. Results indicated that the measurable total phenols contents in the mud treatment (MT) group were significantly reduced, and the total iron contents were significantly increased compared with the bruised treatment group (p < 0.05). The high-performance liquid chromatography results showed that the main polyphenols in LRE were dopa, gallocatechin, and catechin, as well as a small amount of catechol, epicatechin, proanthocyanidin B2, and proanthocyanidin C1. Moreover, the results of color difference and ultraviolet adsorption spectroscopy showed that there were obviously black or brown-gray of dopa (525 nm), gallocatechin (504.5 nm), and catechin (550 and 504.5 nm) with FeCl2. The simulated system treatment of LRE further confirmed that the chromaticity effect of dopa and iron in bruised LRE was similar to that of the MT group, whereas 1% (w/w) ascorbic acid, 2% (w/w) EDTA-2Na, or 3% (w/w) citric acid could solely prohibit the blackening. This suggested that the dopa in LRE and FeCl2 in mud may mainly combine into [2(DOPA-2H+)+Fe3+]- through non-covalent interaction, which leads to the blackening of bruised LRE under neutral conditions. These results can guide the storage of lotus rhizomes and improve the development of the lotus rhizome industry.

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.

Nonenzymatic browning (NEB) reactions often affect the nutritional quality and safety properties of amorphous food solids. Developing a proper approach to control the NEB reaction has been of particular interest in the food industry. An NEB reaction in an amorphous maltose/Whey protein isolates (WPI) matrix containing L-lysine and D-xylose as reactants were studied at ambient temperatures aw ≤ 0.44 and 45~65 °C. The results indicated that the presence of NEB reactants barely disturbed the water sorption behavior of the matrix. The Guggenheim-Anderson-de Boer (GAB) constants and Qst values of the studied samples were affected by storage conditions as the migration of sorbed water among monolayers occurred. The rate of color changes and 5-hydoxymethylfurfural (5-HMF) accumulation on the matrix were accelerated at high ambient temperatures aw, reflecting the extent of NEB reaction increases. Since the strength concept (S) could give a measure of molecular mobility, the extent of the NEB reaction was governed by the molecular mobility of the matrix as the activation energy (Ea) of 5-HMF production minimized at solids with high S values. We found that the S concept had a considerable potential usage in controlling the NEB reaction on amorphous sugar-protein solids. This data set has practical significance in the comprehensive understanding of manipulating the diffusion-limited chemical reactions on low-moisture food solids.

Msalais is a wine fermented from boiled grape juice. Nonenzymatic browning (NEB) greatly affects the quality of Msalais, but to date its mechanism has not been systematically analyzed. In the current study, the evolution of NEB during Msalais production was investigated using models of grape juice. 5-Hydroxymethylfurfural (5-HMF), browning index (BI), yellowness index (YI), sample absorbance at 420 (A420), and b* increased during heating, with a clear transition point at 110 min. The Maillard reaction (MR) was the major contributor to NEB. Vitamin C (VC) facilitated NEB in the late stage of heating. During heating that lasted over 130 min, glucose contributed to NEB more than fructose, while the reverse was true for heating lasting less than 130 min. Proline (Pro) was the most important amino acid in facilitating NEB. BI and A420 decreased during fermentation, while increasing slightly during wine storage. In conclusion, this study identified the evolution of NEB during the Msalais process, which will facilitate the control of traditional Msalais production for improved wine quality.

Nonenzymatic browning during storage of pasteurized shelf-stable orange juice causes a major color deterioration, which negatively affects consumer acceptance of the juice. This study, for the first time, investigated on a kinetic basis the effect of pH and suspected nonenzymatic browning reaction precursors such as ascorbic acid, fructose, and arginine on nonenzymatic browning during accelerated storage (42 °C) using an orange-juice-based model system. The results showed that lowering the pH of the model juice system from 3.8 to 1.5 significantly increased the rate of ascorbic acid degradation, the rate changes (increases and decreases) in different sugars, and the rates of furfural and 5-hydroxymethylfurfural formation. These changes coincided with a higher browning intensity, which became more pronounced toward the end of storage of the juice model system. Similarly, adding more ascorbic acid and fructose largely increased the formation of furfural and 5-hydroxymethylfurfural, respectively, and resulted in a higher browning intensity. In conclusion, lowering the pH of the orange juice or addition of ascorbic acid or fructose will enhance its browning during prolonged storage.

For the first time in literature, this study revealed the participation of polymeric components of orange juice cloud and pulp (such as proteins, arabinogalactan proteins, or protein-pectin complexes) during nonenzymatic browning. In a quest to better understand the nonenzymatic browning of shelf-stable orange juice during storage, the juice was fractionated into different fractions depending on the solubility in water/ethanol and the obtained fractions were characterized. The results showed that brown compounds that were formed during storage of orange juice were distributed over water insoluble (pulp), ethanol insoluble (cloud), and ethanol soluble (serum) fractions. In the ethanol insoluble fraction, the brown compounds are hypothesized to be associated with proteins, arabinogalactan proteins, and/or protein-pectin complexes of this fraction without significantly changing their molecular weight distributions, monosaccharide compositions, and protein contents. The changes in the ethanol soluble fraction including ascorbic acid degradation, acid-catalyzed hydrolysis of sucrose, and formation of furfural and 5-hydroxymethylfurfural were highly correlated to the browning development of the juice during storage.

Lactose reduced dairy products are more prone to Maillard reactions due to the presence of reactive monosaccharides. Conventional β-galactosidases, which are used for lactose hydrolysis in lactose-reduced dairy products, will lead to conversion of lactose into glucose and galactose, where especially galactose is very reactive during Maillard reactions. Some β-galactosidases have transgalactosylating activity and will thus convert lactose into galacto-oligosaccharides (GOS) and hereby limit the release of galactose. The aim of this study was to investigate the extent of participation of GOS in Maillard reactions in comparison to lactose, a 50:50 mixture of glucose and galactose, and galactose exclusively in sodium caseinate-based milk-like model systems heated at 130 and 75 °C at pH 6.8. The GOS system exhibited reduced loss of free amino groups; accumulated less furosine and less of the following advanced glycation end products (AGEs): Nε-carboxyethyl lysine, methylglyoxal-derived hydroimidazolone isomers, glyoxal-derived lysine dimer, and methylglyoxal-derived lysine dimer; and also developed less browning compared to monosaccharide models. However, the GOS-caseinate system accumulated more 3-deoxyglucosone and 3-deoxygalactosone, which resulted in higher concentrations of 5-(hydroxymethyl)furfural and pyrraline. The results indicated that GOS overall participate less readily in Maillard reactions than the monosaccharides investigated but were more prone to degradation to C6 α-dicarbonyls species. Finally, relationship analysis indicated that C6 α-dicarbonyls seemed to primarily increase concentrations of 5-(hydroxymethyl)furfural instead of AGEs. Our results suggest that conversion of lactose into GOS instead of monosaccharides in milk by transgalactosylating β-galactosidases could be a useful strategy for production of lactose-free milk for people with lactose intolerance.

Browning index (BI, ABS520 nm /ABS420 nm ) is a measure of anthocyanin-rich fruit juice pigmentation quality. This study sought to determine the extent to which BI describes anthocyanin quality and degradation in fruit juices. Commercial fruit juices were assayed for monomeric anthocyanin (MA) content, percent polymeric color (%PC), pH, and BI. BI varied, 0.29 to 1.72, among cranberry, cherry, grape, aronia, and pomegranate juices. Principal component analysis (PCA) revealed that BI was strongly inversely associated with %PC, and positively correlated with MAs to a lesser extent. The BI of grape and cherry juices varied linearly with pH from 2.0 to 4.0 in pH-adjusted juices. Cherry and grape juices at pH approximately 2.0 to 4.0 were incubated at 50 °C to induce juice browning. BI and MA decreased, and %PC increased, but the amount of MA degradation was not explained by %PC. In the aged juices, BI and MA were strongly correlated using PCA. In aged grape juice, chromatographic analysis was used characterize anthocyanins, proanthocyanidins, and anthocyanin scission products. Anthocyanin loss and a gain of unresolved components absorbing at 420 nm decreased BI. Proanthocyanidins and co-eluting pigments with varying BI decreased during aging. Scission products did not account for anthocyanin loss. Thus, MA loss more so than the gain in pigments associated with juice proanthocyanidins contribute to the increase in %PC and decline of the BI during accelerated aging of grape juice. Thus, BI is a useful marker of fruit juice quality within juices of the same pH and anthocyanin composition.
UNASSIGNED: Fruit juice pigmentation depends on anthocyanins, pH, and other matrix components. Spectrophotometric methods to determine pigmentation include the browning index (ABS520 nm /ABS420 nm ), pH differential method for monomeric anthocyanin (MA) content, and bisulfite bleaching to determine percent polymeric color (%PC). In this study, anthocyanin-rich fruit juice browning index was strongly dependent on pH and MA content. MA loss, and to a lesser extent, a gain in newly-formed pigments at 420 nm contributed to the browning index change during aging. Therefore, browning index is strongly associated with MA content and is useful for assessing fruit juice quality.

Effects of NaCl, KCl, CaCl2, NaHCO3, and NH4HCO3 on the formation of glucosone, 1-deoxyglucosone, 3-deoxyglucosone, glyoxal, methylglyoxal, diacetyl, 5-hydroxymethyl-2-furfural, and 2-furfural and browning were investigated in cookies. The presence of 1.5% NaCl, 1% KCl, and 1% CaCl2 on flour basis had no effect on α-dicarbonyl compounds, except 1-deoxyglucosone increased in the presence of KCl and CaCl2. The increase in 5-hydroxymethyl-2-furfural formation in the presence of NaCl, KCl, and CaCl2 did not relate to 3-deoxyglucosone formation and pH changes. NaCl, KCl, and CaCl2 increased browning in cookies. Model reaction systems indicated that NaCl, KCl, and CaCl2 enhance browning by increasing furfurals in caramelization. NaCl, KCl, and CaCl2 decreased browning intensity in a heated glucose-glycine system. Use of CaCl2 in cookies may considerably increase furfurals but not α-dicarbonyl compounds. Sodium reduction can be obtained by replacement with potassium without sacrificing the desired consequences of caramelization in sugar-rich baked goods.