Integrated mass spectrometry approach to profile proanthocyanidins occurring in food supplements: Analysis of Potentilla erecta L. rhizomes

Potentilla erecta (L.) is known for the high concentration of proanthocyanidin oligomers (PAs) in its underground parts. The use of its preparations as food supplements and the lack of chemical–analytical studies concerning with an efficient chromatographic separation procedure for these compounds led us to develop a strategy to profile PAs occurring in this species.     

Elemental composition of HULIS in the Pearl River Delta Region, China: results inferred from positive and negative electrospray high resolution mass spectrometric data

The HUmic-LIke Substances (HULIS) fraction isolated from aerosol samples collected at a rural location of the Pearl River Delta Region (PRD), China, during the harvest season was analyzed by both positive and negative mode electrospray ionization (ESI) coupled with an ultrahigh resolution mass spectrometer (UHRMS). With the remarkable resolving power and mass accuracy of ESI-UHRMS, thousands of elemental formulas were identified. Formulas detected in the positive (ESI+) and the negative (ESI-) mode complement each other due to differences in the ionization mechanism, and the use of both provides a more complete characterization of HULIS. Compounds composed of C, H, and O atoms were preferentially detected in ESI- by deprotonation, implying their acidic properties. Tandem MS and Kendrick Mass Defect analysis implies that carboxyl groups are abundant in the CHO compounds. This feature is similar to those of natural fulvic acids, but relatively smaller molecular weights are observed in the HULIS samples. A greater number of reduced nitrogen organic compounds were observed in the ESI+ compared to ESI-. Compounds with biomass burning origin including alkaloids, amino acids, and their derivatives are their probable constituents. Sulfur-containing species were dominantly detected in ESI-. The presence of sulfate fragments in the MS/MS spectra of these species and their high O/S ratios implies that they are mainly organosulfates. Organosulfates and nitrooxy-organosulfates were often the most intensive peaks in the ESI- spectra. They are believed to be products of reactive uptake of photooxidation products of reactive volatile organic compounds by acidic sulfate particles. The elemental compositions deduced from the UHRMS analysis confirm the conclusion from our previous study that biomass burning and SOA formation are both important sources of HULIS in the PRD region.     

Short communication: Space allocation in intensive Mediterranean buffalo production influences the profile of functional biomolecules in milk and dairy products

The aim of the present study was to determine if space allocation influenced the concentration of biomolecules in buffalo milk and dairy products. Intensively housed buffaloes (n = 96) were randomly assigned to 2 groups according to days in milk, parity, and milk yield: group S10 had a space allocation of 10 m² per buffalo and group S15 had a space allocation of 15 m² per buffalo. Individual milk yield was recorded daily. Twice a month, a bulk milk sample was collected for each group, as well as whey, ricotta, and mozzarella cheese, to assess cheese yield and to conduct HPLC-electrospray ionization-tandem mass spectrometry, milk antioxidant activity, and cell viability analyses. We tested milk extracts from the 2 groups in vitro to evaluate their efficacy in counteracting endothelial oxidative damage induced by high glucose. We evaluated reproductive function in 28 buffaloes from each group using the Ovsynch-timed artificial insemination program. We observed no differences in milk quantity or quality in terms of fat, protein, or lactose, and reproductive function did not differ between the 2 groups. Compared with group S10, group S15 had higher concentrations of carnitine (56.7 ± 1.1 vs. 39.8 ± 0.7 mg/L in milk and 40.9 ± 0.8 vs. 31.7 ± 0.7 mg/L in whey), acetyl-l-carnitine (51.9 ± 0.3 vs. 39.7 ± 0.7 mg/L in milk and 41.1 ± 1.7 vs. 28.7 ± 2.6 mg/L in whey), propionyl-l-carnitine (34.8 ± 1.0 vs. 21.0 ± 0.9 mg/L in milk and 26.9 ± 0.8 vs. 17.6 ± 1.2 mg/L in whey), glycine betaine (23.1 ± 1.9 vs. 13.5 ± 1.6 mg/L in milk and 10.7 ± 0.4 vs. 7.9 ± 0.5 mg/L in whey), and δ-valerobetaine (24.2 ± 0.5 vs. 16.7 ± 0.5 mg/L in milk and 22.0 ± 0.9 vs. 15.5 ± 0.7 mg/L in whey). Group S15 also had higher total antioxidant activity than group S10 (56.7 ± 1.9 vs. 46.4 ± 1.13 mM Trolox equivalents). Co-incubation of high-glucose-treated endothelial cells with milk extracts from group S15 improved cell viability compared with cells treated with high glucose only; it also reduced intracellular lipid peroxidation (144.3 ± 0.4 vs. 177.5 ± 1.9%), reactive oxygen species (141.3 ± 0.9 vs. 189.3 ± 4.7 optical density units), and cytokine release (tumor necrosis factor-α, IL-1β, IL-6). Greater space allocation was associated with higher levels of biomolecules in buffalo milk. This could have been the result of improved welfare in buffaloes that were allocated more space.     

Enhancement of hematite bioreduction by natural organic matter

The effects of natural organic matter (NOM), ferrozine, and AQDS (anthraquinone-2,6-disulfonate) on the reduction of hematite (alpha-Fe2O3) by Shewanella putrefaciens CN32 were studied. It has been proposed that NOM enhances the reduction of Fe(III) by means of electron shuttling or by Fe(II) complexation. Previously both mechanisms were studied separately using "functional analogues" (AQDS for electron shuttling and ferrozine for complexation) and are presently compared with seven different NOMs. AQDS enhanced hematite reduction within the first 24 h of incubation, and this had been ascribed to electron shuttling. Most of the NOMs enhanced hematite reduction after 1 day of incubation indicating that these materials could also serve as electron shuttles. The effect of ferrozine was linear with concentration, and all of the NOMs exhibited this behavior. Fe(II) complexation only enhanced hematite reduction after sufficient Fe(II) had accumulated in the system. Fe(II) complexation appeared to alleviate a suppression of the hematite reduction rate caused by accumulation of Fe(II) in the system. Addition of Fe(II) to the hematite suspension, prior to inoculation with CN32, significantly inhibited hematite reduction and greatly diminished the effects of all of the organic materials, although some enhancement was observed due to addition of anthroquinone-2,6-disulfonate. These results demonstrate that NOM can enhance iron reduction by electron shuttling and by complexation mechanisms.     

Enhanced biodegradation of iopromide and trimethoprim in nitrifying activated sludge

Iopromide (an X-ray contrast agent) and trimethoprim (an antibacterial drug) are frequently detected pharmaceuticals in effluents of wastewater treatment plants (WWTPs) and in surface waters due to their persistence and high usage. Laboratory-scale experiments showed that a significantly higher removal rate in nitrifying activated sludge as compared to conventional activated sludge was observed for both iopromide and trimethoprim. When the activity of the nitrifying bacteria was inhibited, the percent removal of iopromide decreased from 97 to 86% while trimethoprim removal decreased from 70 to 25%. The metabolite of iopromide identified when nitrification was not inhibited was a dehydroxylated iopromide at the two side chains. However, when the nitrifying bacteria were inhibited the metabolite identified was a carboxylate, formed during the oxidation of the primary alcohol on the side chain of iopromide. These results suggest that the nitrifying bacteria are important in the observed biodegradation of iopromide in the activated sludge with higher solid retention time (SRT). Results from the laboratory-scale study were corroborated by the observed removal efficiencies in a full-scale municipal WWTP, which showed that iopromide (ranging from 0.10 to 0.27 microg/L) and trimethoprim (ranging from 0.0.08 to 0.53 microg/L) were removed more effectively in the nitrifying activate sludge which has a higher SRT (49 days) than in the conventional activated sludge (SRT of 6 days). In nitrifying activated sludge, the percent removal of iopromide in the WWTP reached 61%, while in conventional activated sludge, average removal was negligible. For trimethoprim, removal was limited to about 1% in the conventional activated sludge, while in the nitrifying activated sludge, the removal was increased to 50%.