Enhancing methane production in anaerobic digestion of waste activated sludge by combined thermal hydrolysis and photocatalysis pretreatment.

Thermal hydrolysis (TH) is promising for sludge pretreatment, but the refractory substances generated at high temperatures inhibit anaerobic digestion. In this study, a novel combined TH and photocatalytic pretreatment method was proposed to improve the anaerobic digestion performance of waste activated sludge. The results showed that the combined pretreatment (170 °C, 0.5 g/L TiO2) increased methane yield by 66 % from 111 ± 5 m L/g VS to 185 ± 5 m L/g VS. After TH pretreatment, photocatalysis further promoted sludge solubilization by destroying extracellular polymeric substances, resulting in an increase in released soluble organic matter from 292 ± 16 mg/L to 4,091 ± 85 mg/L. In addition, photocatalysis improved the biodegradability of sludge by reducing the melanoidin and humic acid contents by 26 % and 20 %, respectively. The proposed novel pretreatment method effectively overcomes the bottleneck of TH technology and provides an alternative pretreatment technology for improving sludge resource recovery.

Exploring Maillard reaction markers and melanoidins to investigate toxicological and antioxidant profiles of optimized expanded snacks from corn/common bean mixtures.

BACKGROUND: Extrusion cooking of cereal-legume flour mixture is an innovative strategy to introduce nutrient-enriched ready-to-eat snacks to the market. However, this thermal process triggers the formation of compounds that could impact safety aspects of these products. Maillard reaction markers and the end products known as melanoidins were evaluated to assess the toxicological and bioactive profiles of extruded snacks from corn-plus-common-bean-flour combinations. Different molecular weight fractions were isolated and purified to analyze their antioxidant activity and to investigate the role of melanoidins. RESULTS: The snack formulated with an 84:16 ratio of corn:common bean flours exhibited an enhanced toxicological profile. It displayed the lowest levels of acrylamide and furanic compounds, along with reduced blockage of lysine residues in the protein. Extrusion increased the antioxidant activity of uncooked flours (30 to 64%) and total phenolic compounds (26 to 50%), and decreased the available lysine (-72.7 to -79.5%). During the fractionation process, it was established that compounds within the range of 3-10 kDa made the greatest contribution to antioxidant activity. The fraction greater than 10 kDa, which included melanoidins, displayed 7 to 33% lower antioxidant activity. The purification of the fraction greater than 10 kDa revealed that pure melanoidins represented approximately one-third of the antioxidant activity in that fraction. Non-covalent adducts linked to the melanoidin core therefore had a relevant role in the antioxidant action of formulated snacks. CONCLUSION: This investigation illustrates the importance of considering both potential risks and associated benefits of compounds formed during the Maillard reaction while developing new extruded snacks. © 2024 The Author(s). Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

In vitro human colonic fermentation of coffee arabinogalactan and melanoidin-rich fractions.

Coffee beverage is a source of dietary fiber composed by arabinogalactans, which can also be associated to proteins and phenolic compounds, originating melanoidins. Human colonic in vitro fermentations of coffee fractions, one rich in melanoidins (Mel) and the other in its parental polysaccharide arabinogalactans (AG), were performed in order to evaluate the metabolites produced by microbiota, namely short-chain fatty acids (SCFA), phenolic compounds, and bile acids. After 48 h of fermentation, a higher fermentability of the carbohydrate fraction of AG (62 %) than that of Mel (27 %) was observed, resulting in a SCFA content of 63 mM and 22 mM, respectively. Supplementation with AG and Mel fractions decreased the acetate:propionate ratio from 4.7 (in the absence of coffee fractions) to 2.5 and 3.5, respectively, suggesting a potential inhibition of HMG-CoA reductase, a rate-limiting enzyme for cholesterol synthesis. The fermentation of coffee fractions yielded dihydroferulic and dihydrocaffeic acids, known to have antioxidant properties. In the presence of Mel, it was observed a decrease (from 0.25 to 0.16 mg/mL) in the production of secondary bile acids, whose high content is associated to the development of several diseases, such as colorectal cancer, neurodegenerative and cardiovascular.

The Maillard reactions: Pathways, consequences, and control.

The century old Maillard reactions continue to draw the interest of researchers in the fields of Food Science and Technology, and Health and Medical Sciences. This chapter seeks to simplify and update this highly complicated, multifaceted topic. The simple nucleophilic attack of an amine onto a carbonyl group gives rise to a series of parallel and subsequent reactions, occurring simultaneously, resulting into a vast array of low and high mass compounds. Recent research has focused on: (1) the formation and transformation of α-dicarbonyl compounds, highly reactive intermediates which are essential in the development of the desired color and flavor of foods, but also lead to the production of the detrimental advanced glycation end products (AGEs); (2) elucidation of the structures of melanoidins in different foods and their beneficial effects on human health; and (3) harmful effects of AGEs on human health. Considering that MRs have both positive and negative consequences, their control to accentuate the former and to mitigate the latter, is also being conscientiously investigated with the use of modern techniques and technology.

Antioxidant and antibrowning properties of Maillard reaction products in food and biological systems.

Oxidative damage refers to the harm caused to biological systems by reactive oxygen species such as free radicals. This damage can contribute to a range of diseases and aging processes in organisms. Moreover, oxidative deterioration of lipids is a serious problem because it reduces the shelf life of food products, degrades their nutritional value, and produces reaction products that could be toxic. Antioxidants are effective compounds for preventing lipid oxidation, and synthetic antioxidants are frequently added to foods due to their high effectiveness and low cost. However, the safety of these antioxidants is a subject that is being discussed in the public more and more. Synthetic antioxidants have been found to have potential negative effects on health due to their ability to accumulate in tissues and disrupt natural antioxidant systems. During thermal processing and storage, foods containing reducing sugars and amino compounds frequently produce Maillard reaction products (MRPs). Through the chelation of metal ions, scavenging of reactive oxygen species, destruction of hydrogen peroxide, and suppression of radical chain reaction, MRPs exhibit excellent antioxidant properties in a variety of food products and biological systems. Also, the capacity of MRPs to chelate metals makes them as a potential inhibitor of the enzymatic browning in fruits and vegetables. In this book chapter, the methods used for the evaluation of antioxidant activity of MRPs are provided. Moreover, the antioxidant and antibrowning activities of MRPs in food and biological systems is discussed. MRPs can generally be isolated and used as commercial preparations of natural antioxidants.

Development and standardization of spectrophotometric assay for quantification of thermal hydrolysis-origin melanoidins and its implication in antioxidant activity evaluation.

Melanoidins are brown recalcitrant polymers originating from the thermal hydrolysis pretreatment (THP) of organic solid waste (OSW). Owing to their various formation pathways and complex structures, there is currently no reliable method to quantify melanoidins. In this study, a spectrophotometric method was developed to determine melanoidins concentration in different OSW. Three typical model Maillard reaction systems (glucose-glycine, glucose/fructose-20 amino acids, and dextran-bovine serum albumin) were used to acquire the characteristic peaks and establish standard curves. The results showed that a standard curve using glucose/fructose-20 amino acids model melanoidins at 280 nm was the optimal quantification method, because it had the best correlation with the physicochemical indicators of melanoidins and semi-quantification results calculated by excitation-emission matrix fluorescence. In addition, the applicability of the proposed method was evaluated using multiple real melanoidins samples extracted from thermally pretreated OSW under different THP conditions and food-derived melanoidins as well, demonstrating its validity and advantages. This study is the first to provide a simple, effective, and accurate method for quantifying THP-origin melanoidins from different sources. Remarkably, as a specific and important application scenario, the proposed quantification method was employed to investigate the concentration dependence of melanoidins antioxidation in thermally pretreated OSW.

Comparison of characterization and composition of melanoidins from three different dried apple slices.

The composition of melanoidins in dried apple that affects quality remains unclear. The composition and structure of melanoidins in dried apple slices by hot air drying (HAAM), instant controlled pressure drop drying (DICAM), and vacuum freeze-drying (FDAM) were investigated. It showed that the melanoidins were highly heterogeneous mixtures with a light-yellow color and blue-green fluorescence, belonging to polysaccharide-type melanoidins. Specifically, HAAM had a large molecular weight (929.5 g/mol) and wide molecular weight distribution, with more double-bond conjugated systems. DICAM (610.9 g/mol), possessing the strongest fluorescence intensity, was mainly composed of compounds with fewer π-conjugated structures and more electron-donating groups. As a control, the low level of Maillard reaction in FDAM resulted in the formation of the smallest molecular weight (458.6 g/mol) with weak fluorescence intensity. Moreover, 10 compounds were tentatively identified in apple melanoidins. This study provides the foundation for the future functional preparation of apple melanoidins.

Effect of brewer's spent grain melanoidins on maillard reaction products during storage of whey protein model systems.

Maillard reaction readily takes place in dairy products because of the association between thermal treatments, extended storage and the matrix composition. Along with the impairment of protein digestion, the formation of glycation and α-dicarbonyl compounds is a concern for quality attributes of whey proteins when used as ingredients. In this paper, we outline the capacity of brewer's spent grain melanoidins in reducing the accumulation of α-dicarbonyl compounds, thus controlling the formation of dietary advanced glycation end-products in accelerated shelf life at 35 °C. Results revealed that brewer's spent grain melanoidins targeted methylglyoxal and glyoxal reactivity leading to the reduction of N-ε-carboxymethyllysine and methylglyoxal-hydroimidazolone up to 27 and 60%, respectively. We here describe that the presence of melanoidins is instrumental in limiting the undesired effects of α-dicarbonyl compounds on whey proteins.

Structure, spectral properties and antioxidant activity of melanoidins extracted from high temperature sterilized lotus rhizome juice.

Melanoidins are complex macromolecular compounds closely associated with the browning phenomenon in high-temperature sterilized lotus rhizome juice (HTSL). This study aimed to preliminarily investigate the structural properties of melanoidins extracted from HTSL. Results showed that the average molecular weight of HTSL melanoidins ranged from 1.48 to 41.40 kDa. Medium and high molecular weight melanoidins were the main contributors to the brown color of HTSL. Sugars, proteins, and phenolics were present in HTSL, among which sugar was the most abundant, with glucose being the predominant monosaccharide in acid degradation products of melanoidins. Through fluorescence and ultraviolet spectral analysis, we found that the melanoidins contained carboxyl and carbonyl compounds, as well as furan and pyran heterocyclic compounds. The infrared spectra and nuclear magnetic resonance spectra revealed a prominent sugar absorption peak, indicating that sugar was the main component of the melanoidins of HTSL. Furthermore, in vitro antioxidant experiments showed that the antioxidant activity of melanoidins was significantly positively correlated with phenolic compounds. Our results indicated that there were differences in the structural properties of melanoidins fractions with different molecular weights. MW-H fraction significantly impacted the color and antioxidant activity of HTSL.

Water-Soluble Coffee Melanoidins Inhibit Digestive Proteases.

Coffee is one of the most popular beverages around the world and its consumption contributes to the daily intake of dietary melanoidins. Despite the emerging physiological role of food melanoidins, their effect on digestive processes has not been studied so far. In this study, the activity of the gastrointestinal enzymes pepsin and trypsin was investigated in the presence of water-soluble coffee melanoidins. The gastric enzyme pepsin is only slightly affected, whereas the intestinal enzyme trypsin is severely inhibited by coffee melanoidins. The intestinal digestibility of casein was significantly inhibited by coffee melanoidins at a concentration achievable by regular coffee consumption. The inhibition of proteolytic enzymes by coffee melanoidins might decrease the nutritional value of dietary proteins.

Isolation, structural characterization and biological activity evaluation of melanoidins from thermally processed cocoa beans, carob kibbles and acorns as potential cytotoxic agents.

The aim of this study was to determine the chemical structure and biological activity of melanoidin fractions derived from cocoa beans, carob kibbles, and acorns roasted at different temperature-time conditions. The results showed that plant origin and roasting conditions had significant effects on the chemical composition, structural features, and morphology of melanoidins. All tested melanoidins exhibited significant antioxidant properties in three in vitro assays. In addition, they show significant in vitro anti-inflammatory activity by reducing lipoxygenase. The results from MTT assay showed that the all studied melanoidins had a cytotoxic effect against SW-480 cells in a dose- and time-dependent manner. Furthermore, the most pronounced activity was observed for acorn melanoidins. This is a unique finding, as the specific cytotoxic effect has not been reported for cocoa, carob and acorn melanoidins, and opens up a great opportunity to develop a potential novel cytotoxic agent against deadly colon cancer in the future.

Protective effects of melanoidins from black garlic on zearalenone-induced toxicity in zebrafish embryonic developmental model.

Zearalenone (ZEN), a ubiquitous mycotoxin that widely occurs in grain and foodstuff may induce serious toxic effects after accumulation in vivo. Melanoidins (MLDs) have shown multiple bio-functional properties such as antioxidant, anti-bacterial and prebiotic activities. Black garlic exhibits several advantages over fresh garlic related to health improvement. In this study, the alleviative effects of black garlic MLDs on ZEN-induced toxicity and the potential mechanisms were studied using zebrafish embryonic developmental model. The results showed that MLDs restored the ZEN-induced adverse influences on zebrafish embryonic development, including delay in hatching time, morphological abnormality and the impairment of nervous development. Further studies showed that MLDs significantly inhibited the ZEN-induced production of reactive oxygen species (ROS) and enhanced the intrinsic antioxidant ability by increasing the activities of superoxide dismutase (SOD), glutathione peroxidase (GSH-Px) and catalase (CAT) and the content of glutathione (GSH). In addition, co-exposure of MLDs significantly inhibited the ZEN-stimulated cellular apoptosis in zebrafish larvae through down-regulation of pro-apoptotic genes of bax, caspase-3 and caspase-9 and up-regulation of anti-apoptotic gene bcl-2. Moreover, MLDs inhibited the in vivo accumulation of ZEN in zebrafish larvae. To sum up, MLDs attenuated the ZEN-induced zebrafish embryonic developmental toxicity through suppression of the oxidative stress and intervention on mitochondria apoptosis pathway as well as inhibiting the absorption of ZEN in zebrafish embryos/larvae. The results suggest that black garlic MLDs have potential to be used as a functional ingredient against the adverse effects of exogenous toxins.

Role of Proteins in the Formation of Melanoidins during Coffee Roasting.

The objective of the study was to investigate structural changes in the protein-rich, high-molecular-weight fraction of coffee during roasting and their contribution to the melanoidin formation in the course of the Maillard reaction. For this purpose, high- and low-molecular-weight fractions of one raw and five coffee beans with an increased roasting degree were analyzed in terms of general (color, molecular weight, functionality, elemental composition) and specific parameters (amino acid composition, Maillard reaction products). It could be demonstrated that the high -molecular-weight fraction undergoes significant changes during roasting, where proteins appear to play an important role in melanoidin formation due to their diverse nucleophilic side chains. Modification of the amino acid side chains with known Maillard reaction products (MRPs) occurs in the early stages of roasting and decreases rapidly as color development progresses. The decrease suggests that MRPs are involved in further reactions and thus extend the functionality of the amino acid side chains, opening further possibilities for protein modification. Overall, the large number of reaction pathways leads to the formation of a well-mixed, continuous melanoidin spectrum covering a wide range of molecular masses. In this process, cross-linking and fragmentation reactions oppose each other, leading to an approximation of the molecular weight.

Characterization of melanoidins in thermal hydrolysis sludge and effects on dewatering performance.

Thermal hydrolysis pretreatment (THP) of sludge can form the refractory brown melanoidins due to the occurrence of the Maillard reaction, which adversely involves the subsequent sludge anaerobic digestion (AD) process. However, details of the generation pattern of melanoidins and how they affect the sludge dewaterability remain largely unknown. This work aims to determine an approach to characterize and quantify the melanoidins created by THP of sludge. On this basis, the effect of melanoidins on sludge dewatering performance was revealed by adding synthetic melanoidins to the mixed sludge. Experimental results showed that three-dimensional fluorescence-region integration (3DEEM-FRI) could effectively distinguish melanoidins from other organic substances and achieve semi-quantitative characterization in sludge. The melanoidins significantly deteriorated the sludge dewaterability, and the lowest solids content of the filter cake (TS) was only 17.78% at the addition of 480 mg (g TS)-1, which was a drop of about 20% compared to the control group. The mechanism investigations indicated that the internal structure of sludge becoming particularly complicated and the opportunities for molecules to collide with each other enlarged because of the contribution of melanoidins, resulting in the increment of the sludge apparent viscosity and consistency coefficient (k), a decline of the flow behavior index (n) and a weakening of flowability. Melanoidins could capture massive water molecules and carry negative charges with the decrease of sludge particle size and zeta potential value, which enhanced the electrostatic repulsion between sludge particles and abated the flocculation ability, thus further aggravating the sludge dewatering performance.

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.

Bioaccessibility and Genoprotective Effect of Melanoidins Obtained from Common and Soft Bread Crusts: Relationship between Melanoidins and Their Bioactivity.

Bread crust constitutes an important by-product of the bakery industry, and its utilization for the isolation of melanoidins to be used as a functional ingredient can enhance its added value and contribute to health. The aim of this study was to evaluate the bioaccessibility, bioactivity, and genoprotective effect of melanoidins derived from bread crust. Bioaccessibility was assessed in gastric, intestinal digestion, and colonic fermentation fractions. The results revealed a relationship between bioaccessible melanoidins and their type (common or soft bread). No cytotoxicity effects were observed for bioaccessible fractions, as assessed by MTT and RTA methods, and they did not affect the distribution of E-cadherin in Caco-2 cells, confirming their ability to maintain membrane integrity. Furthermore, our study demonstrated that the gastrointestinal and colonic fermentation fractions successfully transported across the intestinal barrier, without affecting cell permeability, and showed antioxidant activity on the basolateral side of the cell monolayer. Remarkably, both fractions displayed a significant genoprotective effect in Caco-2 cells. Our findings provide crucial insights into the relationship between the melanoidins and their bioactivity and genoprotective effect. These results demonstrated the potential of bioaccessible melanoidins as valuable bioactive compounds for the development of functional foods, without showing toxic effects on gastrointestinal cells.

Spent coffee grounds as feedstock for the production of biosurfactants and the improved recovery of melanoidins.

Spent coffee grounds (SCG) are wastes generated in high amounts worldwide. Their composition makes them a promising feedstock for biotechnological processes. Here we show that the production of the biosurfactant surfactin by submerged culture of a Bacillus subtilis strain growing on SCG is possible, reaching concentrations up to 8.8 mg/L when using SCG at 8.3 g/L in the medium. In addition, we report a synergy between the production of surfactin and the recovery of melanoidins, an added-value compound already present in SCG. More specifically, the concentration of melanoidins in the culture medium increased between 2.1 and 2.5 times thanks to the presence of the B. subtilis in the culture. Furthermore, we have observed a strong interaction between surfactin and melanoidin aggregates through dynamic light scattering measurements, and that both of them can be co-purified with an acid precipitation. We have also characterized the interfacial and antioxidant properties of the cell-free supernatant and surfactin extract, as well as the distribution of the congeners of the biosurfactant. Altogether, this work describes a promising approach to obtain biosurfactants and antioxidant molecules in a single operation, which can be used to design several new formulations of interest for bioremediation, amendment of soils, food and cosmetics.

Changes in antibacterial activity, colour, and hydrogen peroxide content of Western Australian Jarrah and Marri honeys after storage at different temperatures over time.

AIMS: This study aimed to evaluate the effects of storage and different temperatures on the antibacterial activity and physicochemical characteristics of several types of honey. METHODS AND RESULTS: Honeys stored for 16 weeks at 37 and 45°C showed significant declines in antibacterial activity determined by minimum inhibitory concentrations, the loss of hydrogen peroxide, decreases in honey pH, and increases in honey colour, with changes most pronounced at 45°C. In contrast, honeys stored for 16 weeks at ambient (∼22°C) and cold (4, -20, and -80°C) temperatures showed only minor changes. In a second set of 12 honeys stored for 16-32 months at ambient temperature and then 4°C, honeys showed minor changes in antibacterial activity, increases in colour, and decreases in pH. For a third set of 17 honeys stored for five years at ambient temperature, the honeys showed almost complete loss of hydrogen peroxide and were all significantly darker in colour, but showed varied changes in antibacterial activity. CONCLUSIONS: Heat was detrimental to the antibacterial activity of honeys, as was long-term storage at ambient temperatures for some honeys but not others.

Chemical and Biological Characterization of Green and Processed Coffee Beans from Coffea arabica Varieties.

Coffee is one of the most consumed beverages in the world; its production is based mainly on varieties of the Coffea arabica species. Mexico stands out for its specialty and organic coffee. In Guerrero, the production is done by small indigenous community cooperatives that market their product as raw material. Official Mexico Standards stipulate the requirements for its commercialization within the national territory. In this work, the physical, chemical, and biological characterizations of green, medium, and dark roasted beans from C. arabica varieties were carried out. Analysis by HPLC showed higher chlorogenic acid (55 mg/g) and caffeine (1.8 mg/g) contents in the green beans of the Bourbon and Oro Azteca varieties. The caffeine (3.88 mg/g) and melanoidin (97 and 29 mg/g) contents increased according to the level of roasting; a dissimilar effect was found in the chlorogenic acid content (14.5 mg/g). The adequate nutritional content and the sensory evaluation allowed the classification of dark-roasted coffee as premium coffee (84.25 points) and medium-roasted coffee as specialty coffee (86.25 points). The roasted coffees presented antioxidant activity without cytotoxic effects; the presence of CGA and caffeine supports the beneficial effects of drinking coffee. The results obtained will serve as a basis for making decisions on improvements to the coffees analyzed.

Mechanisms of action of coffee bioactive compounds - a key to unveil the coffee paradox.

The knowledge of the relationship between the chemical structure of food components with their mechanisms of action is crucial for the understanding of diet health benefits. This review relates the chemical variability present in coffee beverages with the mechanisms involved in key physiological events, supporting coffee as a polyvalent functional food. Coffee intake has been related with several health-promoting properties such as neuroprotective (caffeine, chlorogenic acids and melanoidins), anti-inflammatory (caffeine, chlorogenic acids, melanoidins, diterpenes), microbiota modulation (polysaccharides, melanoidins, chlorogenic acids), immunostimulatory (polysaccharides), antidiabetic (trigonelline, chlorogenic acids), antihypertensive (chlorogenic acids) and hypocholesterolemic (polysaccharides, chlorogenic acids, lipids). Nevertheless, caffeine and diterpenes are coffee components with ambivalent effects on health. Additionally, a large range of potentially harmful compounds, including acrylamide, hydroxymethylfurfural, furan, and advanced glycation end products, are formed during the roasting of coffee and are present in the beverages. However, coffee beverages are part of the daily human dietary healthy habits, configuring a coffee paradox.

The multi-targeted bioactive features of coffee compounds reinforce coffee as a functional food beverage.Polysaccharides and melanoidins positively modulate gut microbiota.Caffeine and phenolics are neuroprotective, anti-inflammatory, antidiabetic and antihypertensive.The balance between potential health and harmful compounds configures a coffee paradox.Harmful compounds are present in trace levels in coffee, not conferring toxicity.