Secondary phenolic metabolites play an important role in plant defense mechanisms, and increasing evidence indicates that many are important in human health. To date, few studies have investigated the impact of various agricultural practices on levels of secondary plant metabolites. To address this issue, the total phenolic (TP) content of marionberries, strawberries, and corn grown by sustainable, organic, or conventional cultural practices were measured. Additionally, the effects of three common postharvest processing treatments (freezing, freeze-drying, and air-drying) on the TP content of these agricultural products were also investigated. Statistically higher levels of TPs were consistently found in organically and sustainably grown foods as compared to those produced by conventional agricultural practices. In all samples, freeze-drying preserved higher levels of TPs in comparison with air-drying.

The gboma (Solanum macrocarpon L.) and scarlet eggplants (Solanum aethiopicum L.), which form part of the traditional sub-Saharan African culture, are two of the many neglected crops with potential for increased cultivation or as a genetic resource for improving agronomic traits of the common eggplant. This work is focused on the analysis of glycoalkaloid levels in S. macrocarpon and S. aethiopicum to assess their safety. Liquid chromatography-mass spectrometry was used to quantify glycoalkaloids in S. macrocarpon and S. aethiopicum compared to Solanum melongena L. Fruits of S. aethiopicum and S. melongena contained 0.58-4.56 mg/100 g of alpha-solamargine and 0.17-1 mg/100 g of alpha-solasonine, on a wet basis. S. macrocarpon fruits had much higher values of alpha-solamargine (124-197 mg/100 g) and alpha-solasonine (16-23 mg/100 g). However, the proportions of alpha-solamargine and alpha-solasonine of S. melongena and S. macrocarpon were similar (76-89% of alpha-solamargine), whereas in S. aethiopicum fruit composition was more variable (48-89% of alpha-solamargine). According to these results, the glycoalkaloid levels of S. macrocarpon fruits are 5-10 times higher than the value considered to be safe in foods and might not be considered suitable for human consumption; however, the glycoalkaloid levels of S. aethiopicum were similar to those of S. melongena (about 14% of values considered as toxic) and could be considered as safe for consumption. The incorporation of the cultivated African S. aethiopicum into eggplant breeding programs to develop improved varieties of the common eggplant may represent an alternative to crossing with wild species.

Clingstone peaches contain a wide array of complex secondary plant metabolites and polyphenolics, and increasing evidence indicates that many of these components are important in human health. Oligomeric flavan-3-ol metabolites (procyanidins) are particularly interesting owing to their potent antioxidant activity and protective cardiovascular effects. To date, little information is available on how postharvest and processing conditions impact levels of phenolics and procyanidins in fruit. This research addresses the impact of lye peeling, freezing, storage temperature (4 and 30°C) and three different time-temperature sterilisation combinations on levels of total phenolics (TPs) in Ross clingstone peaches. Additionally, we describe the profile of procyanidin oligomers (monomers through heptamers) in clingstone and freestone peaches and demonstrate a dramatic decrease in procyanidins in thermally processed peaches. TP levels ranged between 316 and 397 mg kg À1 in peeled peaches and between 376 and 609 mg kg À1 in unpeeled peaches. Cold storage at 4°C for 14 days or freezing and storing at À12°C for 3 months produced no loss in TPs. Peaches stored at 30°C for 24 h resulted in a 1.7-fold increase in TPs. Studies of TPs in peaches processed at temperatures of 213°F for 40 min, 220°F for 10 min and 230°F for 2.4 min indicate that processing above 213°F decreases levels of both TPs (up to 21%) and procyanidins (up to 100%). Processing at 213°F for 40 min produced no significant loss in TPs. Furthermore, studies reveal that a 30-43% loss in phenolic levels occurs during the first 3 months in storage after canning. It is clear that both storage and thermal processing conditions profoundly impact the levels of polyphenolics in peaches. More interestingly, these studies indicate that peaches are a rich source of procyanidins, having profiles similar to those found in cocoa, apples, wine and tea.

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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.

Twenty-one flavonol metabolites have been identified by LC/ESI-MS/MS in human urine, including isomers, after the consumption of cooked onions. Metabolites identified include quercetin monoglucuronides, methyl quercetin monoglucuronides, a quercetin monoglucuronide sulfate, quercetin diglucuronides, a methyl quercetin diglucuronide, quercetin glucoside sulfates, methyl quercetin, quercetin, and kaempferol monoglucuronides. The fragmentation patterns of flavonol metabolites obtained by MS/MS were distinctive for some isomers, indicating that fragmentation patterns may be useful predictors of conjugation position. Two isomers of sulfate quercetin glucosides were also found in urine, suggesting that many of the quercetin glucosides in onion are absorbed intact and undergo metabolism to the sulfate conjugate. Additionally, the interindividual variation in urinary quercetin metabolite profiles was determined by comparing the relative level of six different quercetin metabolites excreted in the urine of healthy volunteers. The ranges of quercetin metabolites excreted were similar among volunteers, yet notable differences in the levels of metabolites among individuals were observed. This study demonstrates the potential of monitoring the range of quercetin metabolites to reveal information on interindividual biotransformation capacity in response to dietary manipulations and as a biomarker for flavonol consumption.

The rapid rise in obesity-related diseases has increased interest in oral and dietary agents that disrupt fat metabolism, resulting in the excretion of dietary lipids in the feces. In this study, a rapid and convenient liquid chromatography method to comprehensively analyze fecal lipids in a single injection was developed. An evaporative light-scattering detector (ELSD) for routine analysis or atmosphere pressure chemical ionization tandem mass spectrometry [(+)APCI-MS/MS] for structural confirmation and peak purity was used. The method was applied to characterize lipid components of feces from hamsters fed high-fat diets with either 5% microcrystalline cellulose or 5% hydroxypropyl methylcellulose (HPMC) fibers, to test the effect of HPMC on lipid metabolism. HPMC is a nonfermentable, soluble cellulose fiber. The fecal lipid components identified using this method includes two secondary bile acids, deoxycholic acid, lithocholic acid, and neutral sterols including cholesterol, coprostanol, stigmastanol, and sitosterol. The profile of fecal lipid components was compared between two groups. It was found that the bile acid excretion was increased 2-fold in HPMC-fed hamsters. More interestingly, diacylglycerides and triacylglycerides were detected in feces from hamsters on HPMC-included high-fat diets. We believe that this is the first report of excretion of acylglycerides following neutral soluble fiber feeding.

The glutathionylation of quercetin was investigated in murine hepatic suspensions, in the absence of chemically or enzymatically induced oxidative stress, and in human urine after the consumption of 200 g of cooked onions ( approximately 74 mg of quercetin). In murine hepatic suspensions, 22 metabolites, including glucuronide, sulfate, and glutathione conjugates of quercetin, were identified by LC/ESI-MS/MS. In total, eight glutathione conjugates were identified in these suspension, including three isomeric forms of monoglutathionyl quercetin, two isomers of monoglutathionyl quercetin glucuronide, and three isomers of glutathionyl methyl quercetin. Quinone forms of glutathionyl quercetin and glutathionyl methyl quercetin were also apparent in mass spectra. In humans, several glutathione-related metabolites of quercetin were identified in urine as mercapturic acids of common hydroxyphenylacetic acids generated by the microbial degredation of quercetin in the gut. These include mercaptic acids of dihydroxytoluene, dihydroxybenzaldehyde, dihydroxyphenylacetic acid, dihydroxycinnamic acid, and dihydroxyphenylpropionic acid. Our results suggest that glutathionylation of quercetin occurs in both murine hepatic suspensions and humans and indicate that under certain conditions, quercetin intermediates require inactivation through conjugation with glutathione.