Quinone Levels Research Articles

Precipitation contributes to alleviating pollution of rubber-derived chemicals in receiving watersheds: Combining confluent stormwater runoff from different functional areas

The release of rubber-derived chemicals (RDCs) in road surface runoff has received significant attention. Urban surface runoff is often the confluence of stormwater runoff from specific areas. However, the impact of precipitation on RDCs contamination in confluent stormwater runoff and receiving watersheds remains poorly understood. Herein, we investigated the profiles of RDCs and their transformation products in confluent stormwater runoff and receiving rivers affected by precipitation events. The results showed that 34 RDCs are ubiquitously present in confluent stormwater runoff and surface water, with mean concentrations of 1.03–2749 and 0.28–436 ng/L, respectively. The most dominant target compounds in each category were N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD), 6PPD-quinone, 2-benzothiazolol, and 1,3-diphenylguanidine. Total RDCs concentrations in confluent stormwater runoff decreased spatially from industrial areas to business districts to college towns. A significant decrease in RDCs levels in surface water after rainfall was observed (P < 0.01), indicating that precipitation contributes to alleviating RDCs pollution in receiving watersheds. To our knowledge, this is the first report of N,N'-ditolyl-p-phenylenediamine quinone (DTPD-Q) levels in surface waters in China. The annual mass load of ∑RDCs reached 72,818 kg/y in confluent stormwater runoff, while 38,799 kg/y in surface water. The monitoring of confluent stormwater runoff is an efficient measure for predicting contamination loads from RDCs in rivers. Risk assessment suggested that most RDCs posed at least medium risks to aquatic organisms, especially 6PPD-quinone. The findings help to understand the environmental fate and risks of RDCs in the confluent stormwater runoff and receiving environments after precipitation events.

Comparative Phyto and Physicochemical Parameters of the Therapeutic Plant Syzygium cumini (L.) Skeels in Jaffna District

Syzygium cumini (L.) Skeels (Myrtaceae) is an evergreen tree, grown widely in Sri Lanka. It is regularly recognized as jambolan, black plum, and jamun. It is an extensively used therapeutic herbal in the treatment of innumerable illnesses, particularly in Diabetes mellitus in traditional medicine. The goal of the research was to compare the phytochemical and physicochemical properties between the different parts of jambolana tree which is naturally found in Sri Lanka. Proximate estimation of physicochemical properties of dried matured different parts as bark, leaves, fruits, and seeds of the Syzygium cumini havebeen done in the current study rendering to the standard protocols recommended by the World Health Organization (WHO) and Association of Analytical Chemist (AOAC). This study includes electrical conductivity value, moisture content, fat content, and different ash contents analysis. It was found that the leaves had the highest electrical conductivity (16.67±1.53) and the bark had the lowest electrical conductivity (2.44±0.03). The moisture content of the bark was lower (11.30±0.44) in comparison tothat of the seeds (16.34±0.43). Furthermore, the bark had the highest fat content (1.02±0.03) and acid insoluble ash (2.65±0.89), when compared to the seeds (0.65±0.01) and leaves (1.00±0.88) respectively. The seeds had the highest pH (5.39±0.08); total ash (2.18±0.06) and water-soluble ash (5.25±0.55), while the fruits had the highest sulphated ash (1.99±0.55). Qualitative inspection revealed that hot ethanolic seed extracts contained high levels of flavonoids, tannins, phenols, glycosides, alkaloids, terpenoids and quinones, in addition to other parts, which also had high levels of alkaloid content (81.06 mg/g). The current study will contribute useful data in the precise documentation and validation of various parts of S. cumini and may aid in removing contaminants in the preparation of nutraceuticals or medicine.&#x0D; Keywords: Medicinal Plant, Parts, Parameters, Physicochemical, Phytochemical, Syzygium cumini

Polycyclic aromatic hydrocarbons and their oxygenated derivatives in urban aerosol: levels, chemical profiles, and contribution to PM2.5 oxidative potential

The concentrations of polycyclic aromatic hydrocarbons (PAHs) and quinones, a subgroup of oxygenated PAHs (oxy-PAHs), were measured in PM2.5 samples collected during warm (May–June 2019) and cold (February–March 2020) seasons in the city of Bologna, Italy. Total PAHs concentration was nearly double in winter (6.58 ± 1.03 ng m−3) compared with spring (3.16 ± 0.53 ng m−3), following the trend of the PM2.5 mass concentration. Molecular diagnostic ratios suggested that, together with traffic, biomass burning was the dominant emission source contributing to the peaks of concentration of PM2.5 registered in the cold season. Quinone level was constant in both seasons, being 1.44 ± 0.24 ng m−3, that may be related to the increased secondary formation during warm season, as confirmed by the higher Σoxy-PAHs/ΣPAHs ratio in spring than in winter. The oxidative potential (OP) of the PM2.5 samples was assessed using acellular dithiothreitol (DTT) and ascorbic acid (AA) assays. The obtained responses showed a strong seasonality, with higher volume-normalized (OPV) values in winter than in spring, i.e., OPVDTT: 0.32 ± 0.15 nmol min−1 m−3 vs. 0.08 ± 0.03 nmol min−1 m−3 and OPVAA: 0.72 ± 0.36 nmol min−1 m−3 vs. 0.28 ± 0.21 nmol min−1 m−3. Both OPVDTT and OPVAA responses were significantly associated with total PAHs, as a general descriptor of redox-active PAH derivatives, associated with co-emission from burning sources or secondary atmospheric oxidation of parent PAHs. Otherwise, only winter OPVDTT responses showed a significant correlation with total Ʃoxy-PAHs concentration.

Regulations and mechanisms of 1-methylcyclopropene treatment on browning and quality of fresh-cut lotus (Nelumbo nucifera Gaertn.) root slices

The quality of fresh-cut lotus root slices is greatly affected by enzymatic browning. In this study, we investigated the effects of 1-methylcyclopropene treatment on browning and quality deterioration of lotus root slices. When fresh-cut lotus root slices were immersed in 0.1 mg L−1 1-MCP for 1 h and stored at 10 ℃ for twelve days, microbial growth, respiration, total phenolic content, phenylalanine ammonia lyase activity, polyphenol oxidase activity, and soluble quinone levels in fresh-cut lotus root slices were suppressed. Furthermore, 1-MCP treatment improved the antioxidant capacities, peroxidase activities, superoxide dismutase activities, catalase activities, and DPPH free radical scavenging rates in fresh-cut lotus root slices. In addition, 1-MCP treatment inhibited the production of reactive oxide species, which delayed quality deterioration of fresh-cut lotus root slices. Based on transcriptomics and real-time quantitative PCR results, gene expression levels of NnmetK2, NnACO, NnETR2, NnEIN3, and NnERF1 were up-regulated while expression levels of NnEBF1 were down-regulated. These findings indicate that 1-MCP inhibits ethylene biosynthesis and signal transduction, which suppresses a series of ethylene-induced physiological and biochemical reactions. Based on our findings, we propose a new strategy for inhibiting enzymatic browning in fresh-cut lotus root slices.

Establishment of hairy root culture of Rubia yunnanensis Diels: Production of Rubiaceae-type cyclopeptides and quinones

Rubia yunnanensis is an important medicinal plant with various bioactive secondary metabolites. In order to reduce the dependence on wild populations of the species, we aim to establish in vitro culture system that can produce Rubiaceae-type cyclopeptides (RAs) and quinones. Agrobacterium rhizogenes-mediated transformation of stem segments of in vitro grown R. yunnanensis plants using four A. rhizogenes strains was studied and transformation conditions were optimized. Hairy roots appeared with the highest frequency (68.89%) when stem segments (with leaves) without pre-culture were immersed in A. rhizogenes A4 strain bacterial suspension for 30 min, co-cultured on Murashige and Skoog (MS) solid medium in the dark for three days, and afterwards incubated in darkness. PCR analysis of rolB and rolC genes confirmed transformed nature of six hairy root clones. The hairy roots grew rapidly, especially showing the highest accumulation of biomass in MS liquid medium compared to in vitro grown plants and calli. Histological observation of hairy root revealed anatomical difference in vascular cylinder, where the cells exhibited high mitotic activity characterized by vigorous growth. The UPLC-MS/MS analysis revealed that the amount of RAs in the hairy roots grown in ½MS liquid medium (4.611 μg g−1 DW) was higher than that in in vitro grown plants (0.331 and 4.096 μg g−1 DW for shoots and roots respectively) and calli (1.082 μg g−1 DW), but still far lower than that in the roots of seed-borne plants (80.296 μg g−1 DW). However, the hairy roots accumulated high level of quinones (2320.923 and 5067.801 μg g−1 DW for MS and ½MS liquid media respectively), of the same order of magnitude as the roots of seed-borne plants (7409.973 μg g−1 DW). Hairy root culture of R. yunnanensis, with high accumulation of biomass and production of quinones, may offer an attractive perspective for the production of the RAs and quinones that could be further optimized for pharmaceutical use.

Effect of Chronic Methylphenidate Treatment in a Female Experimental Model of Parkinsonism.

Methylphenidate (MPH) is the most commonly prescribed drug for the treatment of ADHD in males and females. However, a majority of previous studies investigated the effect of MPH in only males, and little is known regarding consequences of female exposure to MPH. This is unfortunate because the few studies that have been conducted indicate that females have a greater sensitivity to MPH. Previous research in male mice has shown that chronic exposure to MPH causes dopaminergic neurons within the nigrostriatal pathway to be more sensitive to the Parkinsonian toxin 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP). However, estrogen has been shown to protect dopaminergic neurons from MPTP neurotoxicity. Therefore, in this study, we test the hypothesis that chronic MPH exposure in female mice will render dopaminergic neurons in the nigrostriatal pathway more sensitive to MPTP, and that estrogen may play a protective role. Interestingly, proestrus females exhibited greater sensitivity to MPTP, with significantly reduced dopaminergic neurons in the SN and significant increases in DA quinone production. Chronic MPH exposure contributed to GSH depletion, but surprisingly, it did not increase dopamine quinone levels or dopaminergic cell loss. There were no significant differences in anestrus animals, with the exception of a depletion in GSH seen when animals received chronic high-dose (10mg/kg) MPH followed by MPTP. Thus, estrogen may actually sensitize neurons to MPTP in this model, and chronic MPH may contribute to GSH depletion within the striatum. This study provides insight into how chronic psychostimulant use may affect males and females differently.

Sulfite oxidation by the quinone-reducing molybdenum sulfite dehydrogenase SoeABC from the bacterium Aquifex aeolicus

The microaerophilic bacterium Aquifex aeolicus is a chemolitoautotroph that uses sulfur compounds as electron sources. The model of oxidation of the energetic sulfur compounds in this bacterium predicts that sulfite would probably be a metabolic intermediate released in the cytoplasm. In this work, we purified and characterized a membrane-bound sulfite dehydrogenase, identified as an SoeABC enzyme, that was previously described as a sulfur reductase. It is a member of the DMSO-reductase family of molybdenum enzymes. This type of enzyme was identified a few years ago but never purified, and biochemical data and kinetic properties were completely lacking. An enzyme catalyzing sulfite oxidation using Nitro-blue tetrazolium as artificial electron acceptor was extracted from the membrane fraction of Aquifex aeolicus. The purified enzyme is a dimer of trimer (αβγ)2 of about 390 kDa. The KM for sulfite and kcat values were 34 μM and 567 s−1 respectively, at pH 8.3 and 55 °C. We furthermore showed that SoeABC reduces a UQ10 analogue, the decyl-ubiquinone, as well, with a KM of 2.6 μM and a kcat of 52.9 s−1. It seems to specifically oxidize sulfite but can work in the reverse direction, reduction of sulfur or tetrathionate, using reduced methyl viologen as electron donor. The close phylogenetic relationship of Soe with sulfur and tetrathionate reductases that we established, perfectly explains this enzymatic ability, although its bidirectionality in vivo still needs to be clarified. Oxygen-consumption measurements confirmed that electrons generated by sulfite oxidation in the cytoplasm enter the respiratory chain at the level of quinones.

Imbalances in the disposition of estrogen and naphthalene in breast cancer patients: a potential biomarker of breast cancer risk

Elevation of naphthoquinones and estrogen quinones, which are reactive metabolites of naphthalene and estrogen, is thought to be an important indicator of naphthalene- and estrogen-induced carcinogenesis. We compared background levels of naphthalene and estrogen quinone-derived adducts in serum albumin (Alb) from 143 women with breast cancer and 119 healthy controls. Cysteinyl adducts of naphthoquinones, including 1,2-naphthoquinone (1,2-NPQ) and 1,4-naphthoquinone (1,4-NPQ), and estrogen quinones, including estrogen-2,3-quinones (E2-2,3-Q) and estrogen-3,4-quinones (E2-3,4-Q), were characterized after adduct cleavage. Levels of estrogen quinones and naphthoquinones were positively correlated in healthy controls, but not in breast cancer patients (p < 0.05). Compared with controls, levels of 1,2-NPQ and E2-3,4-Q were elevated by two- to ten-fold in cancer patients (p < 0.001). To explore the correlation between estrogen- and naphthalene-derived quinone adducts and disease status, we performed linear discriminant analysis of the ratio of 1,2-NPQ-Alb to (1,2-NPQ-Alb plus 1,4-NPQ-Alb) versus the ratio of E2-3,4-Q-2-S-Alb to (E2-2,3-Q-4-S-Alb plus E2-3,4-Q-2-S-Alb) in patients and controls. These two groups were separable using albumin adducts of estrogen quinones and naphthoquinones, with 99.6% overall correct classification rate (overall accuracy). The findings of this study suggest that differences in the disposition of estrogen and naphthalene, and the subsequent elevation of cumulative E2-3,4-Q and 1,2-NPQ may serve as biomarkers of breast cancer risk.

Observed Daily Profiles of Polyaromatic Hydrocarbons and Quinones in the Gas and PM1 Phases: Sources and Secondary Production in a Metropolitan Area of Mexico

The diel variation of meteorological conditions strongly influences the formation processes of secondary air pollutants. However, due to the complexity of sampling highly reactive chemical compounds, significant information about their transformation and source can be lost when sampling over long periods, affecting the representativeness of the samples. In order to determine the contribution of primary and secondary sources to ambient levels of polyaromatic hydrocarbons (PAHs) and quinones, measurements of gas and PM1 phases were conducted at an urban site in the Guadalajara Metropolitan Area (GMA) using a 4-h sampling protocol. The relation between PAHs, quinones, criteria pollutants, and meteorology was also addressed using statistical analyses. Total PAHs (gas phase + PM1 phase) ambient levels ranged between 184.03 ng m−3 from 19:00 to 23:00 h and 607.90 ng m−3 from 07:00 to 11:00 h. These figures both coincide with the highest vehicular activity peak in the morning and at night near the sampling site, highlighting the dominant role of vehicular emissions on PAHs levels. For the gas phase, PAHs ranged from 177.59 to 595.03 ng m−3, while for PM1, they ranged between 4.81 and 17.44 ng m−3. The distribution of the different PAHs compounds between the gas and PM1 phases was consistent with their vapour pressure (p °L) reported in the literature, the PAHs with vapour pressure ≤ 1 × 10−3 Pa were partitioned to the PM1, and PAHs with vapour pressures ≥ 1 × 10−3 Pa were partitioned to the gas phase. PAHs diagnostic ratios confirmed an anthropogenic emission source, suggesting that incomplete gasoline and diesel combustion from motor vehicles represent the major share of primary emissions. Quinones ambient levels ranged between 18.02 ng m−3 at 19:00–23:00 h and 48.78 ng m−3 at 15:00–19:00 h, with significant increases during the daytime. The distribution of quinone species with vapour pressures (p °L) below 1 × 10−4 Pa were primarily partitioned to the PM1, and quinones with vapour pressures above 1 × 10−4 Pa were mainly partitioned to the gas phase. The analysis of the distribution of phases in quinones suggested emissions from primary sources and their consequent degradation in the gas phase, while quinones in PM1 showed mainly secondary formation modulated by UV, temperature, O3, and wind speed. The sampling protocol proposed in this study allowed obtaining detailed information on PAHs and quinone sources and their secondary processing to be compared to existing studies within the GMA.

Ajoene, a Major Organosulfide Found in Crushed Garlic, Induces NAD(P)H:quinone Oxidoreductase Expression Through Nuclear Factor E2-related Factor-2 Activation in Human Breast Epithelial Cells

BackgroundNAD(P)H:quinone oxidoreductase-1 (NQO1) is a widely-distributed flavin adenine dinucleotide-dependent flavoprotein that promotes obligatory 2-electron reductions of quinones, quinoneimines, nitroaromatics, and azo dyes. This reduces quinone levels and thereby minimizes generation of excess reactive oxygen species (ROS) formed by redox cycling, and concurrent depletion of intracellular thiol pools. Ajoene is derived from crushed garlic. It is formed by a reaction involving two allicin molecules, and is composed of allyl sulfide and vinyl disulfide. Ajoene is present in two isomers, E- and Z-form.MethodsExpression of antioxidant enzymes and nuclear factor E2-related factor-2 (Nrf2) was measured by Western blot analysis. NQO1 promoter activity was assessed by the luciferase reporter gene assay. ROS accumulation was monitored by using the fluorescence-generating probe 2′,7′-dichlorofluorescein diacetate. The intracellular glutathione levels were measured by using a commercially available kit.ResultsZ-ajoene significantly up-regulated the expression of representative antioxidant enzyme NQO1 in non-tumorigenic breast epithelial MCF-10A cells at non-toxic concentrations. Z-ajoene enhanced up-regulation and nuclear translocation of Nrf2, which plays a pivotal role in the induction of many genes encoding antioxidant enzymes and other cytoprotective proteins. Z-ajoene treatment also increased the activity of nqo1-promoter harboring antioxidant response element consensus sequences in MCF-10A cells. Silencing of Nrf2 by small interfering RNA abrogated ajoene-induced expression of NQO1. Z-ajoene activated extracellular signal-regulated kinase (ERK). Inhibition of ERK activation by U0126 abrogated ability of Z-ajoene to activate Nrf2 and to induce NQO1 expression. Intracellular ROS accumulation was observed after treatment with Z-ajoene, whereas the E-isoform was not effective. The inhibition of ROS by treatment with N-acetylcysteine, a radical scavenger, abrogated Z-ajoene-induced expression of NQO1 as well as activation of ERK and Nrf2, suggesting that Z-ajoene augments the Nrf2-dependent antioxidant defense via ROS generation and ERK activation.ConclusionsZ-ajoene induces NQO1 expression in MCF-10A cells through ROS-mediated activation of Nrf2.

Female Density-Dependent Chemical Warfare Underlies Fitness Effects of Group Sex Ratio in Flour Beetles

In animals, skewed sex ratios can affect individual fitness via sexual (e.g., intersexual conflict or intrasexual mate competition) or nonsexual (e.g., sex-specific resource competition) interactions. Because most analyses of sex ratio focus on sexual interactions, the relative importance of sexual versus nonsexual mechanisms remains unclear. We tested both mechanisms in the flour beetle Tribolium castaneum, where male-biased sex ratios increase female fitness relative to unbiased or female-biased groups. Although flour beetles show both sexual and nonsexual (resource) competition, we found that sexual interactions did not explain female fitness. Instead, female fecundity was dramatically reduced even after a brief exposure to flour conditioned by other females. Earlier studies suggested that secreted toxins might mediate density-dependent population growth in flour beetles. We identified ethyl benzoquinone and methyl benzoquinone (quinones) as components of adult stink glands that regulate female fecundity. In female-biased groups (i.e., at high female density), females upregulated quinones and suppressed each other’s reproduction. In male-biased groups, low female density and associated low quinone levels maximized fecundity. Thus, females appear to use quinones as weapons for female-specific, density-dependent interference competition. Our results underscore the importance of nonsexual interference competition that may often underlie the fitness consequences of skewed sex ratios.

Cupriavidus necator H16 Uses Flavocytochrome c Sulfide Dehydrogenase To Oxidize Self-Produced and Added Sulfide.

Production of sulfide (H2S, HS-, and S2-) by heterotrophic bacteria during aerobic growth is a common phenomenon. Some bacteria with sulfide:quinone oxidoreductase (SQR) and persulfide dioxygenase (PDO) can oxidize self-produced sulfide to sulfite and thiosulfate, but other bacteria without these enzymes release sulfide into the medium, from which H2S can volatilize into the gas phase. Here, we report that Cupriavidus necator H16, with the fccA and fccB genes encoding flavocytochrome c sulfide dehydrogenases (FCSDs), also oxidized self-produced H2S. A mutant in which fccA and fccB were deleted accumulated and released H2S. When fccA and fccB were expressed in Pseudomonas aeruginosa strain Pa3K with deletions of its sqr and pdo genes, the recombinant rapidly oxidized sulfide to sulfane sulfur. When PDO was also cloned into the recombinant, the recombinant with both FCSD and PDO oxidized sulfide to sulfite and thiosulfate. Thus, the proposed pathway is similar to the pathway catalyzed by SQR and PDO, in which FCSD oxidizes sulfide to polysulfide, polysulfide spontaneously reacts with reduced glutathione (GSH) to produce glutathione persulfide (GSSH), and PDO oxidizes GSSH to sulfite, which chemically reacts with polysulfide to produce thiosulfate. About 20.6% of sequenced bacterial genomes contain SQR, and only 3.9% contain FCSD. This is not a surprise, since SQR is more efficient in conserving energy because it passes electrons from sulfide oxidation into the electron transport chain at the quinone level, while FCSD passes electrons to cytochrome c The transport of electrons from the latter to O2 conserves less energy. FCSDs are grouped into three subgroups, well conserved at the taxonomic level. Thus, our data show the diversity in sulfide oxidation by heterotrophic bacteria.IMPORTANCE Heterotrophic bacteria with SQR and PDO can oxidize self-produced sulfide and do not release H2S into the gas phase. C. necator H16 has FCSD but not SQR, and it does not release H2S. We confirmed that the bacterium used FCSD for the oxidation of self-produced sulfide. The bacterium also oxidized added sulfide. The common presence of SQRs, FCSDs, and PDOs in heterotrophic bacteria suggests the significant role of heterotrophic bacteria in sulfide oxidation, participating in sulfur biogeochemical cycling. Further, FCSDs have been identified in anaerobic photosynthetic bacteria and chemolithotrophic bacteria, but their physiological roles are unknown. We showed that heterotrophic bacteria use FCSDs to oxidize self-produced sulfide and extraneous sulfide, and they may be used for H2S bioremediation.

Profiling quinones in ambient air samples collected from the Athabasca region (Canada)

This paper presents new findings on polycyclic aromatic hydrocarbon oxidation products–quinones that were collected in ambient air samples in the proximity of oil sands exploration. Quinones were characterized for their diurnal concentration variability, phase partitioning, and molecular size distribution. Gas-phase (GP) and particle-phase (PM) ambient air samples were collected separately in the summer; a lower quinone content was observed in the PM samples from continuous 24-h sampling than from combined 12-h sampling (day and night). The daytime/nocturnal samples demonstrated that nighttime conditions led to lower concentrations and some quinones not being detected. The highest quinone levels were associated with wind directions originating from oil sands exploration sites. The statistical correlation with primary pollutants directly emitted from oil sands industrial activities indicated that the bulk of the detected quinones did not originate directly from primary emission sources and that quinone formation paralleled a reduction in primary source NOx levels. This suggests a secondary chemical transformation of primary pollutants as the origin of the determined quinones. Measurements of 19 quinones included five that have not previously been reported in ambient air or in Standard Reference Material 1649a/1649b and seven that have not been previously measured in ambient air in the underivatized form. This is the first paper to report on quinone characterization in secondary organic aerosols originating from oil sands activities, to distinguish chrysenequinone and anthraquinone positional isomers in ambient air, and to report the requirement of daylight conditions for benzo[a]pyrenequinone and naphthacenequinone to be present in ambient air.

Occurrence and Potential Sources of Quinones Associated with PM2.5 in Guadalajara, Mexico

This study aims to establish the influence of primary emission sources and atmospheric transformation process contributing to the concentrations of quinones associated to particulate matter of less than 2.5 µm (PM2.5) in three sites within the Metropolitan Area of Guadalajara (MAG), namely Centro (CEN), Tlaquepaque (TLA) and Las Águilas (AGU). Environmental levels of quinones extracted from PM2.5 filters were analyzed using Gas Chromatography coupled to Mass Spectrometry (GC-MS). Overall, primary emissions in combination with photochemical and oxidation reactions contribute to the presence of quinones in the urban atmosphere of MAG. It was found that quinones in PM2.5 result from the contributions from direct emission sources by incomplete combustion of fossil fuels such as diesel and gasoline that relate mainly to vehicular activity intensity in the three sampling sites selected. However, this also suggests that the occurrence of quinones in MAG can be related to photochemical transformation of the parent Polycyclic Aromatic Hydrocarbons (PAHs), to chemical reactions with oxygenated species, or a combination of both routes. The higher concentration of 1,4-Chrysenequinone during the rainy season compared to the warm-dry season indicates chemical oxidation of chrysene, since the humidity could favor singlet oxygen collision with parent PAH present in the particle phase. On the contrary, 9,10-Anthraquinone/Anthracene and 1,4-Naftoquinone/Naphthalene ratios were higher during the warm-dry season compared to the rainy season, which might indicate a prevalence of the photochemical formation during the warm-dry season favored by the large solar radiation typical of the season. In addition, the estimated percentage of photochemical formation of 9,10-Phenanthrenequinone showed that the occurrence of this compound in Tlaquepaque (TLA) and Las Águilas (AGU) sites is mainly propagated by conditions of high solar radiation such as in the warm-dry season and during long periods of advection of air masses from emission to the reception areas. This was shown by the direct association between the number hourly back trajectories arriving in the TLA and AGU from Centro and other areas in MAG and the highest photochemical formation percentage.

Characterization of the ambient air content of parent polycyclic aromatic hydrocarbons in the Fort McKay region (Canada)

This study presents the characterization of the gas-particle partition and size distribution of seven parent polycyclic aromatic hydrocarbons (PAHs) in ambient air samples collected in the proximity of oil sands exploration and compares their time-integrated concentration levels with nineteen analogous oxidation products - quinones. Gas-phase (GP) and particle-phase (PM) ambient air aerosol samples that were collected separately in summer for either 24 h or 12 h (day and night) revealed a higher PAH partition in the GP than in the PM, with the distribution over tenfold higher for light over heavy PAHs. Diurnal/nocturnal samples demonstrated that night conditions lead to lower concentrations, linking some of the sources of these compounds with daytime activity emissions. PAHs were observed to transform more efficiently in the GP, and quinone levels increased in the PM with time. Correlation data indicated that parent PAHs originated from primary emission sources associated with oil sand activities and that quinone formation paralleled a reduction in PAH levels. The findings of this study shed new light on characterization of PAHs in the Athabasca oil sands region.

6-Shogaol, an active compound of ginger, alleviates allergic dermatitis-like skin lesions via cytokine inhibition by activating the Nrf2 pathway

Allergic dermatitis (AD) clinically presents with skin erythematous plaques, eruption, and elevated serum IgE, and T helper cell type 2 and 1 (Th2 and Th1) cytokine levels. 6-Shogaol [1-(4-hydroxy-methoxyphenyl)-4-decen-one], a pungent compound isolated from ginger, has shown anti-inflammatory effects, but its inhibitory effects on AD are unknown. The aim of this study was to examine whether 6-shogaol inhibits AD-like skin lesions and their underlying mechanism in vivo and in vitro. An AD-like response was induced by tumor necrosis factor-α (TNF-α)+IFN-γ in human keratinocytes or by 2,4-dinitrochlorobenzene (DNCB) in mice. In vivo, 6-shogaol inhibited the development of DNCB-induced AD-like skin lesions and scratching behavior, and showed significant reduction in Th2/1-mediated inflammatory cytokines, IgE, TNF-α, IFN-γ, thymus and activation-regulated chemokine, IL-1, 4, 12, and 13, cyclooxygenase-2, and nitric oxide synthase levels. In vitro, 6-shogaol inhibited reactive oxygen species (ROS) and mitogen-activated protein kinases (MAPKs) signaling, and increased the levels of total glutathione, heme oxygenase-1, and quinone 1 via nuclear factor erythroid 2 related factor 2 (Nrf2) activation. 6-Shogaol can alleviate AD-like skin lesions by inhibiting immune mediators via regulating the ROS/MAPKs/Nrf2 signaling pathway, and may be an effective alternative therapy for AD.

Method development for the measurement of quinone levels in urine

A method was developed for the quantification of 1–4 ring quinones in urine samples using liquid–liquid extraction followed by analysis with gas chromatography–mass spectrometry. Detection limits for the ten quinones analyzed are in the range 1–2 nmol dm −3. The potential use of this approach to monitor urinary quinone levels was then evaluated in urine samples from both Sprague-Dawley rats and human subjects. Rats were exposed to 9,10-phenanthraquinone (PQ) by both injection and ingestion (mixed with solid food and dissolved in drinking water). Urinary levels of PQ were found to increase by up to a factor of ten compared to control samples, and the levels were found to depend on both the dose and duration of exposure. Samples were also collected and analyzed periodically from human subjects over the course of six months. Eight quinones were detected in the samples, with levels varying from below the detection limit up to 3 μmol dm −3.

Circulating antioxidant profile of pregnant women with asthma

One of the most prevalent complications of pregnancy is asthma which is associated with an increased incidence of intrauterine growth restriction. The mechanisms that affect fetal development in pregnancies complicated by asthma are not clearly defined. Antioxidants are particularly important during pregnancy due to their protective role against a state of high oxidative stress as gestation progresses. The current study was designed to characterise the circulating profile of tocopherols and carotenoids in pregnant women with asthma to determine whether asthma severity and dietary intake were associated with an altered antioxidant profile. Maternal dietary intake and plasma and erythrocyte concentrations of tocopherols and carotenoids were examined in women with (n=84) and without asthma (n=47) at 18, 30 and 36 weeks gestation. Tocopherol and carotenoid levels were related to fetal and birth outcomes. Pregnant women with moderate/severe asthma were found to have increased plasma concentrations of total carotenoids (P<0.05), lutein (P<0.05 and α-tocopherol (P<0.02) late in gestation compared to those women with mild asthma and healthy pregnant controls. Moderate/severe asthmatics had higher erythrocyte α-tocopherol quinone levels early in gestation relative to the controls (P<0.02) but this marker of oxidative stress decreased as gestation progressed. Tocopherols and carotenoids were positively associated with birth weight centile (P<0.05). These findings suggest that the maternal system adjusts antioxidant pathways in response to the presence of a high oxidative load induced by asthma during pregnancy in an attempt to ensure continued fetal growth in an adverse environment.

Increased hippocampal quinone reductase 2 in Alzheimer's disease

Quinone reductase 2 (QR2), a detoxifying cytosolic flavoenzyme, is thought to play an important role in the acquisition and loss of memory [3]. We determined the amount of QR2 in the hippocampus, amygdala, and superior frontal gyrus of Alzheimer's disease (AD) patients with dementia by using western blot analysis. The level of QR2 was significantly higher in the hippocampus of AD patients than in that of the control subjects. The relation between QR2 and AD has not yet been determined; however, our results suggest that the increase in hippocampal QR2 might be a cause of AD or might promote the progression of AD by causing an increase in the toxic quinone levels and consequent loss of cognitive function.

Characterization of the size-distribution of aerosols and particle-bound content of oxygenated PAHs, PAHs, and n-alkanes in urban environments in Afghanistan

Abstract Air pollution is a common problem in mega-cities in Asia, resulting in high levels of particulate matter (PM). In this study, 24 h samples of airborne particulate matter (PM 2.5 and PM 10 ) was collected for two weeks in urban locations in Kabul and Mazar-e Sharif, Afghanistan. The samples were analyzed for twenty n -alkanes, fifteen polycyclic aromatic hydrocarbons (PAHs) and eighteen oxygenated PAHs (oxy-PAHs). The results were compared to a reference location in Umea, Sweden. The main objectives were: to characterize the organic fraction in PM 2.5 , with focus on oxy-PAHs, PAHs and n -alkanes, assess relationships between compound groups, and investigate possible source categories. Mean PM 10 , levels were 260 μg m −3 , and 334 μg m −3 and mean PM 2.5 levels were 86 μg/m 3 and 68 μg m −3 in Kabul and Mazar-e Sharif, respectively. The higher ratio of PM 2.5 to PM 10 in Kabul than Mazar-e Sharif or Umea was reflected in the high number of small particles, as collected by a particle counter. Kabul and Mazar-e Sharif had high levels of PAHs and oxy-PAHs compared to Umea and previously reported data from Western countries. Generally, the highest individual levels of oxy-PAHs were found for ketones (0.27–33 ng m −3 ), whereas the quinone levels were lower (0.027–3.1 ng m −3 ). High correlations ( r > 0.96) between PAHs and oxy-PAHs were found at both locations. Diagnostics for n -alkanes, such as the carbon preference index, and the most abundant species, C max , and the presence of unresolved complex mixture indicated a higher contribution from coal and petroleum sources in Kabul. Models generated by principal component analysis (PCA) and positive matrix factorization (PMF) both suggested separate sources for lower molecular weight n -alkanes and higher molecular weight n -alkanes. The PAHs and the oxy-PAHs were not separated in either the PCA or the PMF models, indicating that they had similar sources and are perhaps relatively unspecific as source markers. Nevertheless, the PAHs and oxy-PAHs were good markers for bad air quality in the urban locations in Afghanistan in comparison to data from Western countries. Based on the models and diagnostic ratios it is suggested that traffic and combustion of coal and biomass were the dominating sources of the high levels of particle-bound organic compounds.