A-type Proanthocyanidins Research Articles

Synthesis and Evaluation of Antimicrobial and Antibiofilm Properties of A-Type Procyanidin Analogues against Resistant Bacteria in Food.

Natural A-type procyanidins have shown very interesting biological activities, such as their proven antiadherence properties against pathogenic bacteria. In order to find the structural features responsible for their activities, we describe herein the design and synthesis of six A-type procyanidin analogues and the evaluation of their antimicrobial and antibiofilm properties against 12 resistant bacteria, both Gram positive and Gram negative, isolated from organic foods. The natural A-type procyanidin A-2, which had known antiadherence activity, was also tested as a reference compound for the comparative studies. Within the series, analogue 4, which had a NO2 group on ring A, showed the highest antimicrobial activity (MIC of 10 μg/mL) and was one of the best molecules at preventing biofilm formation (up to 40% decreases at 100 μg/mL) and disrupting preformed biofilms (up to 40% reductions at 0.1 μg/mL). Structure-activity relationships are also analyzed.

Isotopic Exchange HPLC-HRMS/MS Applied to Cyclic Proanthocyanidins in Wine and Cranberries.

Cyclic B-type proanthocyanidins in red wines and grapes have been discovered recently. However, proanthocyanidins of a different chemical structure (non-cyclic A-type proanthocyanidins) already known to be present in cranberries and wine possess an identical theoretical mass. As a matter of fact, the retention times and the MS/MS fragmentations found for the proposed novel cyclic B-type tetrameric proanthocyanidin in red wine and the known tetrameric proanthocyanidin in a cranberry extract are herein shown to be identical. Thus, hydrogen/deuterium (H/D) exchange was applied to HPLC-HRMS/MS to confirm the actual chemical structure of the new oligomeric proanthocyanidins. The comparison of the results in water and deuterium oxide and between wine and cranberry extract indicates that the cyclic B-type tetrameric proanthocyanidin is the actual constituent of the recently proposed novel tetrameric species ([C60H49O24]+, m/z 1153.2608). Surprisingly, the same compound was also identified as the main tetrameric proanthocyanidin in cranberries. Finally, a totally new cyclic B-type hexameric proanthocyanidin ([C90H73O36]+, m/z 1729.3876) belonging to this novel class was identified for the first time in red wine. Graphical Abstract ᅟ.

Inhibition of PDGF-BB-induced proliferation and migration in VSMCs by proanthocyanidin A2: Involvement of KDR and Jak-2/STAT-3/cPLA2 signaling pathways

Proanthocyanidin A2 (PA2), one of A-type proanthocyanidins, has been shown to harbor a broad spectrum of pharmacological activities, including anti-inflammatory, antioxidant, anti-HIV, anti-CDV and anti-α-glucosidase activities. However, little is known about the role for PA2 in regulating PDGF-induced VSMC proliferation and migration. In the present study, we investigated the possible effects of PA2 on PDGF-BB-induced proliferation, migration and inflammation in VSMCs in vitro to mimic a postangioplasty PDGF shedding condition. Herein, the data clearly show that PA2 markedly inhibited proliferation, migration and inflammatory responses at 0–30 μg/ml concentration in VSMCs in vitro. 10–30 μg/ml PA2 inhibited PDGF-mediated NAD(P)H oxidase activation and intracellular ROS formation in VSMCs. Furthermore, the effects exerted by PA2 involve the participation of KDR and Jak-2/STAT-3/cPLA2 signaling pathways. These data also highlight the possible therapeutic use of PA2 in vascular proliferative diseases, where abnormal proliferation and migration play important pathological roles.

Bioactivity Potential of Prunus spinosa L. Flower Extracts: Phytochemical Profiling, Cellular Safety, Pro-inflammatory Enzymes Inhibition and Protective Effects Against Oxidative Stress In Vitro.

Flower extracts of Prunus spinosa L. (blackthorn)—a traditional medicinal plant of Central and Eastern Europe indicated for the treatment of urinary tract disorders, inflammation, and adjunctive therapy of cardiovascular diseases—were evaluated in terms of chemical composition, antioxidant activity, potential anti-inflammatory effects, and cellular safety in function of fractionated extraction. The UHPLC-PDA-ESI-MS3 fingerprinting led to full or partial identification of 57 marker constituents (36 new for the flowers), mostly flavonoids, A-type proanthocyanidins, and phenolic acids, and provided the basis for authentication and standardization of the flower extracts. With the contents up to 584.07 mg/g dry weight (dw), 490.63, 109.43, and 66.77 mg/g dw of total phenolics (TPC), flavonoids, proanthocyanidins, and phenolic acids, respectively, the extracts were proven to be rich sources of polyphenols. In chemical in vitro tests of antioxidant (DPPH, FRAP, TBARS) and enzyme (lipoxygenase and hyaluronidase) inhibitory activity, the extracts effects were profound, dose-, phenolic-, and extraction solvent-dependent. Moreover, at in vivo-relevant levels (1–5 μg/mL) the extracts effectively protected the human plasma components against peroxynitrite-induced damage (reduced the levels of oxidative stress biomarkers: 3-nitrotyrosine, lipid hydroperoxides, and thiobarbituric acid-reactive substances) and enhanced the total antioxidant status of plasma. The effects observed in biological models were in general dose- and TPC-dependent; only for protein nitration the relationships were not significant. Furthermore, in cytotoxicity tests, the extracts did not affect the viability of human peripheral blood mononuclear cells (PBMC), and might be regarded as safe. Among extracts, the defatted methanol-water (7:3, v/v) extract and its diethyl ether and ethyl acetate fractions appear to be the most advantageous for biological applications. As compared to the positive controls, activity of the extracts was favorable, which might be attributed to some synergic effects of their constituents. In conclusion, this research proves that the antioxidant and enzyme inhibitory capacity of phenolic fractions should be counted as one of the mechanisms behind the activity of the flowers reported by traditional medicine and demonstrates the potential of the extracts as alternative ingredients for functional products supporting the treatment of oxidative stress-related pathologies cross-linked with inflammatory changes, especially in cardiovascular protection.

P.3.c.005 - Pre-clinical evaluation of two novel benzamides, LB-102 and 103, for the treatment of schizophrenia

The berries of Vaccinium macrocarpon, cranberry, are widely used for the prevention of urinary tract infections. This species contains A-type proanthocyanidins (PACs), which intervene in the initial phase of the development of urinary tract infections by preventing the adherence of Escherichia coli by their P-type fimbriae to uroepithelial cells. Unfortunately, the existing clinical studies used different cranberry preparations, which were poorly standardized. Because of this, the results were hard to compare, which led sometimes to conflicting results. Currently, PACs are quantified using the rather non-specific spectrophotometric 4-dimethylaminocinnamaldehyde (DMAC) method. In addition, a normal phase HPTLC-densitometric method, a HPLC-UV method and three LC–MS/MS methods for quantification of procyanidin A2 were recently published. All these methods contain some shortcomings and errors. Hence, the development and validation of a fast and sensitive standard addition LC–MS/MS method for the simultaneous quantification of A-type dimers and trimers in a cranberry dry extract was carried out. A linear calibration model could be adopted for dimers and, after logaritmic transformation, for trimers. The maximal interday and interconcentration precision was found to be 4.86% and 4.28% for procyanidin A2, and 5.61% and 7.65% for trimeric PACs, which are all acceptable values for an analytical method using LC–MS/MS. In addition, twelve different cranberry extracts were analyzed by means of the newly validated method and other widely used methods. There appeared to be an enormous variation in dimeric and trimeric PAC content. Comparison of these results with LC–MS/MS analysis without standard addition showed the presence of matrix effects for some of the extracts and proved the necessity of standard addition.A comparison of the well-known and widely used DMAC method, the butanol-HCl assay and this newly developed LC–MS/MS method clearly indicated the need for a reliable method able to quantify A-type PACs, which are considered to be the pharmacologically active constituents of cranberry, since neither the DMAC or butanol-HCl assays are capable of distinguishing between A and B-type PACs and therefore cannot detect adulterations with, for example, extracts with a high B-type PAC content. Hence, the combination of the DMAC method or butanol-HCl assay with this more specific LC–MS/MS assay could overcome these shortcomings.

Isolation of five proanthocyanidins from pear (Pyrus pyrifolia Nakai) fruit peels.

Five proanthocyanidins, two B-type dimers and three A-type trimers, were purified and isolated from the fruit peels of Pyrus pyrifolia Nakai cv. Chuhwangbae. The isolated compounds were identified as (-)-epicatechin gallate-(4β→8)-(-)-epicatechin (Hahashi et al. in Ann Biol Res 3:3200-3207, 2012), (-)-epicatechin-(4β→8)-(-)-epicatechin (procyanidin B2) (Tanrioven and Eksi in Food Chem 93:89-93, 2005), (-)-epicatechin-(4β→8, 2β→O-7)-(-)-epicatechin-(4β→8)-(-)-epicatechin (cinnamtannins B1) (Salta et al. in J. Fun. Food 2: 153-157, 2010), (-)-epicatechin-(4β→8)-(-)-epicatechin-(4β→8, 2β→O-7)-(-)-epicatechin (aesculitannin A) (Challice and Westwood in Phytochemistry 11: 37-44, 1972), and (-)-epicatechin-(4β→6)-(-)-epicatechin-(4β→8, 2β→O→7)-(-)-epicatechin (Es-Safi et al. in J Agric Food Chem 54: 6969-6977, 2006). Their structures were determined by nuclear magnetic resonance and mass spectrometry. The three A-type proanthocyanidin trimers were identified for the first time from pear.

Chemical profiling of guarana seeds (Paullinia cupana) from different geographical origins using UPLC-QTOF-MS combined with chemometrics

Paullinia cupana, commonly known as guarana, is an Amazonian fruit whose seeds are used to produce the powdered guarana, which is rich in caffeine and consumed for its stimulating activity. The metabolic profile of guarana from the two largest producing regions was investigated using UPLC-MS combined with multivariate statistical analysis. The principal component analysis (PCA) showed significant differences between samples produced in the states of Bahia and Amazonas. The metabolites responsible for the differentiation were identified by orthogonal partial least squares discriminant analysis (OPLS-DA). Fourteen phenolic compounds were characterized in guarana powder samples, and catechin, epicatechin, B-type procyanidin dimer, A-type procyanidin trimer and A-type procyanidin dimer were the main compounds responsible for the geographical variation of the samples.

Advantages of a validated UPLC–MS/MS standard addition method for the quantification of A-type dimeric and trimeric proanthocyanidins in cranberry extracts in comparison with well-known quantification methods

The berries of Vaccinium macrocarpon, cranberry, are widely used for the prevention of urinary tract infections. This species contains A-type proanthocyanidins (PACs), which intervene in the initial phase of the development of urinary tract infections by preventing the adherence of Escherichia coli by their P-type fimbriae to uroepithelial cells. Unfortunately, the existing clinical studies used different cranberry preparations, which were poorly standardized. Because of this, the results were hard to compare, which led sometimes to conflicting results. Currently, PACs are quantified using the rather non-specific spectrophotometric 4-dimethylaminocinnamaldehyde (DMAC) method. In addition, a normal phase HPTLC-densitometric method, a HPLC-UV method and three LC–MS/MS methods for quantification of procyanidin A2 were recently published. All these methods contain some shortcomings and errors. Hence, the development and validation of a fast and sensitive standard addition LC–MS/MS method for the simultaneous quantification of A-type dimers and trimers in a cranberry dry extract was carried out. A linear calibration model could be adopted for dimers and, after logaritmic transformation, for trimers. The maximal interday and interconcentration precision was found to be 4.86% and 4.28% for procyanidin A2, and 5.61% and 7.65% for trimeric PACs, which are all acceptable values for an analytical method using LC–MS/MS. In addition, twelve different cranberry extracts were analyzed by means of the newly validated method and other widely used methods. There appeared to be an enormous variation in dimeric and trimeric PAC content. Comparison of these results with LC–MS/MS analysis without standard addition showed the presence of matrix effects for some of the extracts and proved the necessity of standard addition.A comparison of the well-known and widely used DMAC method, the butanol-HCl assay and this newly developed LC–MS/MS method clearly indicated the need for a reliable method able to quantify A-type PACs, which are considered to be the pharmacologically active constituents of cranberry, since neither the DMAC or butanol-HCl assays are capable of distinguishing between A and B-type PACs and therefore cannot detect adulterations with, for example, extracts with a high B-type PAC content. Hence, the combination of the DMAC method or butanol-HCl assay with this more specific LC–MS/MS assay could overcome these shortcomings.

Evaluation of peanut skin and grape seed extracts to inhibit growth of foodborne pathogens

Peanut skin extract (PSE) and grape seed extract (GSE) are derived from waste products in the wine and peanut industries, respectively. Both have high concentrations of polyphenols, known to possess antioxidant and antimicrobial properties. PSE primarily contains “A‐type” procyanidins, while GSE primarily contains “B‐type” procyanidins. These differ structurally, but are both isomers of epicatechin dimers. The objective of this study was to evaluate the antimicrobial effects of PSE containing A‐type procyanidins and GSE containing B‐type procyanidins against select foodborne pathogens (Listeria monocytogenes, Escherichia coli O157:H7, and Salmonella Typhimurium). The minimum inhibitory concentration (MIC) of the two extracts on L. monocytogenes, E. coli O157:H7, and S. Typhimurium was determined using the pour plate method. GSE had a significantly lower MIC (p ≤ .05) than PSE for L. monocytogenes (GSE = 60.6 ppm, PSE > 68.2 ppm) and S. Typhimurium (GSE = 45.7 ppm, PSE = 60.6 ppm), but no difference in inhibition of E. coli O157:H7. Since GSE contributed to greater inhibition, GSE extract was fractionated into monomer‐rich (consisting primarily of catechins, epicatechins, and epicatechin gallates) and oligomer‐rich (consisting of dimers, trimers, tetramers, up to decamers) components. Growth curves of all three pathogens in the presence of full extract, monomer and oligomer fractions were compared separately. None of the extracts inhibited S. Typhimurium growth. Generally, the extract containing greater oligomer components inhibited growth of L. monocytogenes and E. coli O157:H7 when compared to the control. Results indicate that an extract with type B procyanidins higher in oligomers may have greater antimicrobial properties.

Position and orientation of gallated proanthocyanidins in lipid bilayer membranes: influence of polymerization degree and linkage type

It is well known that the biological activity of gallated proanthocyanidins (PAs) is highly structure-dependent. Polymerization degree (DP) and linkage types affect their biological activity greatly. Positions and orientations of gallated PAs in lipid bilayer reveal their structure-function activity at the molecular level. The present work aimed at determining the locations and orientations of epigallocatechin-3-gallate (EGCG) and its derivatives: A-type and B-type EGCG dimers and trimers in 1-palmitoyl-2-oleoyl phosphatidylcholine (POPC) and 1-palmitoyl-2-oleoyl phosphatidylethanolamine (POPE) lipid bilayer via molecular dynamic (MD) simulations. The results showed that EGCG and its derivatives localized in the lipid bilayer or on the bilayer/water interface. Their penetration depths and orientations depended on both DP and linkage types. The penetration depths decreased with the increase of DP, sequencing to be EGCG > EGCG dimers > EGCG trimers. Spatially stretched A-type PAs could form more hydrogen bonds (H-bonds) with deep oxygen atoms of lipid bilayer and have higher affinity to the lipid bilayer than B-type PAs. Our results will provide an explicit evidence for PAs’ distinct biological activities.

Anti-myocardial Ischemia Effect and Components of Litchi Pericarp Extracts.

Litchi (Litchi chinensis Sonn.) is a famous fruit in south China, and it is also effective for chest tightness or chest pain, irritability, flatulence, epigastric pain and neuralgic pain, hernia pain and testicular swelling, cough, etc. It is valued because a great amount of polyphenol was found in litchi pericarp. In this paper, we got litchi pericarp pure extract by a simple purification method, then evaluated its activity to clear oxygen free radicals in vitro, and evaluated its myocardial protection effect in vivo through acute myocardial ischemia rat model. The results showed that the pure extract had protective effect on myocardial ischemia injury in a certain dose-effect relationship, which reflected in the electrocardiogram, myocardial pathological morphology and other indicators such as cardiac function enzymes, serum and myocardial antioxidant capacity, and eNOS, Bcl-2 and Bax gene expression. Furthermore, we analyzed the components of pure extract by UPLC-MS, ESI-MS and NMR. The main components of PLPE were procyanidin which were identified as procyanidin B2(1), (-)-epicatechin(2), epicatechin-(4β→8,2β→O→7)-epicatechin-(4β→8)-epicatechin(3), A-type procyanidin trimer(4), B-type procyanidin dimer(5) and procyanidin A2(6).This study proved that litchi pericarp extract may have antioxidant activity and cardioprotection effect. It suggested that litchi pericarp may be good for cardiovascular disease. Copyright © 2017 John Wiley & Sons, Ltd.

Antiadhesive Activity and Metabolomics Analysis of Rat Urine after Cranberry (Vaccinium macrocarpon Aiton) Administration.

Cranberry (Vaccinium macrocarpon Aiton) is used to treat noncomplicated urinary tract infections (UTIs). A-type procyanidins (PAC-A) are considered the active constituents able to inhibit bacterial adhesion to the urinary epithelium. However, the role of PAC-A in UTIs is debated, because of their poor bioavailability, extensive metabolism, limited knowledge about urinary excretion, and contradictory clinical trials. The effects of 35-day cranberry supplementation (11 mg/kg PAC-A, 4 mg/kg PAC-B) were studied in healthy rats using a ultra performance liquid chromatography-mass spectrometry (UPLC-MS)-based metabolomics approach. Microbial PAC metabolites, such as valeric acid and valerolactone derivatives, were related to cranberry consumption. An increased urinary excretion of glucuronidated metabolites was also observed. In a further experiment, urine samples were collected at 2, 4, 8, and 24 h after cranberry intake and their antiadhesive properties were tested against uropathogenic Escherichia coli. The 8 h samples showed the highest activity. Changes in urinary composition were studied by ultra performance liquid chromatography-time-of-flight (UPLC-QTOF), observing the presence of PAC metabolites. The PAC-A2 levels were measured in all collected samples, and the highest amounts, on the order of ng/mL, were found in the samples collected after 4 h. Results indicate that the antiadhesive activity against uropathogenic bacteria observed after cranberry consumption is ascribable to PAC-A metabolites rather than to a direct PAC-A effect, as the measured PAC-A levels in urine was lower than those reported as active in the literature.

Impact of metal stress on the production of secondary metabolites in Pteris vittata L. and associated rhizosphere bacterial communities.

Plants adapt to metal stress by modifying their metabolism including the production of secondary metabolites in plant tissues. Such changes may impact the diversity and functions of plant associated microbial communities. Our study aimed to evaluate the influence of metals on the secondary metabolism of plants and the indirect impact on rhizosphere bacterial communities. We then compared the secondary metabolites of the hyperaccumulator Pteris vittata L. collected from a contaminated mining site to a non-contaminated site in Vietnam and identified the discriminant metabolites. Our data showed a significant increase in chlorogenic acid derivatives and A-type procyanidin in plant roots at the contaminated site. We hypothesized that the intensive production of these compounds could be part of the antioxidant defense mechanism in response to metals. In parallel, the structure and diversity of bulk soil and rhizosphere communities was studied using high-throughput sequencing. The results showed strong differences in bacterial composition, characterized by the dominance of Proteobacteria and Nitrospira in the contaminated bulk soil, and the enrichment of some potential human pathogens, i.e., Acinetobacter, Mycobacterium, and Cupriavidus in P. vittata's rhizosphere at the mining site. Overall, metal pollution modified the production of P. vittata secondary metabolites and altered the diversity and structure of bacterial communities. Further investigations are needed to understand whether the plant recruits specific bacteria to adapt to metal stress.

Effect of the A-Type Linkage on the Pharmacokinetics and Intestinal Metabolism of Litchi Pericarp Oligomeric Procyanidins.

The bioavailability of A-type procyanidins in vivo has been rarely investigated; as such, this study discusses the effect of A-type linkage and degree of polymerization on the metabolism of procyanidins extracted from litchi pericarp (LPOPC). Sprague-Dawley rats were gavaged with (-)-epicatechin (EC) and LPOPC and sacrificed at different time points after ingestion. A-type linkage procyanidin oligomers inhibited the absorption of EC. Analysis of urinary contents from rats administered with EC, A-type procyanidin dimer (A-2), and A-type procyanidin trimer (A-3) showed distinct native and metabolite profiles for each rat. Rats fed with A-2 and A-3 presented significantly higher levels of shikimic acid and less amount of m(p)-coumaric acid metabolites in vivo and provide insight into the quantitative structure-activity relationship of procyanidin oligomers during metabolism, indicating that procyanidins with A-type linkage could induce an altered metabolic pathway of oligomers in the gastrointestinal system.

Trimeric and Tetrameric A-Type Procyanidins from Peanut Skins.

Peanut skins are a rich source of oligomeric and polymeric procyanidins. The oligomeric fractions are dominated by dimers, trimers, and tetramers. A multistep chromatographic fractionation led to the isolation of four new A-type procyanidins of tri- and tetrameric structures. The structures of the new trimers were defined by NMR, electronic circular dichroism, and MS data as epicatechin-(4β→8,2β→O→7)-epicatechin-(4β→8,2β→O→7)-catechin, peanut procyanidin B (3), and epicatechin-(4β→8,2β→O→7)-epicatechin-(4β→6)-catechin, peanut procyanidin C (4). The new tetramers were defined as epicatechin-(4β→8,2β→O→7)-epicatechin-(4β→6)-epicatechin-(4β→8,2β→O→7)-catechin, peanut procyanidin E (1), and epicatechin-(4β→8,2β→O→7)-epicatechin-(4β→6)-epicatechin-(4β→8,2β→O→7)-epicatechin, peanut procyanidin F (2). In addition, both A-type dimers A1, epicatechin-(4β→8,2β→O→7)-catechin, and A2, epicatechin-(4β→8,2β→O→7)-epicatechin, as well as two known peanut trimers, ent-epicatechin-(4β→6)-epicatechin-(4β→8,2β→O→7)-catechin, peanut procyanidin A (5), and epicatechin-(4β→8)-epicatechin-(4β→8,2β→O→7)-catechin, peanut procyanidin D (6), were also isolated. Dimer A1, the four trimers, and two tetramers were evaluated for anti-inflammatory activity in an in vitro assay, in which LPS-stimulated macrophages were responding with secretion of TNF-α, a pro-inflammatory cytokine. Tetramer F (2) was the most potent, suppressing TNF-α secretion to 82% at 8.7 μM (10 μg/mL), while tetramer E (1) at the same concentrations caused a 4% suppression. The results of the TNF-α secretion inhibition indicate that small structural differences, as in peanut procyanidin tetramers E and F, can be strongly differentiated in biological systems.

Anti-aging and redox state regulation effects of A-type proanthocyanidins-rich cranberry concentrate and its comparison with grape seed extract in mice

We investigated the anti-aging and redox state regulation effects by A-type proanthocyanidins (PACs)-rich cranberry concentrate (CBC) and its comparison with B-type PACs-rich grape seed extract (GSE). Using the Q-Extractive mass spectrometry, PACs dimer A and B were identified as predominant phenolic compounds of CBC and GSE, respectively, while epicatechin was present in both extracts. Using the d-galactose-induced aging mice model, effects were investigated via an 8-week oral gavage considering water-soluble vitamin E as the positive control. Both CBC and GSE reduced hepatic and brain thiobarbituric acid reactive substances, and plasma 8-isoprostane levels by 30–57%, 24–30% and 11–62%, respectively, and decreased brain and plasma monoamine oxidase activities by 27–59% and 65–71%, respectively. CBC could improve hepatic glutathione peroxidase activity by 42%, while GSE increased hepatic superoxide dismutase activity by 13%. Therefore, both extracts exerted anti-aging effects probably via regulating in vivo redox state. However, neither generated any effect on catalase activities.

5-(3′,4′-Dihydroxyphenyl)-γ-valerolactone and its sulphate conjugates, representative circulating metabolites of flavan-3-ols, exhibit anti-adhesive activity against uropathogenic Escherichia coli in bladder epithelial cells

Urinary tract infections (UTI) are mostly caused by uropathogenic Escherichia coli (UPEC). Cranberry-based products have shown preventive effects against UTI, and this has been partially attributed to their A-type proanthocyanidin content. However, recent evidence reports phenyl-γ-valerolactones as the most relevant urinary metabolites of cranberry procyanidins, and candidates these compounds as plausible responsible for the protective effects of cranberries against UTI. This paper studied the inhibition of the adherence of UPEC ATCC®53503™ to T24 bladder epithelial cells by physiological concentrations of differently sulphated dihydroxyphenyl-γ-valerolactones. Moreover, the transformations of these molecules in the cell media were evaluated by UHPLC-MSn. All dihydroxyphenyl-γ-valerolactone derivatives showed anti-adhesive activity at 100μM, while 5-(3′-hydroxyphenyl)-γ-valerolactone-4-O-sulphate also showed neuro-protective effects at 50μM. Some compounds underwent extensive metabolism during cell incubation, mainly deconjugation of sulphate moieties and opening of the lactone ring. These results shed light on the flavan-3-ol metabolites behind the prophylactic effect of cranberries against UTI.

A-type proanthocyanidins selectively target acute myeloid leukemia cells in vitro and in vivo

A-type proanthocyanidins selectively target acute myeloid leukemia cells in vitro and in vivo

Retention of polyphenols in blueberries (Vaccinium corymbosum) after different cooking methods, using UHPLC–DAD–MS based metabolomics

This study investigated the impacts of baking, boiling and microwaving methods on polyphenols in blueberries, using ultra-high performance liquid chromatography (UHPLC) with a photodiode array detector (PDA) and mass spectrometer (MS). Twenty-eight characteristic peaks were found in blueberries of which 25 were significantly affected by cooking. The retention of each compound was calculated based on its peak areas in PDA chromatograms and expressed as ratio (%) of its peak area in cooked to fresh blueberries. The retention of total anthocyanins ranged from 74.3–76.4%, 52.9–77.4%, and 58.0–72.3%, and the values for other polyphenols ranged from 77.1–88.7%, 76.0–86.7%, 66.6–76.8%, respectively, after baking, boiling, and microwaving treatments. Caffeoylquinic acid was the predominant peak in both cooked and fresh blueberries. Its concentrations in blueberries baked for 5min or boiled for 1, 3, and 10min were not significantly different from those in fresh samples (p>0.05). An A-type procyanidin trimer was found to be the most unstable polyphenol; its concentrations decreased to 53.0%, 42.8%, and 36.1% of that in fresh blueberries, respectively, after 15-min baking, 10-min boiling, and 45-s microwaving. Compared to other polyphenols, caffeoylquinic acid, catechin and quercetin glycosides were the most stable. In general, microwaving led to the highest losses of polyphenols when cooking blueberries.

A computational tool for accelerated analysis of oligomeric proanthocyanidins in plants

A computational tool was developed to facilitate proanthocyanidin analysis using data collected by ultra-high-performance liquid chromatography-diode array detection-high resolution accurate mass-mass spectrometry (UHPLC-DAD-HRAM-MS). Both identification and semi-quantitation of proanthocyanidins can be achieved by the developed computational tool. It can extract proanthocyanidin chromatographic peaks, deconvolute the isotopic patterns of A-type, B-type, and multi-charged proanthocyanidins ions, and predict proanthocyanidin structures. Proanthocyanidins were quantified by an external calibration curve of catechin and molar relative response factors (MRRFs) of proanthocyanidins. Quantitation results including concentrations of total proanthocyanidins, individual proanthocyanidins, and proanthocyanidins with different degrees of polymerization and different types of linkage were calculated by the program and exported into an Excel spreadsheet automatically. The program was applied to the analysis of seven plant materials including apple, cranberry, dark chocolate, grape seed extract, jujube, litchi, and mangosteen. The identification results were compared with the results obtained by manual processing. The program can greatly save the time needed for the data analysis of proanthocyanidins.