Polymeric Proanthocyanidins Research Articles

Evaluation of the antioxidant activity and prebiotic properties of mangosteen peel proanthocyanidin extracts through simulated in vitro digestion and colonic fermentation

The biological activity of mangosteen peel proanthocyanidin extracts is related to digestive properties and colonic metabolism. Therefore, the study's aim was to investigate the dynamics of proanthocyanidin extracts during in vitro digestion and colonic fermentation, their protective effects against oxidative damage in PEC-J2 cells, and their interactions with the intestinal flora. The results showed that epicatechin and proanthocyanidin B2 were the most abundant in proanthocyanidin. In addition, the catechin was increased by 27.7 ± 0.2 μg/mL. The total phenol content, total flavonoid content, and proanthocyanidin content of mangosteen peel were reduced by 32.36%, 90.63%, and 78.06%, respectively. However, the antioxidant capacity was increased by two-fold, protecting against oxidative damage in cells. Proanthocyanidin polymers that are not digested by the gastrointestinal tract go to the colon, where they are metabolized by microorganisms to produce short-chain fatty acids (SCFAs). Proanthocyanidin extracts modulated the microbial flora structure: the relative abundance of Phascolarctobacterium, Roseburia, Faecalibacterium, Coprococcu, and Clostridium sensu stricto all increased significantly. The ratio of Bacteroides to Firmicutes increased, and Bifidobacterium grew and multiplied. This study improves the utilization of mangosteen peel and provides a theoretical basis for the scientific evaluation of the antioxidant activity and gut microbiota modulation of mangosteen peel.

Comprehensive Study of Sustainable Pressurized Liquid Extractions to Obtain Bioavailable Antioxidant Phenolic Compounds from Grape Seed By-Products

Few investigations have been conducted to evaluate pressurized liquid extraction (PLE) technology as a sustainable method for the recovery of phenolic compounds of grape seed by-products. In this study, PLE combined with an experimental design was evaluated for optimizing the sustainable extraction of phenolic compounds from grape seed by-products. The solvent ethanol content (X1, 0–100%), temperature (X2, 20–100 °C) and time (X3, 1–11 min) were studied as independent experimental factors. Yield, TPC, antioxidant activity and phenolic composition were analyzed as optimized dependent variables. Two optimal extraction conditions at different temperatures (20 °C and 100 °C) were found, but thermal degradations at 100 °C allowed for selecting the optimal condition as 75% ethanol, 11 min and 20 °C. The optimal extracts showed high phenolic content (TPC = 350.80 ± 3.97 mg GAE/g extract) and antioxidant activity (ABTS, 9.31 ± 0.33 mmol Trolox/g extract), mainly composed of polymeric and mono-oligomeric flavan-3-ols. The digestion process reduced the TPC and antioxidant activity due to the low bioaccessibility of the flavan-3-ols, mainly as catechin, epicatechin and polymeric proanthocyanidin losses during the digestion process. However, increases in the antioxidant activity of the basolateral side (DDPH, 0.061 ± 0.000 mmol Trolox/g extract) were determined after in vitro transepithelial transport, which is a consequence of bioavailable catechin and epicatechin and reduced amounts of dimer B2, dimer B1, epicatechin gallate and gallic acid. Consequently, PLE combined with hydroalcoholic solvents at a low temperature resulted in a valuable methodology to obtain sustainable extracts from grape seed by-products (contributing to the circular economy), containing bioavailable phenolic compounds, which are able to increase the antioxidant status.

Polyphenols and Phenolic Glucosides in Antibacterial Twig Extracts of Naturally Occurring Salix myrsinifolia (Salisb.), S. phylicifolia (L.) and S. starkeana (Willd.) and the Cultivated Hybrid S. x pendulina (Wender.).

(1) Background: Salix species occurring in Finland have not been well studied for their antimicrobial potential, despite their frequent use for lung and stomach problems in traditional medicine. Thus, twig extracts of three species of Salix that are found naturally in Finland and one cultivated species were screened for their antimicrobial properties against human pathogenic bacteria. S. starkeana and S. x pendulina were screened for antibacterial effects for the first time. (2) Methods: An agar diffusion and a microplate method were used for the screenings. Time-kill effects were measured using a plate-count and a microplate method. A DPPH-method using a qualitative TLC-analysis was used to detect antioxidant compounds in antimicrobial extracts. Metabolites from a S. myrsinifolia extract showing good antibacterial effects were identified using UPLC/QTOF-MS. (3) Results: A methanol extract of S. starkeana was particularly active against B. cereus (MIC 625 µg/mL), and a methanol extract of S. myrsinifolia showed good activity against S. aureus and B. cereus (MIC 1250 µg/mL) and showed bactericidal effects during a 24 h incubation of B. cereus. Moreover, a decoction of S. myrsinifolia resulted in good growth inhibition against P. aeruginosa. Our UPLC/QTOF-MS results indicated that proanthocyanidins (PAs), and especially the dimer procyanidin B1 (m/z 577) and other procyanidin derivatives, including highly polymerized proanthocyanidins, were abundant in S. myrsinifolia methanol extracts. Procyanidin B1 and its monomer catechin, as well as taxifolin and p-hydroxycinnamic acid, all present in S. myrsinifolia twigs, effectively inhibited B. cereus (MIC 250 µg/mL). (4) Conclusions: This study indicates that Finnish Salix species contain an abundance of antibacterial condensed tannins, phenolic acids and other polyphenols that deserve further research for the antibacterial mechanisms of action.

Effect of Chinese quince proanthocyanidins on the inhibition of heterocyclic amines and quality of fried chicken meatballs and tofu.

Heterocyclic amines (HCAs) have potential carcinogenic and mutagenic activity and are generated in cooked protein-rich foods. Adding proanthocyanidins (PAs) to these foods before frying is an effective way to reduce HCAs. In this study, polymeric PAs (PPA) and ultrasound-assisted acid-catalyzed/catechin nucleophilic depolymerized PAs (UAPA, a type of oligomeric PA) were prepared from Chinese quince fruits (CQF). Different levels of PPA and UAPA (0.05%, 0.1%, and 0.15%) were added to chicken meatballs and tofu; then these foods were fried, and the content of HCAs in them after frying was investigated. The results showed that PPA and, particularly, UAPA significantly inhibited the formation of HCAs in fried meatballs and tofu, and this inhibition was dose-dependent. The inhibition of HCAs by both PPA and UAPA was stronger in the chicken meatballs than in fried tofu. The level of total HCAs was significantly reduced by 57.84% (from 11.93 to 5.03ng/g) after treatment of meatballs with 0.15% UAPA, with inhibition rates of 78.94%, 50.37%, and 17.81% for norharman, harman, and 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), respectively. Of note, there was a negative correlation between water, lipid, protein, creatine, and glucose content and HCA content in the crust, interior, and whole (crust-plus-interior) measurements of all fried samples. Interestingly, PPA and UAPA were found more effective in inhibiting HCAs in the exterior crust than in the interior of the fried chicken meatballs. These results provide evidence that further studies on the reduction of the formation of harmful HCAs in fried foods by adding CQF PAs could be valuable to the fried food industry. PRACTICAL APPLICATION: Chinese quince proanthocyanidins treatments significantly inhibited the generation of heterocyclic amines (HCAs) in chicken meatballs and tofu when deep-fried. These results suggest that Chinese quince proanthocyanidins can be used as natural food additive for reducing HCAs in fried foods, laying the foundation for using Chinese quince fruit proanthocyanidins for HCA inhibition in the food industry.

Evaluation of biological activity and prebiotic properties of proanthocyanidins with different degrees of polymerization through simulated digestion and in vitro fermentation by human fecal microbiota

The bioactive activity of proanthocyanidins (PAs) is closely associated with their degree of polymerization (DP), however, the effects of PAs with different DP on digestion and gut microbiota have remained unclear. To investigate this, we conducted in vitro simulated digestion and colonic fermentation studies on samples of PAs with different DP. The results showed that PAs was influenced by both protein precipitation and enzymolysis, resulting in a decrease in functional activity. PAs with a high DP were more sensitive to the gastrointestinal environment. The significant clustering trend in colonic fermentation verified the reliability of multivariate statistical techniques for screening samples with distinct functional differences. The gut microbiota analysis showed that oligomeric PAs had a stronger promoting effect on beneficial bacteria, while high polymeric PAs had a greater inhibitory effect on harmful bacteria. This study offers new insights into the biological activity and microbiological mechanisms of PAs with different DP.

Proanthocyanidins biotransformed by Saccharomyces cerevisiae prevent the pathogenesis of steatosis and progression to steatohepatitis in vitro

Oligomeric and polymeric proanthocyanidins (PAC) were biotransformed with Saccharomyces cerevisiae to improve bioavailability and bioactivity. Biotransformation significantly increased the bioavailability of PAC in vitro and generated many metabolites, most notably, 3-aminophenol, pyrogallol, phloroglucinol, 4-hydroxyphenylacetamide, 2,4-dihydroxy-6-methylbenzaldehyde, 2,4,6-trihydroxyacetophenone, and 2-hydroxyphenylacetic, 3-aminosalicylic, dihydroxybenzoic, 2-hydroxycinnamic, 3-phenyllactic, and gallic acids. The bioactivity of biotransformed (BT)-PAC and non-BT-PAC was compared using palmitic acid (PA)-induced steatosis/nonalcoholic fatty liver disease (NAFLD) and PA + bacterial lipopolysaccharide-induced nonalcoholic steatohepatitis (NASH) models of AML12 hepatocytes. BT-PAC reduced the PA-induced cellular oxidative stress and lipid accumulation by activating the nuclear factor erythroid 2-related factor 2 (Nrf2)/antioxidant response element (ARE) pathway and modulating key regulators of cellular lipid metabolism. BT-PAC reduced the progression of steatosis to NASH in vitro by suppressing toll-like receptor 4-mediated cellular inflammation. Non-BT-PAC was less potent in the reduction of cellular lipotoxicity and inflammation. S. cerevisiae-mediated biotransformation significantly enhances the bioavailability of PAC and the bioactivity against steatosis and NASH.

Presence of Highly Polymerized Proanthocyanidins in Pulp and Peel of Unripe Bananas (Musa Sp.) from the French West Indies

Presence of Highly Polymerized Proanthocyanidins in Pulp and Peel of Unripe Bananas (Musa Sp.) from the French West Indies

Bassia longifolia (= Madhuca longifolia): Isolation of flavan-3-ols and their contribution to the antibacterial and antidiabetic activity in vitro

Bassia longifoliaKOENIG (= Madhuca longifolia (L.) is an evergreen tree that is widely distributed throughout Nepal, India, and Sri Lanka. The bark has various traditional uses: as a paste in the treatment of cuts and wounds or internally as a decoction that is given to diabetic patients. Chemical-analytical and pharmacological investigations regarding the bark are not sufficiently available. We focused on the isolation of flavan-3-ols from the methanolic extract and their contribution to the described traditional uses in wound healing and diabetes treatment. Therefore, an antibacterial assay and an α-glucosidase assay were performed. The isolation process was performed by a combination of Sephadex®-, MCI®-Gel-, and RP-18 chromatography. The structures of the isolated compounds were elucidated by 1H- and 13C-NMR-spectroscopy including COSY, ROESY, HSQC, and HMBC methods. Optical characterization was performed by polarimetry and circular dichroism. Two monomeric, seven dimeric, six trimeric, and one tetrameric flavan-3-ols were found including one dimer and three trimers with rare epiafzelechin units. Two compounds were isolated for the first time. A fraction containing higher oligomeric and polymeric proanthocyanidins (PAs) was examined by 13C NMR spectroscopy and revealed an average degree of polymerization of 8–9. PA with cis-configurated subunits predominated at 90 % and the presence of further monohydroxylated flavan-3-ols was revealed. Minimal inhibitory concentrations (MICs) were investigated by the serial microdilution broth assay with Staphylococcus aureus. The bacterial suspension was inoculated on agar plates for determining the MICs. The α-glucosidase assay was performed in 96 well plates with α-glucosidase from Bacillus stearothermophilus. For the detection of enzyme inhibition, p-nitrophenyl-α-d-glucopyranoside was used as a substrate and after incubation absorbance was measured at 405 nm. Antibacterial effects were only found for fractions enriched with PAs or containing higher oligomeric and polymeric flavan-3-ols. All tested substances showed high α-glucosidase inhibition. Whereby 4β→8 conjugated dimers and the monomers showed the lowest inhibition, procyanidin (PC) B5 as 4β→6 conjugated and cinnamtannin A2 as tetrameric flavan-3-ol showed the highest. PAs with epiafzelechin units are rarely found in nature but their reoccurring appearance in B. longifolia could be characteristic of this plant. For its traditional uses, the antibacterial activity of the PA-enriched fractions could contribute to the wound healing process when applied to the injured skin. Moreover, all tested substances and fractions showed α-glucosidase inhibition, which could also explain the use of a decoction in the treatment of diabetes. In conclusion, pharmacological investigations could provide scientific evidence for traditional uses of B. longifolia.

Outstanding adsorption capacity of iron oxide synthesized with extract of açaí berry residue: kinetic, isotherm, and thermodynamic study for dye removal.

Contamination of water by toxic dyes is a serious environmental problem. Adsorbents prepared by an environmentally safe route have stood out for application in pollutant removal. Herein, iron oxide-based nanomaterial composed of Fe(III)-OOH and Fe(II/III) bound to proanthocyanidins, with particles in the order of 20 nm, was prepared by green synthesis assisted by extract of açaí (Euterpe oleracea Mart.) berry seeds from an agro-industrial residue. The nanomaterial was applied in the adsorption of cationic dyes. Screening tests were carried out for methylene blue (MB), resulting in an outstanding maximum adsorption capacity of 531.8 mg g-1 at 343 K, pH 10, 180 min. The kinetics followed a pseudo-second-order model and the isotherm of Fritz-Schülnder provided the best fit. Thermodynamic data show an endothermic process with entropy increase, typical of chemisorption. The proposed mechanism is based on the multilayer formation over a heterogeneous adsorbent surface, with chemical and electrostatic interactions of MB with the iron oxide nanoparticles and with the proanthocyanidins. The high adsorption efficiency was attributed to the network formed by the polymeric proanthocyanidins that entangled and protected the iron oxide nanoparticles, which allowed the reuse of the nanomaterial for seven cycles without loss of adsorption efficiency.

The interaction and physicochemical properties of the starch-polyphenol complex: Polymeric proanthocyanidins and maize starch with different amylose/amylopectin ratios

This study investigated the impact of polymeric proanthocyanidins (PPC) on the physicochemical characteristics of maize starch with varying amylose content, and their potential interaction mechanism. PPC with a lower content (1 %) reduced the viscoelasticity of the high amylose maize starch (HAM) system, inhibited amylose rearrangement, and enhanced its fluidity. However, excessive PPC restrained the interaction between PPC and amylose. In contrast to HAM, PPC improved the gelation ability of waxy maize starch (WAM) as PPC concentration was raised. PPC suppressed the recrystallization of starch during storage, and PPC had a superior inhibition influence on the retrogradation of WAM in comparison to HAM. This indicated that amylopectin was more likely to interact with PPC than amylose. Hydrogen bonds were the main driving force between PPC and starch chains, which was clarified by Fourier transform-infrared, nuclear magnetic resonance, X-ray diffraction, iodine bonding reaction, and dynamic light scattering data. Additionally, the mechanism of interaction between PPC and the two starch components may be similar, and variance in physicochemical attributes can be primarily credited to the percentage of amylose to amylopectin in starch.

Effects of Global Warming on Grapevine Berries Phenolic Compounds—A Review

The steadfast propensity to global warming has had a severe impact on overall viticulture. Given the observed increase in growing season temperatures in Europe (+1.7 °C from 1950 to 2004), between 2000 and 2049, it is assumed that temperatures for major wine regions will increase on average by about +0.42 °C per decade and will generally increase by +2.04 °C. Phenolic compound development is affected by environmental parameters such as ultraviolet (UV) radiation, sunlight, maximum and minimum temperatures, and grapevine water status. Proanthocyanidins, flavan-3-ol monomers, and other pigmented polymers are impacted by soil management and canopy handling strategies, as well as obtaining a microclimate around the developing bunch. This review, after a necessary summary of the synthesis of phenolic compounds in the berry (flavonoids and non-flavonoids) to let the lector delve into the topic, describes the impact of climate change and therefore of environmental factors on their accumulation and storage throughout ripening and harvesting. For example, high berry temperatures can reduce the total concentrations of skin anthocyanin; a 35 °C temperature entirely obstructed anthocyanin synthesis, and instead quercetin 3-glucoside could be enhanced with exposure to solar radiation. In addition, increments via water deficit in the relative abundance of methoxylated anthocyanins were also found. The vineyard management strategies to mitigate the degradation of phenolic compounds and preserve their concentration are also further discussed. Finally, it is believed that it is necessary today to establish an elastic and variable approach towards the single wine year, moving away from the concept of product standardization.

The Effect of Grape Seed Extract on Lipid Profile in Diabetic Mice

The aim of this work is to evaluate the role of Grape Seed extracts (GSE) from three grape cultivars (Ahmer, Halawani, and Kamali) grown in Iraq as well as pomace on lipid profile in diabetic mice. Fifty adult female mice were divided into five groups. Negative control (untreatment), positive control (treated) diabetic, and diabetic mice treated with GSE. After six weeks; serum and liver tissue homogenate parameters were evaluated. HPLC results showed that Ahmer (red grape seeds) has highest concentration of proanthocyanidins polymers catechine, procyanidin, and epicatechine (796, 170, and 244) μg/g, respectively For that it was chosen for mice dosage, while the lowest amounts were in pomace 489, 99, and 143 μg/g, respectively. Oral dose of grape seed natural extract (600 mg/kg/day) reduced the level of lipid profile: TC, TG, LDL, and VLDL, (106.83±2.13, 84.66±4.27,13.83±1.16 and 21.33±1.21) respectively, except HDL which respectively was increased to 76.33±1.03. GSE were normalized the elevated levels of kidneys and liver functions. Similarly, Liver histological analysis shows that GSE groups exhibited morphology near to that of the control group.

Boosting the Antioxidant Potential of Polymeric Proanthocyanidins in Litchi (Litchi chinensis Sonn.) Pericarp via Biotransformation of Utilizing Lactobacillus Plantarum.

In order to enhance the efficient utilization of polymeric proanthocyanidins from litchi pericarp, a process for transforming litchis' polymeric proanthocyanidins (LPPCs) by using Lactobacilli has been established for products with highly antioxidative properties. Lactobacillus plantarum was selected to enhance the transformation effect. The transformation rate of LPPCs reached 78.36%. The content of litchis' oligomeric proanthocyanidins (LOPCs) in the products achieved 302.84 μg grape seed proanthocyanidins (GPS)/mg DW, while that of total phenols was 1077.93 gallic acid equivalents (GAE) μg/mg DW. Seven kinds of substances have been identified in the products by using the HPLC-QTOF-MS/MS method, among which 4-hydroxycinnamic acid, 3,4-dihydroxy-cinnamic acid, and proanthocyanidin A2 were major components. The in vitro antioxidative activity of the products after transformation was significantly (p < 0.05) higher than those of LOPCs and LPPCs. The scavenging activity of the transformed products for DPPH free radicals was 1.71 times that of LOPCs. The rate of inhibiting conjugated diene hydroperoxides (CD-POV) was 2.0 times that of LPPCs. The scavenging activity of the products for ABTS free radicals was 11.5 times that of LPPCs. The ORAC value of the products was 4.13 times that of LPPCs. In general, this study realizes the transformation of polymeric proanthocyanidins into high-activity small-molecule substances.

Mechanistic Understanding of Tyrosinase Inhibition by Polymeric Proanthocyanidins from Acacia confusa Stem Bark and Their Effect on the Browning Resistance of Fresh-Cut Asparagus Lettuce.

Tyrosinase inhibitors are capable of preventing unfavorable enzymatic browning of fruits and vegetables. In this study, the capacity of Acacia confusa stem bark proanthocyanidins (ASBPs) to inhibit tyrosinase activity was evaluated. ASBPs were shown to be a high-potential inhibitor of tyrosinase with IC50 values of 92.49 ± 4.70 and 61.74 ± 8.93 μg/mL when using L-tyrosine and L-DOPA as the substrate, respectively. The structural elucidation performed with UV-vis, FT-IR spectroscopy, ESI-MS and thiolysis coupled to HPLC-ESI-MS suggested that ASBPs had structural heterogeneity in monomer units and interflavan linkages and consisted mainly of procyanidins dominant with B-type linkages. To gain insights into the inhibitory mechanisms of ASBPs against tyrosinase, different spectroscopic and molecular docking methods were further conducted. Results validated that ASBPs possessed the ability to chelate copper ions and could prevent the oxidation process of substrates by tyrosinase. The hydrogen bond formed with Lys-376 residue played a key role in the binding force of ASBPs with tyrosinase that induced a certain alteration in the microenvironment and secondary structure of tyrosinase, resulting in the enzymatic activity being ultimately restricted. It was also observed that ASBPs treatment effectively inhibited the activities of PPO and POD to retard the surface browning of fresh-cut asparagus lettuce and thus extended their shelf-life. The results provided preliminary evidence supporting the exploitation of ASBPs into potential antibrowning agents for the fresh-cut food industry.

Hepatotoxicity of polymeric proanthocyanidins is caused by translocation of bacterial lipopolysaccharides through impaired gut epithelium

Polymeric proanthocyanidins (P-PAC) induced hepatotoxicity in C57BL/6 mice. Mice were supplemented with P-PAC alone or with a mixture of probiotic bacteria (PB), Lactobacillus, Bifidobacterium, and Akkermansia muciniphila for 14 consecutive days. The liver tissues of sacrificed mice were analyzed by mass spectrometry to identify and quantify the P-PAC metabolites. Potential P-PAC metabolites, 2-hydroxyphenylacetic acid and pyrocatechol were detected in higher concentrations and 4-hydroxybenzoic acid was detected exclusively in the mice supplemented with P-PAC and PB. Supplementation with P-PAC alone or with PB caused no shift in the α-diversity of mice gut microbiota. P-PAC induced nonalcoholic steatohepatitis in mice through increasing liver exposure to intestinal bacterial lipopolysaccharides by reducing expression of gut epithelial tight junction proteins, claudin-3 and occludin. Lipopolysaccharide concentrations in the livers of mice supplemented with P-PAC were significantly high compared to the control mice. Furthermore, P-PAC downregulated the expressions of claudin-3 and claudin-4 tight junction proteins in cultured Caco-2 cell monolayers. PB biotransformed P-PAC into bioavailable metabolites and potentially reduced the toxicity of P-PAC. The toxicity of P-PAC and their synbiotics need to be critically evaluated for the safety of human consumption.

Green Fabrication of Agglomeration-Reductive and Electrochemical-Active Reduced Graphene Oxide/Polymerized Proanthocyanidins Electrode for High-Performance Supercapacitor

Reduced graphene oxide (rGO) has been regarded as a promising electrode material for supercapacitors. However, its application has been restricted by the corrosive reducing agent, inevitable structure agglomeration, and limited electric double-layer capacitor (EDLC) performance. Here, we develop a 3D redox-active rGO/polymerized proanthocyanidins hybrid for high-performance supercapacitance. Using a green and effective hydrothermal process, oligomeric procyanidins (OPCs) have acted as an eco-friendly reductant for GO reduction. It also worked as a polymeric proanthocyanidin (GSP) precursor for the enhancement of pseudocapacitance, where GSP acted as a spacer for inhibiting the agglomeration of rGO/GSP sheets and improving the total specific capacitance. As a result, the as-prepared rGO/GSP composites display a cooperative energy storage mechanism of an electrochemical double-layer capacitor (EDLC) and a pseudocapacitor, with an increased specific capacitance from 141 F g–1 at 2 A g–1 for the pure rGO to 402 F g–1 at 2 A g–1 for the rGO/GSP hybrids. Meanwhile, the rGO/GSP-based symmetrical supercapacitor provides a high specific capacitance of 185 F g–1 at 0.8 A g–1, an energy density of 25.8 Wh kg–1 at a power density of 0.8 kW kg–1, and a good cycling stability with 60.8% capacitance retention over 10000 cycles at 2 A g–1. Such an excellent electrochemical performance comes from the agglomeration reduction structure and synergistic effects between the highly conductive graphene and pseudocapacitive GSP.

New technology for large preparation of a series of bioactive polyphenols from by-products of vinification

Grape pomaces or vinification by-products are abundant and rich in polyphenols, particularly proanthocyanidins. During the last three decades, grape and wine polyphenols, particularly catechins (CATs) and oligomeric proanthocyanidins (OPCs) have attracted considerable attention of the international scientific community, due essentially to their potential health-beneficial effects, related to their protective action towards cardiovascular disease and the oxygen free radical scavenger capacity. Such phenolic compounds have been proved to be the key components responsible for the health-beneficial effects of red wine. Furthermore, although the most widely recognized antioxidants are Vitamins A, C, and E, scientific research has shown that OPCs are likely the most powerful antioxidants known. Although various OPCs have been available in the market, they are generally very expensive due to the high cost of their production. As a consequence, the development of efficient methods for large-scale preparation of these bioactive compounds have still a challenging task for scientists. In this communication, we will present a new and efficient technology for large preparation of bioactive polyphenols from vinification by-products (grape seed and grape skin). On one hand, polymeric proanthocyanidins were transformed into a series of low- molecule-weight bioactive compounds using various degradation methods. On the other hand, High-Speed Countcurrent Chromatography (HSCCC), as a relative new separation technology for natural product preparation, was applied to large and efficient isolation of these bioactive compounds.

Metabolic Fate of Orally Ingested Proanthocyanidins through the Digestive Tract.

Proanthocyanidins (PACs), which are oligomers or polymers of flavan-3ols with potent antioxidative activity, are well known to exert a variety of beneficial health effects. Nonetheless, their bioaccessibility and bioavailability have been poorly assessed. In this review, we focused on the metabolic fate of PACs through the digestive tract. When oligomeric and polymeric PACs are orally ingested, a large portion of the PACs reach the colon, where a small portion is subjected to microbial degradation to phenolic acids and valerolactones, despite the possibility that slight depolymerization of PACs occurs in the stomach and small intestine. Valerolactones, as microbiota-generated catabolites of PACs, may contribute to some of the health benefits of orally ingested PACs. The remaining portion interacts with gut microbiota, resulting in improved microbial diversity and, thereby, contributing to improved health. For instance, an increased amount of beneficial gut bacteria (e.g., Akkermansia muciniphila and butyrate-producing bacteria) could ameliorate host metabolic functions, and a lowered ratio of Firmicutes/Bacteroidetes at the phylum level could mitigate obesity-related metabolic disorders.

Degradation of polymeric polyproanthocyanidins from black chokeberry by microwave-assisted nucleophilic technique of sulfite/catechin: Reaction kinetics, antioxidation and structural analysis

Microwave was employed to enhance the degradation of polymeric proanthocyanidins from black chokeberry using the nucleophilic technique of sulfite/catechin. Based on the degradation effect and kinetics, it was found that increasing the microwave time, microwave power, microwave temperature, sulfite concentration, and mass ratio of raw material to catechins was favourable for the degradation reaction. The degradation kinetics conformed to a random first-order degradation model. The antioxidant activity of the degraded products was analysed using DPPH and O2− assay, which suggested that the scavenging effect of the products was improved. FT-IR and 1H NMR analyses showed that the main functional groups were not destroyed. Using MALDI-TOF/MS to study the components of the degradation products, it was found that the molecular weight distribution became narrower, and the compositions were more single. Polyproanthocyanidins were reduced to oligomers. This study suggested that microwave-assisted nucleophilic techniques could produce oligomeric proanthocyanidins with remarkably improved functionalities.

Structure analysis and tyrosinase, melanogenesis, α-glucosidase, and nonenzymatic glycation inhibitory activities of polymeric proanthocyanidins from the pulp of Crataegus pinnatifida Bge.

Crataegus pinnatifida Bge. is a worthwhile industrial crop for its extensive application in Chinese herbal pharmaceuticals, food, and other industries. In this study, proanthocyanidins were extracted from the pulp of Crataegus pinnatifida Bge., and the structure, antityrosinase, antimelanogenesis, anti-α-glucosidase, and anti-glycation activities of these compounds were systematically elucidated. The combined utilization of high-performance liquid chromatography-electrospray ionization-mass spectrometry (HPLC-ESI-MS), matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF MS), and nuclear magnetic resonance (NMR) demonstrated that the proanthocyanidins were B-type procyanidin polymers consisting of epicatechin . These polymers were efficient, reversible, and competitive inhibitors of both tyrosinase and α-glucosidase with IC 50 values of 0.10 ± 0.01 mg/mL (for monophenolase), 0.16 ± 0.02 mg/mL (for diphenolase), and 0.50 ± 0.02 µg/mL, respectively. Moreover, the process of nonenzymatic glycation was also delayed by proanthocyanidins. Further cell assays suggested that these polymers strongly inhibited intracellular tyrosinase activity and melanogenesis and induced apoptosis in mouse melanoma cells. The results of circular dichroism (CD), molecular docking , and molecular dynamics (MD) consistently revealed that the inhibition of procyanidins on the two enzymes was primarily driven by hydrogen bonding and hydrophobic interactions, and the binding of epicatechin caused structural stretching and conformational modification of tyrosinase. Consequently, this study confirms novel tyrosinase, melanogenesis, α-glucosidase, and nonenzymatic glycation inhibitors, which might offer scientific evidence for potential applications in the cosmetics and pharmaceutical industries. • Proanthocyanidins can be produced industrially for a yield of 11.08%. • Various biological activities of proanthocyanidins enabled their wide applications. • Hydrogen bond and hydrophobic interaction loosened tyrosinase secondary structures. • Proanthocyanidins can reduce melanogenesis by down-regulating tyrosinase proteins.