Synergistic effects of superfine grinding and high hydrostatic pressure on the contents, distribution, digestive behaviors and antioxidant activities of polyphenols in barley leaves.

Barley leaves (BLs) naturally contained abundant phenolics, most of which are hardly completely released from food matrix during gastrointestinal digestion. Superfine grinding (SFG) and high hydrostatic pressure (HHP) are generally used to treat the functional plants due to their effectiveness to cell wall-breaking and improvement of nutraceutical bioavailability. Thus, this study investigated the synergistic effects of SFG and HHP (100, 300, 500 MPa/20 min) on the bioaccessbility of typical phenolics in BLs during the simulated in-vitro digestion. The results demonstrated that the highest bioaccessbility (40.98%) was found in the ultrafine sample with HHP at 500 MPa. CLSM and SEM confirmed SFG led to microstructurally rapture of BLs. Moreover, the recovery index of ABTS radical scavenging activity and FRAP of HHP-treated ultrafine and fine BLs samples maximumly increased by 53.62% and 9.61%, respectively. This study is expecting to provide the theoretical basis to improve the consumer acceptance of BLs.

Effects of Chlorogenic Acid on Lowering IgE-Binding Capacity of Soybean 7S: Comparison between Covalent and Noncovalent Interaction.

Allergenicity of soybean 7S protein (7S) troubles many people around the world. However, many processing methods for lowering allergenicity is invalid. Interaction of 7S with phenolic acids, such as chlorogenic acid (CHA), to structurally modify 7S may lower the allergenicity. Hence, the effects of covalent (C-I, periodate oxidation method) and noncovalent interactions (NC-I) of 7S with CHA in different concentrations (0.3, 0.5, and 1.0 mM) on lowering 7S allergenicity were investigated in this study. The results demonstrated that C-I led to higher binding efficiency (C-0.3:28.51 ± 2.13%) than NC-I (N-0.3:22.66 ± 1.75%). The C-I decreased the α-helix content (C-1:21.06%), while the NC-I increased the random coil content (N-1:24.39%). The covalent 7S-CHA complexes of different concentrations had lower IgE binding capacity (C-0.3:37.38 ± 0.61; C-0.5:34.89 ± 0.80; C-1:35.69 ± 0.61%) compared with that of natural 7S (100%), while the noncovalent 7S-CHA complexes showed concentration-dependent inhibition of IgE binding capacity (N-0.3:57.89 ± 1.23; N-0.5:46.91 ± 1.57; N-1:40.79 ± 0.22%). Both interactions produced binding to known linear epitopes. This study provides the theoretical basis for the CHA application in soybean products to lower soybean allergenicity.

High hydrostatic pressure induced gastrointestinal digestion behaviors of quercetin-loaded casein delivery systems under different calcium concentration.

Casein micelle has a structure of outer hydrophilicity and inner hydrophobicity, its typical digestion characteristic is gastric coagulation. Based on calcium content as the key factor to control this process, high hydrostatic pressure (HHP) was firstly used to modify the micelle structure by mediating the tight connection between casein molecules themselves and with colloidal calcium, then the quercetin-loaded delivery systems were prepared. And in order to investigate the effect of exogenous calcium, calcium chloride was added for digestion. The results indicated that HHP broke the limitation of casein micelles as delivery carriers for hydrophobic components and increased the EE from 51.18 ± 3.07 % to 76.17 ± 3.41 %. During gastric digestion, higher pressure and exogenous calcium synergistically increased the clotting ability and inhibited the release of quercetin. In the small intestine, curds decomposed more slowly under higher pressure and calcium concentration, so the degradation of quercetin was effectively inhibited.

The aggregation of casein micelles induced by Ca2+ during in vitro digestion: effects on the release of loaded anthocyanins.

Colloidal calcium phosphate (CCP) confers a modifiable structure to micellar casein (MC), which endows it with potential advantages as a delivery carrier. However, it is difficult to achieve multipattern release of the core material in the intestine with MC as a single wall. In this study, we prepared an anthocyanin-casein-based delivery system utilizing MC with different freezing degrees as the wall material with the objective of achieving the controlled release of anthocyanin as the model core in the intestine. The results showed that freezing could significantly reduce the CCP level up to 50%. Static in vitro simulated digestion with the addition of exogenous Ca2+ showed that the designed delivery system exhibited low anthocyanin release (15%-35%) in the gastric tract. The pattern of release in the intestine depended on the CCP dissociation degree. High and low dissociation degrees corresponded to slow release (from 15% to 65% within 2 h) and burst release (from 35% to 90% within 5 min), respectively. WAXS/SAXS analysis revealed that exogenous serum Ca2+ inherent in simulated gastric fluid and endogenous serum Ca2+ induced by CCP dissociation was synergistically involved in the reconstitution of CCP-mediated nanoclusters and large aggregates. The freezing degree of MC determined the endogenous serum Ca2+ level, which influenced the gastric aggregation behavior of wall MC and ultimately led to a fairly different gastrointestinal release behavior of anthocyanins.

Gastric aggregation of micellar casein powders induced by high hydrostatic pressure: Effect of serum Ca2+ level.

Micellar casein (MC) has a unique gastric colloidal behavior in response to Ca2+ cross-linking, and its aggregation properties are closely related to pepsin and gastric acid. In this study, MC with different levels of colloidal calcium phosphate (CCP) was obtained by high hydrostatic pressure (HHP) at different pressures, followed by spray drying to obtain the powders. Different amounts of calcium chloride (exogenous Ca2+) were added to MC powders prior to in vitro simulated digestion to investigate the effect of exogenous serum Ca2+ levels on the aggregation behavior and the structure change of curds generated in gastric tract. The results revealed that HHP induced the emergence of more Ca2+-binding sites, thus Ca2+ was more likely to bind to MC matrix with low CCP levels. Meanwhile, high serum Ca2+ level provided more opportunities to form aggregates. The Highest pressure (500 MPa) with the highest Ca2+ level (5 mM) caused the lowest solubility aggregates, which were only 30% at the end of gastric digestion (120 min), half of the control sample (0 MPa with 0.15 mM Ca2+). The results of wide-angle X-ray scattering / small-angle X-ray scattering suggested that both pepsin and gastric acid-induced aggregation via Ca2+ as a bridge. For pepsin, Ca2+ cross-linked between para-κ-casein; For gastric acid, Ca2+ recombined phosphorylation sites and caused cross-linking of casein subunits.

Toward the bioactive potential of myricitrin in food production: state-of-the-art green extraction and trends in biosynthesis.

Myricitrin is a member of flavonols, natural phenolic compounds extracted from plant resources. It has gained great attention for various biological activities, such as anti-inflammatory, anti-cancer, anti-diabetic, as well as cardio-/neuro-/hepatoprotective activities. These effects have been demonstrated in both in vitro and in vivo models, making myricitrin a favorable candidate for the exploitation of novel functional foods with potential protective or preventive effects against diseases. This review summarized the health benefits of myricitrin and attempted to uncover its action mechanism, expecting to provide a theoretical basis for their application. Despite enormous bioactive potential of myricitrin, low production, high cost, and environmental damage caused by extracting it from plant resources greatly constrain its practical application. Fortunately, innovative, green, and sustainable extraction techniques are emerging to extract myricitrin, which function as alternatives to conventional techniques. Additionally, biosynthesis based on synthetic biology plays an essential role in industrial-scale manufacturing, which has not been reported for myricitrin exclusively. The construction of microbial cell factories is absolutely an appealing and competitive option to produce myricitrin in large-scale manufacturing. Consequently, state-of-the-art green extraction techniques and trends in biosynthesis were reviewed and discussed to endow an innovative perspective for the large-scale production of myricitrin.

From polyphenol to o-quinone: Occurrence, significance, and intervention strategies in foods and health implications.

Polyphenol oxidation is a chemical process impairing food freshness and other desirable qualities, which has become a serious problem in fruit and vegetable processing industry. It is crucial to understand the mechanisms involved in these detrimental alterations. o-Quinones are primarily generated by polyphenols with di/tri-phenolic groups through enzymatic oxidation and/or auto-oxidation. They are highly reactive species, which not only readily suffer the attack by nucleophiles but also powerfully oxidize other molecules presenting lower redox potentials via electron transfer reactions. These reactions and subsequent complicated reactions are capable of initiating quality losses in foods, such as browning, aroma loss, and nutritional decline. To attenuate these adverse influences, a variety of technologies have emerged to restrain polyphenol oxidation via governing different factors, especially polyphenol oxidases and oxygen. Despite tremendous efforts devoted, to date, the loss of food quality caused by quinones has remained a great challenge in the food processing industry. Furthermore, o-quinones are responsible for the chemopreventive effects and/or toxicity of the parent catechols on human health, the mechanisms by which are quite complex. Herein, this review focuses on the generation and reactivity of o-quinones, attempting to clarify mechanisms involved in the quality deterioration of foods and health implications for humans. Potential innovative inhibitors and technologies are also presented to intervene in o-quinone formation and subsequent reactions. In future, the feasibility of these inhibitory strategies should be evaluated, and further exploration on biological targets of o-quinones is of great necessity.

Combination of α-lactalbumin and gum arabic for microencapsulation of L-menthol: The effects on flavor release during storage and rehydration.

L-menthol-containing food products generally show the flavor loss during storage due to their high volatility. The hydrophobicity of L-menthol also causes the inadequate flavor release during rehydration. In this study, the stability of L-menthol was enhanced by microencapsulation and the effect of different powder drying techniques was also investigated. The highest efficiency (76.58-78.66 %) and loading content (18.58-28.35 mg/g) of encapsulations were obtained by using a mass ratio of 2:1(α-LA: GA). Then they were dried by non-thermal spray freeze drying (SFD) technique compared to spray drying (SD) and freeze-drying (FD) process. The SFD particles were shown to be spherical and porous with the highest porosity (86.82 %). α-LA/GA based microparticles with spherical shapes were demonstrated to largely enhance flavor retention during high humidity storage. In addition, the porous structures of SFD powders could cause rapid rehydration in liquid models, and the release behaviors of loaded L-menthol followed the Fickian diffusion. Consequently, the SFD technique shows great potential to produce microparticles by regulating the release behaviors of L-menthol during storage and rehydration.

Targeted delivery of nutraceuticals derived from food for the treatment of obesity and its related complications.

Nutraceuticals which are abundant in foods have attracted much attention due to their bioactive activities of anti-obesity, anti-hyperlipidemia and anti-atherosclerosis. Unfortunately, the poor bioavailability severely undermines their envisioned benefits. Therefore, there is an urgent need to develop suitable delivery systems to promote the benefits of their biological activity. Targeted drug delivery system (TDDS) is a novel drug delivery system that can selectively concentrate drugs on targets in the body, improve the bioavailability of agents and reduce side effects. This emerging drug delivery system provides a new strategy for the treatment of obesity with nutraceuticals and would be a promising alternative to be widely used in the food field. This review summarizes the recent studies on the application in the targeted delivery of nutraceuticals for treating obesity and its related complications, especially the available receptors and their corresponding ligands for TDDS and the evaluation methods of the targeting ability.

The effect of Maillard reaction on the lactose crystallization and flavor release in lactose/WPI/inulin encapsulation.

The crystallization of lactose usually causes the structural collapse and core material escape of flavor encapsulations. The objective of this study was to investigate the effects of different grafting degrees of WPI-inulin Maillard reaction products on the lactose crystallization and the subsequent release behaviors. Ethyl acetate was chosen as the model volatile flavor and the encapsulations were prepared by freeze-drying. The results found that the encapsulation efficiency was significantly increased from 30% to over 80% by using MRPs as wall materials. Those microparticles showed the greater flavor retention and lower moisture adsorption. In addition, the encapsulations produced by the proper Maillard reaction times (e.g., 48 h and 72 h) could effectively delay the lactose crystallization and thus improve the structural stability of the matrix. This innovation finding aims to use the Maillard reaction to control the crystallization behaviors and enhance the usefulness of high-lactose containing products in encapsulation systems.

Investigation of the Quinone-quinone and Quinone-catechol products using 13C labeling, UPLC-Q-TOF/MS and UPLC-Q-Exactive Orbitrap/MS.

Quinones are highly reactive oxidants and play an essential role in inducing quality deterioration of fruit and vegetable products. Here, a novel stable isotope-labeling approach in combination with high-resolution tandem mass spectrometry UPLC-Q-TOF/MS and UPLC-Q-Exactive Orbitrap/MS, was successfully applied in tracking quinone reaction pathways in both real wines and model reaction systems. Unexpectedly, the binding products of quinone-quinone and quinone-catechol that are not derived from either nucleophilic reaction or redox reaction were discovered and showed the significant high peak area.Self-coupling reactions of semiquinone radicals might provide a possible interpretation for the formation of quinone-quinone products, and a charge transfer reaction coupled with a complementary donor-acceptor interaction is feasibly responsible for the products with a quinone-catechol structure. These findings endow a new perspective for quinone metabolic pathway in foods.

A method on acrylamide elimination: Comparing and tracing reaction pathways of acrylamide and catechin (catechin quinone) using UHPLC-Q-exactive orbitrap mass spectrometry.

Acrylamide (AA) elimination is significant in thermal-processing foods that rich in carbohydrate and asparagine. Here, catechin (CAT) and its quinone were utilized to investigate and evaluate the reaction rate of AA's characteristics (electrophilicity, oxidizing ability, and nucleophilicity) and trace the reaction pathways to eliminate AA in model system at 25 °C and 150 °C. It is revealed that AA prefers nucleophilic additions with quinone (kAA-CATQ = 1.1E-2 min-1 > kAA-CAT = 3.1E-3 min-1). It is prone to react with the B ring of CAT (kAA-4MC = 1.4E-3 min-1) via the redox reaction, rather than the A ring (kAA-PHL = 1.0E-4 min-1) through the electrophilic reaction. For the investigation of unknown products resulting from the above reactions, a process incorporating mechanism and tentative product speculation was implemented. Thirteen products were partially detected based on the extracted ion chromatography and MS spectrum from UHPLC-Q-Exactive Orbitrap Mass Spectrometry. These results provide a new perspective to eliminate AA in thermal-processing foods.

Polyphenol mediated non-enzymatic browning and its inhibition in apple juice.

Non-enzymatic browning is a severe problem in juice industry. Here, polyphenol mediated non-enzymatic browning and its inhibition in apple juice were investigated. Epicatechin (R = -0.83), catechin (CAT, R = -0.79), chlorogenic acid (CGA, R = 0.65) and caffeic acid (CAF, R = 0.65) were strongly correlated with browning. CAT and chlorogenic acid quinone (CGAQ) decreased during storage with the fastest CAT degradation rate (kCGA-enriched = 1.97 × 10-3 mg·L-1·h-1 and kCAT-enriched = 2.09 × 10-3 mg·L-1·h-1) at the initial stage, but CGA and catechin quinone (CATQ) hardly changed. It was possible that CGAQ oxidized CAT at initial stage, leading to the generation of CATQ but less browning. Then the formed CATQ reacted with CAT through the complex reactions, leading to the accumulation of yellow polymers, which might explain why browning increased faster during the secondary and tertiary stages. In addition, glutathione could effectively inhibit browning compared to ascorbic acid and oxygen blocking methods.

Quinone-mediated non-enzymatic browning in model systems during long-term storage.

Non-enzymatic browning induced by polyphenol oxidation is an essential problem during the processing and storage of fruit and vegetable products. Here, the non-enzymatic browning mechanism between catechin (CAT), chlorogenic acid (CQA) and their corresponding quinones was investigated in model systems during the 32-d long-term storage. The results showed that CAT and catechin quinone (CATQ), which contains both A ring with a resorcinol structure and an o-diphenol B ring, are important precursors for browning, while chlorogenic acid (CQA) has a minor effect on browning. Chlorogenic acid quinone (CQAQ)-mediated CAT oxidation (kCAT-degradation = 0.0458 mol·L-1·d-1) was faster than CAT autoxidation (kCAT-degradation = 0.0006 mol·L-1·d-1), and there was no significant difference between CQAQ-mediated CAT oxidation and CATQ-mediated CQA oxidation. These indicate that CQAQ oxidizes CAT to CATQ quickly, and CATQ reacts with CAT subsequently through complex reactions to produce brown pigments in model systems during long-term storage.

Non-enzymatic browning induced by chlorogenic acid quinone mediated catechin oxidation.

Non-enzymatic oxidation has become a significant issue in the juice industry, inducing browning, flavor deterioration, and nutrient degradation, where catechin oxidation plays a vital role. Here, a novel chlorogenic acid quinone-mediated catechin oxidation was compared with the autoxidation pathway, where the former reaction was significantly faster (0.1326 L·mol-1·min-1) than the autoxidation rate of 4.25E-5 L·mol-1·min-1. The significance of the chlorogenic acid quinone-mediated catechin oxidation was further confirmed in the apple juice showing that chlorogenic acid quinone decreased faster in catechin enriched juice than in chlorogenic acid enriched juice. In addition, chlorogenic acid and catechin quinone hardly changed, but catechin and chlorogenic acid quinone kept decreasing during the browning process. These suggested that chlorogenic acid quinone mediated oxidation dominated the non-enzymatic browning in juice and might act as a self-perpetuating oxidizer, catalyzing the formation of catechin quinone constantly.

Impact of high hydrostatic pressure on the micellar structures and physicochemical stability of casein nanoemulsion loading quercetin.

Natural casein is a highly structured protein and the characteristic of self-assembly makes the formation of micelles, thus negatively limiting the applications. High hydrostatic pressure (HHP), as a novel non-thermal process, can modify the structures of protein and improve the related functionalities. In this study, micellar casein was subjected to HHP treatment from 100 to 500 MPa, which then loaded quercetin and formed the nanoemulsion. The thermal, pH, ions and physical stability of nanoemulsion were comprehensively investigated. The results showed 300-500 MPa could effectively disintegrate the micellar structures of natural casein by dissociating colloidal calcium phosphate, which significantly improved the emulsifying activity and encapsulation efficiency. However, 500 MPa caused the nanoemulsion loading most quercetin and subsequently showed the better physical and ions stability in comparison with control and 100-400 MPa. Therefore, HHP is expected to modify the high-order structure of casein, which becomes the ideal nano-vehicles for hydrophobic bioactive substances.

Glycated α-lactalbumin based micelles for quercetin delivery: Physicochemical stability and fate of simulated digestion.

Glycated protein is a kind of promising material that can improve the bioavailability of bioactive compounds and achieve sustained release under digestion. In this study, the α-lactalbumin (ALA)-dextran conjugates synthesized by Maillard reaction were fabricated to load and protect quercetin. Quercetin-loaded micelles stabilized by the ALA-dextran conjugates 1:4 showed the smallest size (428.57 ± 5.64 nm) with highest encapsulation efficiency (94.38% ± 0.50%) of quercetin. Compared to ALA/dextran mixture complex, the conjugates-based micelles had better pH, ionic strength and photothermal stability. Furthermore, the micelles composed of the conjugates 1:2 and 1:4 showed the best controlled release effect during the simulated digestion, releasing 62.41% and 66.15% of quercetin from the total encapsulated contents, respectively, which was mainly related to the resistance of glycated ALA to the enzymes. The findings indicated that ALA-dextran conjugates could be effectively designed for the ideal delivery system of hydrophobic bioactive compounds in food industry.

A novel method combining stable isotopic labeling and high-resolution mass spectrometry to trace the quinone reaction products in wines.

Quinone formation is a key initial step of wine oxidation. Nucleophiles sacrificially react with quinones to sustain color and aroma, but due to the complexity of wine, determining the identity of the constitutive nucleophile has been challenging. Here we apply a novel stable-isotope labelling approach combined with high-resolution mass spectrometry, using 13C6-labelled ortho-quinone. This allows for the specific detection of quinone reaction products with M and M + 6x peak feature-pairs in real wines. Analysis using MetExtract II successfully identified 225 quinone reaction suspects in negative mode in Sauvignon blanc wine, and 120 in Cabernet Sauvignon. Ten quinone reaction products with the most abundant peak areas were tentatively identified using a mass/structure workflow. It appears that sulfides largely quench quinones in white wines, whereas flavonoids are the dominant reactants in red wines. The latter result demonstrates how skin/seed extraction preserves red wine.

The in-vitro digestion behaviors of micellar casein acting as wall materials in spray-dried microparticles: The relationships between colloidal calcium phosphate and the release of loaded blueberry anthocyanins.

Micellar casein (MC) is a natural carrier for delivering various bioactive substances, and its gastrointestinal digestion behavior has an important impact on the loaded materials. Studies have shown that the digestion behavior of MC is dominated by colloidal calcium phosphate (CCP) in micelle structure. In this paper, The MCs with different CCP levels were used as the carriers to prepare spray-dried microparticles loaded with blueberry anthocyanins (ACNs), then the release of ACNs during digestion was investigated. The results found that the microparticles with less CCP showed the faster dissolution and quicker protein hydrolysis, which caused weaker curd ability. The coagulation was believed as the critical issue to influence the digestion and release behaviors. Therefore, lowering CCP resulted in significantly more ACNs released. This study demonstrated the possibility of using CCP levels to control MC digestion behaviors, which can further determine the release of loaded bioactive substances in casein-based delivery systems.