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1.
The major constituents in grape seed and pine bark extracts are proanthocyanidins. To evaluate material available to consumers, select lots were analyzed using high-performance liquid chromatography, gas chromatography/mass spectrometry (GC/MS), liquid chromatography/mass spectrometry (LC/MS), gel permeation chromatography (GPC), and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). Atmospheric pressure chemical ionization (APCI) LC/MS was used to identify monomers, dimers, and trimers present. GC/MS analyses led to the identification of ethyl esters of hexadecanoic acid, linoleic acid, and oleic acid, as well as smaller phenolic and terpene components. The GPC molecular weight (MW) distribution indicated components ranging from approximately 162 to approximately 5500 MW (pine bark less than 1180 MW and grape seed approximately 1180 to approximately 5000 MW). MALDI-TOF MS analyses showed that pine bark did not contain oligomers with odd numbers of gallate units and grape seed contained oligomers with both odd and even numbers of gallate. Reflectron MALDI-TOF MS identified oligomers up to a pentamer and heptamer, and linear MALDI-TOF MS showed a mass range nearly double that of reflectron analyses.  相似文献   

2.
The structure of a polymeric proanthocyanidin fraction isolated from pear juice was characterized by NMR, ESI/MS, and MALDI-TOF/MS analyses, and its antioxidant activity was investigated using the DPPH free radical scavenging method. The results obtained from 13C NMR analysis showed the predominance of signals representative of procyanidins. Typical signals in the chemical shift region between 70 and 90 ppm demonstrated the exclusive presence of epicatechin units. The results obtained through negative ESI/MS analysis showed singly and doubly charged ions corresponding to the molecular mass of procyanidins with a degree of polymerization up to 22. The spectra obtained through MALDI-TOF/MS analysis revealed the presence of two series of tannin oligomers. Supporting the observations from NMR spectroscopy, the first series consists of well-resolved tannin identified as procyanidin polymers units with chain lengths of up to 25. A second series of monogalloyl flavan-3-ols polymers with polymerization degree up to 25 were also detected. This is the first mass spectrometric evidence confirming the existence of galloylated procyanidin oligomers in pear fruits. Within each of these oligomers, various signals exist suggesting the presence of several oligomeric tannins. The antioxidant properties of the polymeric fraction were investigated through reduction of the DPPH free radical, and the results obtained showed that the polymeric fraction exhibited a higher antioxidant power compared to those of (+)-catechin and B3 procyanidin dimer.  相似文献   

3.
Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) was employed to characterize the polygalloyl polyflavan-3-ols (PGPF) in grape seed extracts. Masses corresponding to a series of PGPF units inclusive of nonamers were observed in the positive-ion reflectron mode. Masses of PGPF inclusive of undecamers were observed in the positive-ion linear mode, providing the first known evidence of PGPF of this size. Soluble PGPF of grape seed extracts were precipitated by complexation with Yb(3+). The PGPF were then recovered by dissolving the precipitate in water and removing the Yb(3+) by a weakly acidic cation-exchange resin (Amberlite IRP-64). Comparisons of HPLC chromatograms of the crude grape seed extract prior to precipitation with Yb(3+) and after recovery of the PGPF indicated that 96% of the phenolic compounds were precipitated and 99% of the precipitated PGPF were recovered by cation-exchange resin. These results indicate that MALDI-TOF MS is able to determine the mass distribution of complex mixtures of oligomeric PGPF and that precipitation of PGPF by Yb(3+) is useful for isolation and quantification.  相似文献   

4.
A reverse phase C(18) HPLC method with potential for high automated throughput has been developed for the quantitative analysis of polymeric procyanidins (tannins) in grape seed extracts. Chromatography gave rise to 13 distinct UV-absorbing peaks with good baseline separation. The UV-absorbing peak eluting last is distinct and therefore easily quantified. Biochemical analyses including ultrafiltration, protein precipitation, and Sephadex LH20 chromatography combined with electrospray mass spectrometric analyses establish that this peak predominantly contains polymeric procyanidins. The polymers, which appear to be galloylated to various degrees and seem to fragment in a characteristic manner during electrospray mass spectrometry, are well separated from catechins and procyanidin oligomers of up to 4 units. The recovery of polymeric grape seed tannins with this HPLC method was 86%, which is similar to the 89% recovery achieved with commercial quebracho tannins. The concentration of tannins in seeds from ripe Vitis vinifera cv. Shiraz grapes ranged from 1360 to 2830 mg/kg of berries.  相似文献   

5.
Three newly formed Port wine pigments were isolated by Toyopearl HW-40(s) gel chromatography and semipreparative HPLC. Furthermore, the pigments were identified by mass spectrometry (LC/MS) and NMR techniques (1D and 2D). These anthocyanin-derived pigments showed UV-visible spectra different from those of the original grape anthocyanins. These pigments correspond to malvidin 3-glucoside linked through a vinyl bond to either (+)-catechin, (-)-epicatechin, or procyanidin dimer B3 [(+)-catechin-(+)-catechin]. NMR data of these pigments are reported for the first time.  相似文献   

6.
Among the methods that have been developed for anthocyanin characterization, matrix-assisted laser desorption ionization-time-of-flight mass spectrometry (MALDI-TOF MS) offers several analytical advantages in terms of speed, minimal sample handling, specificity, and reliability, without requiring any previous chromatographic separation. This study used MALDI-TOF MS to profile the anthocyanins from the berry skins of 23 red grape varieties clustered as (i) authentic Vitis vinifera grapes, (ii) American hybrid cultivars, and (iii) Casavecchia cultivars, previously characterized as functional crosses of V. vinifera with nondefined hybrid grapevines. Anthocyanin profiling demonstrated evidence of several varietal traits that enabled the differentiation of authentic V. vinifera from hybrid cultivars on a molecular basis. In particular, acyl 3,5-O-diglucoside anthocyanins were established as easily monitored molecular markers of the hybrid varieties. It was also demonstrated that MALDI-post source decay MS is a powerful tool to differentiate isobaric 3,5-O-diglucosides and their derivatives, which prevail in hybrid cultivars, from acylated 3-O-glucoside anthocyanins.  相似文献   

7.
Monomeric and oligomeric procyanidins present in cocoa and chocolate were separated and identified using a modified normal-phase high-performance liquid chromatography (HPLC) method coupled with on-line mass spectrometry (MS) analysis using an atmospheric pressure ionization electrospray chamber. The chromatographic separation was achieved using a silica stationary phase in combination with a gradient ascending in polarity. This qualitative report confirms the presence of a complex series of procyanidins in raw cocoa and certain chocolates using HPLC/MS techniques. Although both cocoa and chocolate contained monomeric and oligomeric procyanidin units 2-10, only use of negative mode provided MS data for the higher oligomers (i.e., >pentamer). Application of this method for qualitative analysis of proanthocyanidins in other food products and confirmation of this method as a reliable quantitative tool for determining levels of procyanidins in cocoa, chocolate, and other food products are currently being investigated.  相似文献   

8.
Blueberries and cranberries were analyzed for procyanidins using normal-phase HPLC/MS. Monomers, identified as (+)-catechin and (-)-epicatechin, and a series of oligomers were detected in blueberries, and MS data confirmed that the oligomers consisted of (epi)catechin units that were exclusively singly linked (B-type). The procyanidin "fingerprints" were similar for Tifblue and Rubel but higher than that for lowbush blueberries. In whole cranberries, (-)-epicatechin was present, along with a complex series of oligomers. Both A-type (contained only one double linkage per oligomer) and B-type oligomers were present. Two commercial cranberry juices exhibited similar procyanidin profiles, except that one contained increased quantities. There were processing effects on the procyanidin content of cranberry extract and juices when compared to those of the unprocessed fruits. Monomer, dimers, and A-type trimers were the primary procyanidins, with only trace levels of the B-type trimers and A-type tetramers and with an absence of the higher oligomers in cranberry extract and juices.  相似文献   

9.
Normal-phase liquid chromatography/mass spectrometry (LC/MS) was used to determine the levels and fate of procyanidins in frozen and canned Ross clingstone peaches as well as in the syrup used in the canning over a 3 month period. Procyanidin oligomers, monomers through undecamers, were identified in Ross clingstone peaches. Optimized methods allowed for the quantitation of oligomers through octamers. The profile of procyanidins in peaches is similar to profiles found in grapes, chocolate, and beverages linked to health benefits such as tea and wine. The monomer content in frozen peeled peaches was found to be 19.59 mg/kg. Dimers (39.59 mg/kg) and trimers (38.81 mg/kg) constituted the largest percent composition of oligomers in the peaches. Tetramers through octamers were present in levels of 17.81, 12.43, 10.62, 3.94 and 1.75 mg/kg, respectively. Thermal processing resulted in an 11% reduction in monomers, a 9% reduction in dimers, a 12% reduction in trimers, a 6% reduction in tetramers, and a 5% reduction in pentamers. Hexamers and heptamers demonstrated an approximate 30% loss, and octamers were no longer detected. Analysis of the syrup after thermal processing indicates that there is a migration of procyanidin monomers through hexamers into the syrup that can account for the losses observed during the canning process. Storage of canned peaches for 3 months demonstrated a time-related loss in higher oligomers and that by 3 months oligomers larger than tetramers are not observed. At 3 months postcanning, levels of monomers had decreased by 10%, dimers by 16%, trimers by 45%, and tetramers by 80%. A similar trend was observed in the canning syrup.  相似文献   

10.
In this study, we investigated the absorption of apple procyanidins, namely, apple condensed tannins (ACTs), in rats using the Porter method and high-performance liquid chromatography/tandem mass spectrometry. The apple procyanidin concentrations in the rat plasma reached a maximum 2 h after administration and decreased thereafter. To investigate the limits of the absorption of apple procyanidins in the polymerization degree, we administered the procyanidin oligomer fraction, which was separated from ACT using normal-phase chromatography according to the degree of polymerization. Procyanidins from each dimer to pentamer group were detected in the plasma by the Porter method. Moreover, by the study using reconstituted procyanidins, polymeric procyanidins influenced the absorption of procyanidin oligomers. These results suggest that ACTs are absorbed and directly involved in physiological functions in the rats.  相似文献   

11.
Antioxidants such as vitamin C, vitamin E, and carotenoids have been reported to prevent the progression of experimentally induced cataracts. However, little is known of the effect of procyanidins, a powerful antioxidant, on cataract formation. This paper investigates the anticataract activity of grape seed extract (GSE, which contains 38.5% procyanidins) in hereditary cataractous rats (ICR/f rats). The ICR/f rats were fed a standard diet containing 0 or 0.213% GSE [0.082% procyanidins in the diet (w/w)] for 27 days. The GSE significantly prevented and postponed development of cataract formation by evaluation of slit lamp observations of the rats' eyes. Lens weight and malondialdehyde concentration in the lens and plasma cholesteryl ester hydroperoxide (ChE-OOH) level induced by CuSO4 were significantly lower in the GSE group compared with the control group. The rats were also fed for 14 days either the diet containing 0.085% procyanidin dimer to tetramer fraction (0.085% as the procyanidins), the diet containing 0.090% procyanidin pentamer to heptamer fraction (0.085% as the procyanidins), or the diet containing 0.093% procyanidin oligomers more than decamer fraction (0.085% as the procyanidins). The ChE-OOH levels in the procyanidin pentamer to heptamer and procyanidin oligomers more than decamer groups were significantly lower than in the procyanidin dimer to tetramer group. These results suggested that procyanidins and their antioxidative metabolites prevented the progression of cataract formation by their antioxidative action. The larger molecular procyanidins in the GSE might contribute this anticataract activity.  相似文献   

12.
Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) was used to characterize the structural diversity of polyflavans in Ruby Red sorghum [Sorghum bicolor (L.) Moench]. Deionization of the polyflavan fractions with Dowex 50 x 8-400 cation-exchange resin and subsequent addition of cesium trifluoroacetate ((133)Cs) allowed the detection of exclusively [M + Cs](+) ions. MALDI-TOF MS of the polyflavans that eluate from Sephadex LH-20 columns with methanol and acetone detected a series of masses corresponding to heteropolyflavan-3-ols differing in degree of hydroxylation and nature of the interflavan bond (A-type and B-type). MALDI-TOF MS of the Sephadex-ethanol/methanol (v/v) eluate revealed a series of masses corresponding to heteropolyflavan-5-O-beta-glucosides that vary in the extent of hydroxylation and contain a flavanone (eriodictyol or eriodictyol-5-O-beta-glucoside) as the terminal unit. The combination of liquid chromatographic separation and MALDI-TOF MS to characterize sorghum polyflavans indicates that the structural heterogeneity is much greater than previously described.  相似文献   

13.
Beta-1,2,3,4,6-penta-O-galloyl-D-glucopyranose (PGG) and soluble complexes of PGG with bovine serum albumin (BSA) were characterized by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). PGG was also characterized by electrospray ionization mass spectrometry (ESI-MS). Similar fragmentation patterns of PGG were found in ESI-MS and MALDI-TOF MS. The apparent stoichiometries of non-covalent BSA-PGG complexes were determined by MALDI-TOF MS.  相似文献   

14.
Grape and its cell culture extracts are rich in flavonoids and stilbenes that are biologically active. The objective of this study was to evaluate possible inhibitory effects of grape (a Vitis hybrid Bailey Alicant A) cell culture extract and subfractions on human DNA topoisomerase II catalytic activity and to characterize constituents in the most potent fractions. At 5 microg/mL, grape cell crude extract and Toyopearl (TP) fractions 2-6 provided significantly greater inhibition of topoisomerase II catalytic activity than quercetin, a chemopreventive agent previously known as a topoisomerase catalytic inhibitor. The most potent topoisomerase II catalytic inhibitors from grape cell culture extracts in descending order of potency were TP fractions 4 and 6 (IC(50) = 0.28-0.29 microg/mL), TP-3 (IC(50) = 0.74 microg/mL), and crude extract (IC(50) = 1.02 microg/mL); each was significantly more potent than resveratrol (IC(50) = 18.0 microg/mL), another well-known chemopreventive topoisomerase II catalytic inhibitor. Using both high-performance liquid chromatography and liquid chromatography electrospray ionization mass spectrometry, constituents in TP-4 and TP-6 were characterized. These constituents included cyanidin-3,5-diglucoside, malvidin-3-acetylglucoside, peonidin-3-coumaryl-5-diglucoside, procyanidin B(1), procyanidin B(2), procyanidin B(5), procyanidin dimer digallate, procyanidin C(1), myricetin, and rutin, none of which have been previously characterized from grape cell cultures. The significant potency especially of TP-4 and TP-6 from grape cell cultures suggests that these fractions may have potential as chemopreventive agents.  相似文献   

15.
Monomeric and oligomeric proanthocyanidins present in a range of plant-derived foods and beverages were separated by degree of polymerization and identified using a modified normal-phase high-performance liquid chromatography (HPLC) method coupled with on-line mass spectrometry (MS) analysis using an atmospheric pressure ionization electrospray chamber. In addition, ultraviolet (UV) and fluorescence detection were used to monitor the separation of proanthocyanidins, with fluorescence detection demonstrating both increased sensitivity and the ability to reduce interfering signals from other components present in the food and beverage matrices as compared to UV detection. This qualitative study demonstrates the ability of this HPLC/MS technique to separate singly and doubly linked procyanidins, prodelphinidins, and copolymer oligomers, including their galloylated derivatives, present in a range of food and beverage samples.  相似文献   

16.
The fruits of the date palm (Phoenix dactylifera) are consumed throughout the world and are an important part of the diet in the Middle East. Dates at the rutab and tamar maturity and ripening stages contain a wide array of phenolic antioxidants, but little is known about the composition of phenolic compounds in dates at the khalal stage of ripening. In the current study, the flavonoid glycoside and procyanidin compositions of dates of the cultivar Deglet Noor harvested at the khalal stage of maturity were characterized using liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI/MS/MS). Procyanidin oligomers through decamers were identified in extracts of these dates. Higher molecular weight polymers, undecamers through heptadecamers, were also apparent from mass spectra. Thirteen flavonoid glycosides of luteolin, quercetin, and apigenin, 19 when considering isomeric forms, were also identified. Mass spectra indicate that both methylated and sulfated forms of luteolin and quercetin are present as mono-, di-, and triglycosylated conjugates whereas apigenin is present as only the diglycoside. LC-ESI/MS/MS spectra indicate that quercetin and luteolin formed primarily O-glycosidic linkages whereas apigenin is present as the C-glycoside.  相似文献   

17.
Interest in the molecular composition of almonds is growing, due to their popularity in a wide variety of food formulations. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) is a powerful new technique that can be used to rapidly identify and quantify possible bioactive compounds in these popular tree nuts. Four flavonol glycosides were identified in almond seedcoats for the first time: isorhamnetin rutinoside, isorhamnetin glucoside, kaempferol rutinoside, and kaempferol glucoside. A MALDI-TOF MS methodology was developed using rutin (quercetin-3-rutinoside) as an internal standard to quantitatively determine each of the four flavonol glycosides. Results of MALDI-TOF MS analysis were verified by high performance liquid chromatography.  相似文献   

18.
Oligomeric proanthocyanidins constitute a group of water-soluble polyphenolic tannins that are present in the female inflorescences (up to 5% dry wt) of the hop plant (Humulus lupulus). Humans are exposed to hop proanthocyanidins through consumption of beer. Proanthocyanidins from hops were characterized for their chemical structure and their in vitro biological activities. Chemically, they consist mainly of oligomeric catechins ranging from dimers to octamers, with minor amounts of catechin oligomers containing one or two gallocatechin units. The chemical structures of four procyanidin dimers (B1, B2, B3, and B4) and one trimer, epicatechin-(4beta-->8)-catechin-(4alpha-->8)-catechin (TR), were elucidated using mass spectrometry, NMR spectroscopy, and chemical degradation. When tested as a mixture, the hop oligomeric proanthocyanidins (PC) were found to be potent inhibitors of neuronal nitric oxide synthase (nNOS) activity. Among the oligomers tested, procyanidin B2 was most inhibitory against nNOS activity. Procyanidin B3, catechin, and epicatechin were noninhibitory against nNOS activity. PC and the individual oligomers were all strong inhibitors of 3-morpholinosydnonimine (SIN-1)-induced oxidation of LDL, with procyanidin B3 showing the highest antioxidant activity at 0.1 microg/mL. The catechin trimer (TR) exhibited antioxidant activity more than 1 order of magnitude greater than that of alpha-tocopherol or ascorbic acid on a molar basis.  相似文献   

19.
Negative-ion mode matrix-assisted laser desorption/ionization (MALDI) time-of-flight mass spectrometry (TOF-MS) was used for the characterization of storage, neutral oligosaccharides extracted from Jerusalem artichoke, red onion, and wheat. The oligosaccharides from the real samples were analyzed with 2,4,6-trihydroxyacetophenone as the most convenient matrix that was selected in advance with the standard carbohydrate samples (inulin and maltooligosaccharides). The oligosaccharides from Jerusalem artichoke and red onion (similarly as inulin) produced [M - H](-) peaks as the main distribution, which reflects their nonreducing composition. On the contrary, the cross-ring fragmentations [M - H - 120](-) formed the main distribution in the mass spectra of hydrolyzed wheat starch similarly to reducing maltooligosaccharides and dextrans. The negative-ion mode MALDI-TOF MS is capable of recognizing reducing and nonreducing oligosaccharides. Such a simple differentiation of malto or inulin type of oligosaccharides is not possible in the positive-ion mode.  相似文献   

20.
Analysis of intact glucosinolates by MALDI-TOF mass spectrometry   总被引：4，自引：0，他引：4  
Glucosinolates are naturally occurring plant compounds that may be important in the dietary prevention of cancer. This study shows that they can be detected in their intact form by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) with a high degree of sensitivity. The methodology was used to characterize a number of individual glucosinolates either produced by synthetic chemistry or isolated from plants. The method was used for crude plant extracts to rapidly examine the glucosinolate profile of the plant. The results for a range of plant extracts showed good agreement with previous LC-MS analysis of the desulfoglucosinolates from the same samples.  相似文献   

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