Targeted mutations induced by a single acetylaminofluorene DNA adduct in mammalian cells and bacteria

International Nuclear Information System (INIS)

Moryia, M.; Takeshita, M.; Johnson, F.; Peden, K.; Will, S.; Grollman, A.P.

1988-01-01

Mutagenic specificity of 2-acetylaminofluorene (AAF) has been established in mammalian cells and several strains of bacteria by using a shuttle plasmid vector containing a single N-(deoxyguanosin-8-yl)acetylaminofluorene (C8-dG-AAF) adduct. The nucleotide sequence of the gene conferring tetracycline resistance was modified by conservative codon replacement so as to accommodate the sequence d(CCTTCGCTAC) flanked by two restriction sites, Bsm I and Xho I. The corresponding synthetic oligodeoxynucleotide underwent reaction with 2-(N-acetoxy-N-acetylamino)-fluorene (AAAF), forming a single dG-AAF adduct. This modified oligodeoxynucleotide was hybridized to its complementary strand and ligated between the Bsm I and Xho I sites of the vector. Plasmids containing the C8-dG-AAF adduct were used to transfect simian virus 40-transformed simian kidney (COS-1) cells and to transform several AB strains of Escherichia coli. Colonies containing mutant plasmides were detected by hybridization to 32 P-labeled oligodeoxynucleotides. Presence of the single DNA adduct increased the mutation frequency by 8-fold in both COS cells and E. coli. Over 80% of mutations detected in both systems were targeted and represented G x C → C x G or G x C → T x A transversions or single nucleotide deletions. The authors conclude that modification of a deoxyguanosine residue with AAF preferentially induces mutations targeted at this site when a plasmid containing a single C8-dG-AAF adduct is introduced into mammalian cells or bacteria

Effects of climate-induced changes in isoprene emissions after the eruption of Mount Pinatubo

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P. J. Telford

2010-08-01

Full Text Available In the 1990s the rates of increase of greenhouse gas concentrations, most notably of methane, were observed to change, for reasons that have yet to be fully determined. This period included the eruption of Mt. Pinatubo and an El Niño warm event, both of which affect biogeochemical processes, by changes in temperature, precipitation and radiation. We examine the impact of these changes in climate on global isoprene emissions and the effect these climate dependent emissions have on the hydroxy radical, OH, the dominant sink for methane. We model a reduction of isoprene emissions in the early 1990s, with a maximum decrease of 40 Tg(C/yr in late 1992 and early 1993, a change of 9%. This reduction is caused by the cooler, drier conditions following the eruption of Mt. Pinatubo. Isoprene emissions are reduced both directly, by changes in temperature and a soil moisture dependent suppression factor, and indirectly, through reductions in the total biomass. The reduction in isoprene emissions causes increases of tropospheric OH which lead to an increased sink for methane of up to 5 Tg(CH₄/year, comparable to estimated source changes over the time period studied. There remain many uncertainties in the emission and oxidation of isoprene which may affect the exact size of this effect, but its magnitude is large enough that it should remain important.

Isoprene photochemistry over the Amazon rainforest

Science.gov (United States)

Liu, Yingjun; Brito, Joel; Dorris, Matthew R.; Rivera-Rios, Jean C.; Seco, Roger; Bates, Kelvin H.; Artaxo, Paulo; Duvoisin, Sergio; Keutsch, Frank N.; Kim, Saewung; Goldstein, Allen H.; Guenther, Alex B.; Manzi, Antonio O.; Souza, Rodrigo A. F.; Springston, Stephen R.; Watson, Thomas B.; McKinney, Karena A.

2016-01-01

Isoprene photooxidation is a major driver of atmospheric chemistry over forested regions. Isoprene reacts with hydroxyl radicals (OH) and molecular oxygen to produce isoprene peroxy radicals (ISOPOO). These radicals can react with hydroperoxyl radicals (HO2) to dominantly produce hydroxyhydroperoxides (ISOPOOH). They can also react with nitric oxide (NO) to largely produce methyl vinyl ketone (MVK) and methacrolein (MACR). Unimolecular isomerization and bimolecular reactions with organic peroxy radicals are also possible. There is uncertainty about the relative importance of each of these pathways in the atmosphere and possible changes because of anthropogenic pollution. Herein, measurements of ISOPOOH and MVK + MACR concentrations are reported over the central region of the Amazon basin during the wet season. The research site, downwind of an urban region, intercepted both background and polluted air masses during the GoAmazon2014/5 Experiment. Under background conditions, the confidence interval for the ratio of the ISOPOOH concentration to that of MVK + MACR spanned 0.4–0.6. This result implies a ratio of the reaction rate of ISOPOO with HO2 to that with NO of approximately unity. A value of unity is significantly smaller than simulated at present by global chemical transport models for this important, nominally low-NO, forested region of Earth. Under polluted conditions, when the concentrations of reactive nitrogen compounds were high (>1 ppb), ISOPOOH concentrations dropped below the instrumental detection limit (<60 ppt). This abrupt shift in isoprene photooxidation, sparked by human activities, speaks to ongoing and possible future changes in the photochemistry active over the Amazon rainforest. PMID:27185928

Airborne observations of total RONO2: new constraints on the yield and lifetime of isoprene nitrates

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W. H. Brune

2009-02-01

Full Text Available Formation of isoprene nitrates (INs is an important free radical chain termination step ending production of ozone and possibly affecting formation of secondary organic aerosol. Isoprene nitrates also represent a potentially large, unmeasured contribution to OH reactivity and are a major pathway for the removal of nitrogen oxides from the atmosphere. Current assessments indicate that formation rates of isoprene nitrates are uncertain to a factor of 2–3 and the subsequent fate of isoprene nitrates remains largely unconstrained by laboratory, field or modeling studies. Measurements of total alkyl and multifunctional nitrates (ΣANs, NO2, total peroxy nitrates (ΣPNs, HNO3, CH2O, isoprene and other VOC were obtained from the NASA DC-8 aircraft during summer 2004 over the continental US during the INTEX-NA campaign. These observations represent the first characterization of ΣANs over a wide range of land surface types and in the lower free troposphere. ΣANs were a significant, 12–20%, fraction of NOy throughout the experimental domain and ΣANs were more abundant when isoprene was high. We use the observed hydrocarbon species to calculate the relative contributions of ΣAN precursors to their production. These calculations indicate that isoprene represents at least three quarters of the ΣAN source in the summertime continental boundary layer of the US. An observed correlation between ΣANs and CH2O is used to place constraints on nitrate yields from isoprene oxidation, atmospheric lifetimes of the resulting nitrates and recycling efficiencies of nitrates during subsequent oxidation. We find reasonable fits to the data using sets of production rates, lifetimes and recycling efficiencies of INs as follows (4.4%, 16 h, 97%, (8%, 2.5 h, 79% and (12%, 95 min, 67%. The analysis indicates that the lifetime of ΣANs as a pool of compounds is considerably longer than the lifetime of the individual isoprene nitrates to reaction with OH, implying that

Modelling atmospheric OH-reactivity in a boreal forest ecosystem

DEFF Research Database (Denmark)

Mogensen, D.; Smolander, S.; Sogachev, Andrey

2011-01-01

We have modelled the total atmospheric OH-reactivity in a boreal forest and investigated the individual contributions from gas phase inorganic species, isoprene, monoterpenes, and methane along with other important VOCs. Daily and seasonal variation in OH-reactivity for the year 2008 was examined...

Isoprene photochemistry over the Amazon rainforest.

Science.gov (United States)

Liu, Yingjun; Brito, Joel; Dorris, Matthew R; Rivera-Rios, Jean C; Seco, Roger; Bates, Kelvin H; Artaxo, Paulo; Duvoisin, Sergio; Keutsch, Frank N; Kim, Saewung; Goldstein, Allen H; Guenther, Alex B; Manzi, Antonio O; Souza, Rodrigo A F; Springston, Stephen R; Watson, Thomas B; McKinney, Karena A; Martin, Scot T

2016-05-31

Isoprene photooxidation is a major driver of atmospheric chemistry over forested regions. Isoprene reacts with hydroxyl radicals (OH) and molecular oxygen to produce isoprene peroxy radicals (ISOPOO). These radicals can react with hydroperoxyl radicals (HO2) to dominantly produce hydroxyhydroperoxides (ISOPOOH). They can also react with nitric oxide (NO) to largely produce methyl vinyl ketone (MVK) and methacrolein (MACR). Unimolecular isomerization and bimolecular reactions with organic peroxy radicals are also possible. There is uncertainty about the relative importance of each of these pathways in the atmosphere and possible changes because of anthropogenic pollution. Herein, measurements of ISOPOOH and MVK + MACR concentrations are reported over the central region of the Amazon basin during the wet season. The research site, downwind of an urban region, intercepted both background and polluted air masses during the GoAmazon2014/5 Experiment. Under background conditions, the confidence interval for the ratio of the ISOPOOH concentration to that of MVK + MACR spanned 0.4-0.6. This result implies a ratio of the reaction rate of ISOPOO with HO2 to that with NO of approximately unity. A value of unity is significantly smaller than simulated at present by global chemical transport models for this important, nominally low-NO, forested region of Earth. Under polluted conditions, when the concentrations of reactive nitrogen compounds were high (>1 ppb), ISOPOOH concentrations dropped below the instrumental detection limit (Amazon rainforest.

Formaldehyde production from isoprene oxidation across NOx regimes

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G. M. Wolfe

2016-03-01

Full Text Available The chemical link between isoprene and formaldehyde (HCHO is a strong, nonlinear function of NOx (i.e., NO + NO2. This relationship is a linchpin for top-down isoprene emission inventory verification from orbital HCHO column observations. It is also a benchmark for overall photochemical mechanism performance with regard to VOC oxidation. Using a comprehensive suite of airborne in situ observations over the southeast US, we quantify HCHO production across the urban–rural spectrum. Analysis of isoprene and its major first-generation oxidation products allows us to define both a "prompt" yield of HCHO (molecules of HCHO produced per molecule of freshly emitted isoprene and the background HCHO mixing ratio (from oxidation of longer-lived hydrocarbons. Over the range of observed NOx values (roughly 0.1–2 ppbv, the prompt yield increases by a factor of 3 (from 0.3 to 0.9 ppbv ppbv−1, while background HCHO increases by a factor of 2 (from 1.6 to 3.3 ppbv. We apply the same method to evaluate the performance of both a global chemical transport model (AM3 and a measurement-constrained 0-D steady-state box model. Both models reproduce the NOx dependence of the prompt HCHO yield, illustrating that models with updated isoprene oxidation mechanisms can adequately capture the link between HCHO and recent isoprene emissions. On the other hand, both models underestimate background HCHO mixing ratios, suggesting missing HCHO precursors, inadequate representation of later-generation isoprene degradation and/or underestimated hydroxyl radical concentrations. Detailed process rates from the box model simulation demonstrate a 3-fold increase in HCHO production across the range of observed NOx values, driven by a 100 % increase in OH and a 40 % increase in branching of organic peroxy radical reactions to produce HCHO.

Evidence for phosphorus bonding in phosphorus trichloride-methanol adduct: a matrix isolation infrared and ab initio computational study.

Science.gov (United States)

Joshi, Prasad Ramesh; Ramanathan, N; Sundararajan, K; Sankaran, K

2015-04-09

The weak interaction between PCl3 and CH3OH was investigated using matrix isolation infrared spectroscopy and ab initio computations. In a nitrogen matrix at low temperature, the noncovalent adduct was generated and characterized using Fourier transform infrared spectroscopy. Computations were performed at B3LYP/6-311++G(d,p), B3LYP/aug-cc-pVDZ, and MP2/6-311++G(d,p) levels of theory to optimize the possible geometries of PCl3-CH3OH adducts. Computations revealed two minima on the potential energy surface, of which, the global minimum is stabilized by a noncovalent P···O interaction, known as a pnictogen bonding (phosphorus bonding or P-bonding). The local minimum corresponded to a cyclic adduct, stabilized by the conventional hydrogen bonding (Cl···H-O and Cl···H-C interactions). Experimentally, 1:1 P-bonded PCl3-CH3OH adduct in nitrogen matrix was identified, where shifts in the P-Cl modes of PCl3, O-C, and O-H modes of CH3OH submolecules were observed. The observed vibrational frequencies of the P-bonded adduct in a nitrogen matrix agreed well with the computed frequencies. Furthermore, computations also predicted that the P-bonded adduct is stronger than H-bonded adduct by ∼1.56 kcal/mol. Atoms in molecules and natural bond orbital analyses were performed to understand the nature of interactions and effect of charge transfer interaction on the stability of the adducts.

Biogenic and anthropogenic isoprene in the near-surface urban atmosphere--a case study in Essen, Germany.

Science.gov (United States)

Wagner, Patrick; Kuttler, Wilhelm

2014-03-15

Isoprene is emitted in large quantities by vegetation, exhaled by human beings and released in small quantities by road traffic. As a result of its high reactivity, isoprene is an important ozone precursor in the troposphere and can play a key role in atmospheric chemistry. Measurements of isoprene in urban areas in Central Europe are scarce. Thus, in Essen, Germany, the isoprene concentration was measured at various sites during different seasons using two compact online GC-PID systems. Isoprene concentrations were compared with those of benzene and toluene, which represent typical anthropogenic VOCs. In the summer, the diurnal variation in isoprene concentration was dependent on the biogenic emissions in the city. It was found that its maximum concentration occurred during the day, in contrast to the benzene and toluene concentrations. During the measurement period in the summer of 2012, the average hourly isoprene concentrations reached 0.13 to 0.17 ppb between 10 and 20 LST. At high air temperatures, the isoprene concentration exceeded the benzene and toluene concentrations at many of the sites. Isoprene became more important than toluene with regard to ozone formation in the city area during the afternoon hours of summer days with high air temperatures. This finding was demonstrated by the contributions to OH reactivity and ozone-forming potential. It contradicts the results of other studies, which were based on daily or seasonal average values. With an isoprene/benzene ratio of 0.02, the contribution of anthropogenic isoprene decreased substantially to a very low level during the last 20 years in Central Europe due to a strong reduction in road traffic emissions. In the vicinity of many people, isoprene concentrations of up to 0.54 ppb and isoprene/benzene ratios of up to 1.34 were found in the atmosphere due to isoprene exhaled by humans. Copyright © 2013. Published by Elsevier B.V.

DNA adduct formation by the ubiquitous environmental pollutant 3-nitrobenzanthrone and its metabolites in rats

International Nuclear Information System (INIS)

Arlt, Volker M.; Sorg, Bernd L.; Osborne, Martin; Hewer, Alan; Seidel, Albrecht; Schmeiser, Heinz H.; Phillips, David H.

2003-01-01

Diesel exhaust is known to induce tumours in animals and is suspected of being carcinogenic in humans. Of the compounds found in diesel exhaust, 3-nitrobenzanthrone (3-NBA) is an extremely potent mutagen and suspected human carcinogen forming multiple DNA adducts in vitro. 3-Aminobenzanthrone (3-ABA), 3-acetylaminobenzanthrone (3-Ac-ABA), and N-acetyl-N-hydroxy-3-aminobenzanthrone (N-Ac-N-OH-ABA) were identified as 3-NBA metabolites. In order to gain insight into the pathways of metabolic activation leading to 3-NBA-derived DNA adducts we treated Wistar rats intraperitoneally with 2 mg/kg body weight of 3-NBA, 3-ABA, 3-Ac-ABA, or N-Ac-N-OH-ABA and compared DNA adducts present in different organs. With each compound either four or five DNA adduct spots were detected by TLC in all tissues examined (lung, liver, kidney, heart, pancreas, and colon) using the nuclease P1 or butanol enrichment version of the 32 P-postlabelling method, respectively. Using HPLC co-chromatographic analysis we showed that all major 3-NBA-DNA adducts produced in vivo in rats are derived from reductive metabolites bound to purine bases and lack an N-acetyl group. Our results indicate that 3-NBA metabolites (3-ABA, 3-Ac-ABA and N-Ac-N-OH-ABA) undergo several biotransformations and that N-hydroxy-3-aminobenzanthrone (N-OH-ABA) appears to be the common intermediate in 3-NBA-derived DNA adduct formation. Therefore, 3-NBA-DNA adducts are useful biomarkers for exposure to 3-NBA and its metabolites and may help to identify enzymes involved in their metabolic activation

o-Toluidine blood protein adducts: HPLC analysis with fluorescence detection after a single dose in the adult male rat

International Nuclear Information System (INIS)

Cheever, K.L.; DeBord, G.D.; Swearengin, T.F.

1991-01-01

Hemoglobin (Hb) and albumin (Alb) adducts of the suspect human carcinogen o-toluidine (OT) were quantified in blood samples collected from rats after a single i.p. injection. Mild alkaline hydrolysis of Hb-adducted [ 14 C]OT followed by extraction with ethylacetate resulted in recovery of 66% of the bound radioactivity. HPLC analysis revealed a single radiolabeled peak which was identified as OT by GC-MS. In subsequent experiments the Hb and Alb adduct levels were determined by HPLC analysis of this split product using fluorescence detection. 4-Ethylaniline was used as internal standard. The detection limit for OT was approximately 450 pg/injection of 5 pmol. mg Hb. Mean adduct levels for Hb increased rapidly over the first 4 hr with the highest (ng/mg Hb ± SD) 3.7 ± 0.5 detected 24 hr after OT (50 mg/kg body wt). In contrast, adduct levels for pooled Alb samples increased from 0.7 ng/mg Alb at 2 hr to 2.5 ng/mg Alb at 4 hr, but were not detectable 24 hr after OT (50 mg/kg body wt). In contrast, adduct levels for pooled Alb samples increased from 0.7 ng/mg Alb at 2 hr to 2.5 ng/mg Alb at 4 hr, but were not detectable 24 hr after dosing. Hb adducts showed a linear relationship for OT doses of 10, 20, 40, 50, and 100 mg/kg body wt. The Hb adduct t 1/2 (11.2 days) was determined after a single 100 mg/kg OT dose. Hb adduct levels were quantifiable (1.3 ± 0.2 ng/mg Hb) by HPLC/fluorescence 28 days after 100 mg/kg OT

The long persistence of pyrrolizidine alkaloid-derived DNA adducts in vivo: kinetic study following single and multiple exposures in male ICR mice.

Science.gov (United States)

Zhu, Lin; Xue, Junyi; Xia, Qingsu; Fu, Peter P; Lin, Ge

2017-02-01

Pyrrolizidine alkaloid (PA)-containing plants are widespread in the world and the most common poisonous plants affecting livestock, wildlife, and humans. Our previous studies demonstrated that PA-derived DNA adducts can potentially be a common biological biomarker of PA-induced liver tumor formation. In order to validate the use of these PA-derived DNA adducts as a biomarker, it is necessary to understand the basic kinetics of the PA-derived DNA adducts formed in vivo. In this study, we studied the dose-dependent response and kinetics of PA-derived DNA adduct formation and removal in male ICR mice orally administered with a single dose (40 mg/kg) or multiple doses (10 mg/kg/day) of retrorsine, a representative carcinogenic PA. In the single-dose exposure, the PA-derived DNA adducts exhibited dose-dependent linearity and persisted for up to 4 weeks. The removal of the adducts following a single-dose exposure to retrorsine was biphasic with half-lives of 9 h (t 1/2α ) and 301 h (~12.5 days, t 1/2β ). In the 8-week multiple exposure study, a marked accumulation of PA-derived DNA adducts without attaining a steady state was observed. The removal of adducts after the multiple exposure also demonstrated a biphasic pattern but with much extended half-lives of 176 h (~7.33 days, t 1/2α ) and 1736 h (~72.3 days, t 1/2β ). The lifetime of PA-derived DNA adducts was more than 8 weeks following the multiple-dose treatment. The significant persistence of PA-derived DNA adducts in vivo supports their role in serving as a biomarker of PA exposure.

In situ measurements of isoprene and monoterpenes within a south-east Asian tropical rainforest

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C. E. Jones

2011-07-01

Full Text Available Biogenic volatile organic compounds (BVOCs emitted from tropical rainforests comprise a substantial fraction of global atmospheric VOC emissions, however there are only relatively limited measurements of these species in tropical rainforest regions. We present observations of isoprene, α-pinene, camphene, Δ-3-carene, γ-terpinene and limonene, as well as oxygenated VOCs (OVOCs of biogenic origin such as methacrolein, in ambient air above a tropical rainforest in Malaysian Borneo during the Oxidant and Particle Photochemical Processes above a south-east Asian tropical rainforest (OP3 project in 2008. Daytime composition was dominated by isoprene, with an average mixing ratio of the order of ~1 ppb. γ-terpinene, limonene and camphene were the most abundant monoterpenes, with average daytime mixing ratios of 102, 71 and 66 ppt respectively, and with an average monoterpene toisoprene ratio of 0.3 during sunlit hours, compared to 2.0 at night. Limonene and camphene abundances were seen to be related to both temperature and light conditions. In contrast, γ-terpinene emission continued into the late afternoon/evening, under relatively low temperature and light conditions. The contributions of isoprene, monoterpenes and other classes of VOC to the volatile carbon budget and OH reactivity have been summarised for this rainforest location. We observe good agreement between surface and aircraft measurements of boundary layer isoprene and methacrolein above the natural rainforest, suggesting that the ground-level observations are broadly representative of isoprene emissions from this region.

Isoprene emission from Indian trees

Science.gov (United States)

Varshney, C. K.; Singh, Abhai Pratap

2003-12-01

Isoprene is the most dominant non-methane volatile organic compound (NMVOC) emitted by plants. NMVOCs play an important role in regulating the composition of atmospheric trace gases including global concentration of tropospheric ozone. Our present knowledge about NMVOCs emission is mainly from studies on temperate tree species. So far information on biogenic NMVOCs emission from tropical tree species is limited. In this study, isoprene emission rates from 40 tropical Indian tree species belonging to 33 genera and 17 families were measured for the first time using a dynamic flow through enclosure chamber technique. The isoprene emission rate from plants (30°C and PAR 1000 μmolm-2s-1) ranged from undetectable to 81.5 μg g-1 h-1 and values were found to be comparable with other studies on tropical tree species. Tree species screened for isoprene emission in the present study may be grouped into the four categories, proposed by [2001], namely, 18 species were negligible or BDL isoprene emitting (Morus alba Linn., which were earlier reported as BDL or non isoprene emitters in US [, 1998; , 2001] were found to be appreciably high isoprene emitters (0.61-21.60 μg g-1 h-1) in the present study.

Effect of isoprene emissions from major forests on ozone formation in the city of Shanghai, China

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F. Geng

2011-10-01

Full Text Available Ambient surface level concentrations of isoprene (C₅H₈ were measured in the major forest regions located south of Shanghai, China. Because there is a large coverage of broad-leaved trees in this region, high concentrations of isoprene were measured, ranging from 1 to 6 ppbv. A regional dynamical/chemical model (WRF-Chem is applied for studying the effect of such high concentrations of isoprene on the ozone production in the city of Shanghai. The evaluation of the model shows that the calculated isoprene concentrations agree with the measured concentrations when the measured isoprene concentrations are lower than 3 ppb, but underestimate the measurements when the measured values are higher than 3 ppb. Isoprene was underestimated only at sampling sites near large bamboo plantations, a high isoprene source, indicating the need to include geospatially resolved bamboo distributions in the biogenic emission model. The assessment of the impact of isoprene on ozone formation suggests that the concentrations of peroxy radicals (RO₂ are significantly enhanced due to the oxidation of isoprene, with a maximum of 30 ppt. However, the enhancement of RO₂ is confined to the forested regions. Because the concentrations of NO_x were low in the forest regions, the ozone production due to the oxidation of isoprene (C₅H₈ + OH → → RO₂ + NO → → O₃ is low (less than 2–3 ppb h⁻¹. The calculation further suggests that the oxidation of isoprene leads to the enhancement of carbonyls (such as formaldehyde and acetaldehyde in the regions downwind of the forests, due to continuous oxidation of isoprene in the forest air. As a result, the concentrations of HO₂ radical are enhanced, resulting from the photo-disassociation of formaldehyde and acetaldehyde. Because the enhancement of HO₂ radical occurs in regions downwind of the forests

Self-assembly in solvates of 2,4-diamino-6-(4-methyl- phenyl)-1,3,5-triazine and in its molecular adducts with some aliphatic dicarboxylic acids

Science.gov (United States)

Nandy, Purnendu; Nayak, Amrita; Biswas, Sharmita Nandy; Pedireddi, V. R.

2016-03-01

Solid state structures of 2,4-diamino-6-(4-methylphenyl)-1,3,5-triazine, 1, in the form of methanol and dimethylsulfoxide (DMSO) solvates, as well as supramolecular assemblies of 1 with various aliphatic dicarboxylic acids, oxalic (a), malonic (b), succinic (c), glutaric (d) and adipic (e) have been reported. Analysis of the assemblies has been carried out by single crystal X-ray diffraction and thermal methods. Triazine 1 yields anhydrous molecular adducts with acids a-d, upon co-crystallization either from CH3OH and DMSO solvents. However acid e gives anhydrous adduct from DMSO solvent, while it gives a methanol adduct from CH3OH. Structure determination reveals that molecular adducts 1a, 1d and 1e are in a 2:1 ratio of 1 and the corresponding acid. However the ratio is 1:1, in 1b, perhaps due to the involvement of one of the acid groups in the intramolecular hydrogen bonding and in adduct 1c the ratio observed is 3:2. Structural features in all these assemblies have been rationalised in terms of various recognition patterns formed between the acceptor and donor groups. A noteworthy feature is that -COOH groups in acid a establish interaction with 1 through amino groups, while such interactions are observed to be through hetero -N atoms in case of the acids b-e.

Direct observation of OH production from the ozonolysis of olefins

Science.gov (United States)

Donahue, Neil M.; Kroll, Jesse H.; Anderson, James G.; Demerjian, Kenneth L.

Ozone olefin reactions may be a significant source of OH in the urban atmosphere, but current evidence for OH production is indirect and contested. We report the first direct observation of OH radicals from the reaction of ozone with a series of olefins (ethene, isoprene, trans-2-butene and 2,3 dimethyl-2-butene) in 4-6 torr of nitrogen. Using LIF to directly observe the steady-state of OH produced by the initial ozone-olefin reaction and subsequently destroyed by the OH-olefin reaction, we are able to establish OH yields broadly consistent with indirect values. The identification of the OH is unequivocal, and there is no indication that it is produced by a secondary process. To support these observations, we present a complete ab-initio potential energy surface for the O3-ethene reaction, extending from the reactants to available products.

Comprehensive measurements of atmospheric OH reactivity and trace species within a suburban forest near Tokyo during AQUAS-TAMA campaign

Science.gov (United States)

Ramasamy, Sathiyamurthi; Nagai, Yoshihide; Takeuchi, Nobuhiro; Yamasaki, Shohei; Shoji, Koki; Ida, Akira; Jones, Charlotte; Tsurumaru, Hiroshi; Suzuki, Yuhi; Yoshino, Ayako; Shimada, Kojiro; Nakashima, Yoshihiro; Kato, Shungo; Hatakeyama, Shiro; Matsuda, Kazuhide; Kajii, Yoshizumi

2018-07-01

Total OH reactivity, which gives the instantaneous loss rate of OH radicals due to reactive species, is an invaluable technique to understand regional air quality, as it gives the overall reactivity of the air mass, the fraction of each trace species reactive to OH, the fraction of missing sinks, O3 formation potential, etc. Total OH reactivity measurement was conducted in a small suburban forest located ∼30 km from Tokyo during the air quality study at field museum TAMA (AQUAS-TAMA) campaign in early autumn 2012 and summer 2013. The average measured OH reactivities during that autumn and summer were 7.4 s-1 and 11.4 s-1, respectively. In summer, isoprene was the major contributor, accounting for 28.2% of the OH reactivity, as a result of enhanced light-dependent biogenic emission, whereas NO2 was major contributor in autumn, accounting for 19.6%, due to the diminished contribution from isoprene as a result of lower solar strength. Higher missing OH reactivity 34% was determined in summer, and linear regression analysis showed that oxygenated VOCs could be the potential candidates for missing OH reactivity. Lower missing OH reactivity 25% was determined in autumn and it was significantly reduced (11%) if the interference of peroxy radicals to the measured OH reactivity were considered.

The reactions of p-nitroacetophenone with H and OH radicals

International Nuclear Information System (INIS)

Whillans, D.W.

1977-01-01

Reactions of the radiation sensitizer p-nitroacetophenone (PNAP) with H and OH radicals have been studied in detail. PNAP reacts with OH (k = (3.3 + 0.3) X 10 9 dm 3 mol -1 s -1 ), presumably in the main by ring addition, to produce a relatively weak absorption with a minor peak at 410 nm (epsilon approximately 2,000 dm 3 mol -1 cm -1 ). In contrast the electron adduct has a very strong absorption with peaks at 350 nm (epsilon approximately 18,200 dm 3 mol -1 cm -1 ) and 550 nm (epsilon approximately 2650 dm 3 mol -1 cm -1 ), in good agreement with literature values. At pH 1 the protonated adduct shows a single peak at 330 nm (epsilon approximately 20,500 dm 3 mol -1 cm -1 ). The spectra produced by reaction of PNAP with H atoms (k = (6 + - 0. 5) x 10 8 dm 3 mol -1 s -1 ) is intermediate between those with OH and with e - sub(aq), with peaks at 350 (epsilon approximately 7100 dm 3 mol -1 cm -1 ) and 550 nm (750 dm 3 mol -1 cm -1 ) at neutral pH and near 325 nm (epsilon approximately 7100 dm 3 mol -1 cm -1 ) at pH 1, but with significant shoulders near 410 nm. These data are consistent with a mechanism whereby H atoms react partially by addition to the nitro group (approximately 30%) and partially by ring addition (approximately 70%). (author)

Total OH reactivity study from VOC photochemical oxidation in the SAPHIR chamber

Science.gov (United States)

Yu, Z.; Tillmann, R.; Hohaus, T.; Fuchs, H.; Novelli, A.; Wegener, R.; Kaminski, M.; Schmitt, S. H.; Wahner, A.; Kiendler-Scharr, A.

2015-12-01

It is well known that hydroxyl radicals (OH) act as a dominant reactive species in the degradation of VOCs in the atmosphere. In recent field studies, directly measured total OH reactivity often showed poor agreement with OH reactivity calculated from VOC measurements (e.g. Nölscher et al., 2013; Lu et al., 2012a). This "missing OH reactivity" is attributed to unaccounted biogenic VOC emissions and/or oxidation products. The comparison of total OH reactivity being directly measured and calculated from single component measurements of VOCs and their oxidation products gives us a further understanding on the source of unmeasured reactive species in the atmosphere. This allows also the determination of the magnitude of the contribution of primary VOC emissions and their oxidation products to the missing OH reactivity. A series of experiments was carried out in the atmosphere simulation chamber SAPHIR in Jülich, Germany, to explore in detail the photochemical degradation of VOCs (isoprene, ß-pinene, limonene, and D6-benzene) by OH. The total OH reactivity was determined from the measurement of VOCs and their oxidation products by a Proton Transfer Reaction Time of Flight Mass Spectrometer (PTR-TOF-MS) with a GC/MS/FID system, and directly measured by a laser-induced fluorescence (LIF) at the same time. The comparison between these two total OH reactivity measurements showed an increase of missing OH reactivity in the presence of oxidation products of VOCs, indicating a strong contribution to missing OH reactivity from uncharacterized oxidation products.

Formation of nitro products from the gas-phase OH radical-initiated reactions of toluene, naphthalene, and biphenyl: effect of NO2 concentration.

Science.gov (United States)

Nishino, Noriko; Atkinson, Roger; Arey, Janet

2008-12-15

Aromatic hydrocarbons, including polycyclic aromatic hydrocarbons (PAHs), are released into the atmosphere principally during incomplete combustion and account for approximately 20% of nonmethane organic compounds in urban air. Reaction with OH radicals is the dominant atmospheric chemical loss process for aromatic hydrocarbons, leading mainly to the formation of an OH-aromatic or OH-PAH adduct which then reacts with O2 and/or NO2. For OH-monocyclic aromatic adducts, reaction with O2 dominates under atmospheric conditions; however, no data are available concerning the relative importance of reactions of OH-PAH adducts with O2 and NO2. We have measured formation yields of 3-nitrotoluene, 1- and 2-nitronaphthalene, and 3-nitrobiphenyl from the OH radical-initiated reactions of toluene, naphthalene, and biphenyl as a function of NO2 concentration. Our data showthatthe OH-aromatic adduct reactions with O2 and NO2 are of equal importance in the atmosphere at NO2 mixing ratios of approximately 3.3 ppmV for toluene, approximately 0.06 ppmV for naphthalene, and approximately 0.6 ppmV for biphenyl. Ambient concentrations of toluene, naphthalene, and biphenyl and their nitrated products measured at a site in the Los Angeles air basin are consistent with our laboratory measurements.

Experimental and theoretical studies of the reaction of the OH radical with alkyl sulfides: 3. Kinetics and mechanism of the OH initiated oxidation of dimethyl, dipropyl, and dibutyl sulfides: reactivity trends in the alkyl sulfides and development of a predictive expression for the reaction of OH with DMS.

Science.gov (United States)

Williams, M B; Campuzano-Jost, P; Hynes, A J; Pounds, A J

2009-06-18

A pulsed laser photolysis-pulsed laser-induced fluorescence technique has been employed to measure rate coefficients for the OH-initiated oxidation of dimethyl sulfide (DMS), its deuterated analog (DMS-d(6)), dipropyl sulfide (DPS), and dibutyl sulfide (DBS). Effective rate coefficients have been measured as a function of the partial pressure of O(2) over the temperature range of 240-295 K and at 200 and 600 Torr total pressure. We report the first observations of an O(2) enhancement in the effective rate coefficients for the reactions of OH with DPS and DBS. All observations are consistent with oxidation proceeding via a two-channel oxidation mechanism involving abstraction and addition channels. Structures and thermochemistry of the DPSOH and DBSOH adducts were calculated. Calculated bond strengths of adducts increase with alkyl substitution but are comparable to that of the DMSOH adduct and are consistent with experimental observations. Reactivity trends across the series of alkyl sulfide (C(2)-C(8)) reactions are analyzed. All reactions proceed via a two-channel mechanism involving either an H-atom abstraction or the formation of an OH adduct that can then react with O(2). Measurements presented in this work, in conjunction with previous measurements, have been used to develop a predictive expression for the OH-initiated oxidation of DMS. This expression is based on the elementary rate coefficients in the two-channel mechanism. The expression can calculate the effective rate coefficient for the reaction of OH with DMS over the range of 200-300 K, 0-760 Torr, and 0-100% partial pressure of O(2). This expression expands on previously published work but is applicable to DMS oxidation throughout the troposphere.

Reactions of OH Radicals with Tris (1,10-Phenanthroline) Iron (II) Studied by Pulse Radiolysis

DEFF Research Database (Denmark)

Siekierska Floryan, E.; Pagsberg, Palle Bjørn

1976-01-01

The reaction of OH radicals with aqueous tris(1,10-phenanthroline)iron(II) leads to the formation of an adduct, which exhibits a broad absorption band at rmpH = 6, λmax = 460 nm, and epsilon (Porson)460 = 6700 (molar, decadic, 1 mol−1 cm−1). The rate of formation of the adduct is first order...... in complex concentration with a bimolecular rate constant Image independent of pH in the range pH 3–11. The adduct decays by mixed-order kinetics, but at 310 nm a second-order formation of a decay product can be directly observed. The reaction of OH radicals with aqueous 1,10-phenanthroline leads also...... to the formation of an adduct which absorbs in the whole visible region with a maximum at 425 nm and ε425 = 2612 (molar, decadic, 1 mol−1 cm−1) in neutral solution. The adduct exhibits a red shift in acidic and alkaline media. The formation is first order in 1,10-phenanthroline with a bimolecular rate constant...

Comparison of OH concentration measurements by DOAS and LIF during SAPHIR chamber experiments at high OH reactivity and low NO concentration

Directory of Open Access Journals (Sweden)

H. Fuchs

2012-07-01

Full Text Available During recent field campaigns, hydroxyl radical (OH concentrations that were measured by laser-induced fluorescence (LIF were up to a factor of ten larger than predicted by current chemical models for conditions of high OH reactivity and low NO concentration. These discrepancies, which were observed in forests and urban-influenced rural environments, are so far not entirely understood. In summer 2011, a series of experiments was carried out in the atmosphere simulation chamber SAPHIR in Jülich, Germany, in order to investigate the photochemical degradation of isoprene, methyl-vinyl ketone (MVK, methacrolein (MACR and aromatic compounds by OH. Conditions were similar to those experienced during the PRIDE-PRD2006 campaign in the Pearl River Delta (PRD, China, in 2006, where a large difference between OH measurements and model predictions was found. During experiments in SAPHIR, OH was simultaneously detected by two independent instruments: LIF and differential optical absorption spectroscopy (DOAS. Because DOAS is an inherently calibration-free technique, DOAS measurements are regarded as a reference standard. The comparison of the two techniques was used to investigate potential artifacts in the LIF measurements for PRD-like conditions of OH reactivities of 10 to 30 s⁻¹ and NO mixing ratios of 0.1 to 0.3 ppbv. The analysis of twenty experiment days shows good agreement. The linear regression of the combined data set (averaged to the DOAS time resolution, 2495 data points yields a slope of 1.02 ± 0.01 with an intercept of (0.10 ± 0.03 × 10⁶ cm⁻³ and a linear correlation coefficient of R² = 0.86. This indicates that the sensitivity of the LIF instrument is well-defined by its calibration procedure. No hints for artifacts are observed for isoprene, MACR, and different aromatic compounds. LIF measurements were approximately 30–40% (median larger than those by DOAS after MVK (20 ppbv and

VIIRS Marine Isoprene Product and Initial Applications

Science.gov (United States)

Tong, D.; Wang, M.; Wang, B.; Pan, L.; Lee, P.; Goldberg, M.

2017-12-01

Isoprene is a reactive biogenic hydrocarbon that affects atmospheric chemistry, aerosol loading, and cloud formation. We have developed a marine isoprene emission algorithm based on ocean color data from the Visible Infrared Imaging Radiometer Suite (VIIRS) onboard the Suomi National Polar-orbiting Partnership (SNPP). and global meteorology simulated by NOAA Global Forecasting System (GFS). This algorithm is implemented to generate a multi-year data record (2012-2015) of marine isoprene. The product was validated using historic ocean observations of marine isoprene, as well as in-situ data collected during two recent cruises (SPACES/OASIS in 2014 and ASTRA-OMZ in 2015). Result shows that the VIIRS product has captured the seasonal and spatial variability of global oceanic isoprene emission, which is controlled by a myriad of biological and environmental variables including chlorophyll-a concentration, phytoplankton functional types, seawater light attenuation rate, wind speed, and sea surface temperature. The VIIRS isoprene emission displays considerable seasonal and spatial variations, with peaks in spring over seawater abundant with nutrient inputs. Year to year variations are small, with the annual global emissions ranging from 0.20 to 0.25 Tg C/yr. This new dataset provides the first multi-year observations of global isoprene emissions that can be used to study a variety of environmental issues such as coastal air quality, global aerosol, and cloud formation. Some "early-adopter" applications of this product are briefly discussed.

Isoprene emission from tropical tree species

International Nuclear Information System (INIS)

Padhy, P.K.; Varshney, C.K.

2005-01-01

Foliar emission of isoprene was measured in nine commonly growing tree species of Delhi, India. Dynamic flow enclosure technique was used and gas samples were collected onto Tenax-GC/Carboseive cartridges, which were then attached to the sample injection system in the gas chromatograph (GC). Eluting compounds were analysed using a flame ionisation detector (FID). Out of the nine tree species, isoprene emission was found in six species (Eucalyptus sp., Ficus benghalensis, Ficus religiosa, Mangifera indica, Melia azedarach, and Syzygium jambolanum), whereas, in the remaining three tree species (Alstonia scholaris, Azadirachta indica, and Cassia fistula) no isoprene emission was detected or the levels of emission were negligible or below the detection limit (BDL). Among six tree species, the highest hourly emission (10.2±6.8 μg g -1 leaf dry weight, average of five seasons) was observed in Ficus religiosa, while minimum emission was from Melia azedarach (2.2±4.9 μg g -1 leaf dry weight, average of five seasons). Isoprene emission (average of six species), over five seasons, was found to vary between 3.9 and 8.5 μg g -1 leaf dry weight during the rainy season. In addition, significant diurnal variation in isoprene emission was observed in each species. The preliminary estimate made in this study on the annual biogenic VOC emission from India may probably be the first of its kind from this part of the world. - Isoprene flux (diurnal and seasonal) from some tropical tree species was estimated and a regional comparison was made

Isoprene emission from tropical tree species

Energy Technology Data Exchange (ETDEWEB)

Padhy, P.K. [School of Environmental Sciences, Jawaharlal Nehru University, New Delhi 110 067 (India)]. E-mail: padhypk2003@yahoo.com; Varshney, C.K. [School of Environmental Sciences, Jawaharlal Nehru University, New Delhi 110 067 (India)

2005-05-01

Foliar emission of isoprene was measured in nine commonly growing tree species of Delhi, India. Dynamic flow enclosure technique was used and gas samples were collected onto Tenax-GC/Carboseive cartridges, which were then attached to the sample injection system in the gas chromatograph (GC). Eluting compounds were analysed using a flame ionisation detector (FID). Out of the nine tree species, isoprene emission was found in six species (Eucalyptus sp., Ficus benghalensis, Ficus religiosa, Mangifera indica, Melia azedarach, and Syzygium jambolanum), whereas, in the remaining three tree species (Alstonia scholaris, Azadirachta indica, and Cassia fistula) no isoprene emission was detected or the levels of emission were negligible or below the detection limit (BDL). Among six tree species, the highest hourly emission (10.2{+-}6.8 {mu}g g{sup -1} leaf dry weight, average of five seasons) was observed in Ficus religiosa, while minimum emission was from Melia azedarach (2.2{+-}4.9 {mu}g g{sup -1} leaf dry weight, average of five seasons). Isoprene emission (average of six species), over five seasons, was found to vary between 3.9 and 8.5 {mu}g g{sup -1} leaf dry weight during the rainy season. In addition, significant diurnal variation in isoprene emission was observed in each species. The preliminary estimate made in this study on the annual biogenic VOC emission from India may probably be the first of its kind from this part of the world. - Isoprene flux (diurnal and seasonal) from some tropical tree species was estimated and a regional comparison was made.

Atmospheric fates of Criegee intermediates in the ozonolysis of isoprene.

Science.gov (United States)

Nguyen, Tran B; Tyndall, Geoffrey S; Crounse, John D; Teng, Alexander P; Bates, Kelvin H; Schwantes, Rebecca H; Coggon, Matthew M; Zhang, Li; Feiner, Philip; Milller, David O; Skog, Kate M; Rivera-Rios, Jean C; Dorris, Matthew; Olson, Kevin F; Koss, Abigail; Wild, Robert J; Brown, Steven S; Goldstein, Allen H; de Gouw, Joost A; Brune, William H; Keutsch, Frank N; Seinfeld, John H; Wennberg, Paul O

2016-04-21

We use a large laboratory, modeling, and field dataset to investigate the isoprene + O3 reaction, with the goal of better understanding the fates of the C1 and C4 Criegee intermediates in the atmosphere. Although ozonolysis can produce several distinct Criegee intermediates, the C1 stabilized Criegee (CH2OO, 61 ± 9%) is the only one observed to react bimolecularly. We suggest that the C4 Criegees have a low stabilization fraction and propose pathways for their decomposition. Both prompt and non-prompt reactions are important in the production of OH (28% ± 5%) and formaldehyde (81% ± 16%). The yields of unimolecular products (OH, formaldehyde, methacrolein (42 ± 6%) and methyl vinyl ketone (18 ± 6%)) are fairly insensitive to water, i.e., changes in yields in response to water vapor (≤4% absolute) are within the error of the analysis. We propose a comprehensive reaction mechanism that can be incorporated into atmospheric models, which reproduces laboratory data over a wide range of relative humidities. The mechanism proposes that CH2OO + H2O (k(H2O)∼ 1 × 10(-15) cm(3) molec(-1) s(-1)) yields 73% hydroxymethyl hydroperoxide (HMHP), 6% formaldehyde + H2O2, and 21% formic acid + H2O; and CH2OO + (H2O)2 (k(H2O)2∼ 1 × 10(-12) cm(3) molec(-1) s(-1)) yields 40% HMHP, 6% formaldehyde + H2O2, and 54% formic acid + H2O. Competitive rate determinations (kSO2/k(H2O)n=1,2∼ 2.2 (±0.3) × 10(4)) and field observations suggest that water vapor is a sink for greater than 98% of CH2OO in a Southeastern US forest, even during pollution episodes ([SO2] ∼ 10 ppb). The importance of the CH2OO + (H2O)n reaction is demonstrated by high HMHP mixing ratios observed over the forest canopy. We find that CH2OO does not substantially affect the lifetime of SO2 or HCOOH in the Southeast US, e.g., CH2OO + SO2 reaction is a minor contribution (production by stabilized Criegees is likely unimportant in regions dominated by the reactivity of ozone with isoprene. In contrast

Imidazolidinone adducts of peptides and hemoglobin

International Nuclear Information System (INIS)

San George, R.C.; Hoberman, H.D.

1986-01-01

Acetaldehyde reacts selectively with the terminal amino groups of the α and β chains of hemoglobin to form stable adducts, the structures of which, based on 13 C NMR studies, are proposed to be diastereomeric 2-methyl imidazolidin-4-ones. In this scheme, acetaldelhyde forms a reversible Schiff base with the α-amino groups of the polypeptide chains which cyclize with the amide nitrogen of the first peptide bond to form the stable imidazolidinone adducts. In support of this mechanism, the authors found that in following the reaction of the peptide val-gly-gly with [1,2- 13 C] acetaldehyde, 13 C NMR resonances attributed to a Schiff base (δ = 170 ppm) were observed which slowly disappeared prior to appearance of resonances from a pair of stable adducts (δ = 70 and 71 ppm) believed to be the diastereomeric imidazolidinones. Schiff base formation appeared to limit the overall rate. Tetraglycine reacted in a similar manner but with a resonance from a single stable adduct observed representing the enantiomeric imidazolidinone adducts of this peptide. Peptides with proline in position 2 should be incapable of forming imidazolidinones, and the authors found that ala-pro-gly did in fact fail to form a stable adduct with acetaldehyde. The 2-methyl imidazolidin-4-one adducts of hemoglobin may be useful in determining the contribution of the amino terminal groups to the structure and functional properties of hemoglobins

Phosphoramide mustard exposure induces DNA adduct formation and the DNA damage repair response in rat ovarian granulosa cells

Energy Technology Data Exchange (ETDEWEB)

Ganesan, Shanthi, E-mail: shanthig@iastate.edu; Keating, Aileen F., E-mail: akeating@iastate.edu

2015-02-01

Phosphoramide mustard (PM), the ovotoxic metabolite of the anti-cancer agent cyclophosphamide (CPA), destroys rapidly dividing cells by forming NOR-G-OH, NOR-G and G-NOR-G adducts with DNA, potentially leading to DNA damage. A previous study demonstrated that PM induces ovarian DNA damage in rat ovaries. To investigate whether PM induces DNA adduct formation, DNA damage and induction of the DNA repair response, rat spontaneously immortalized granulosa cells (SIGCs) were treated with vehicle control (1% DMSO) or PM (3 or 6 μM) for 24 or 48 h. Cell viability was reduced (P < 0.05) after 48 h of exposure to 3 or 6 μM PM. The NOR-G-OH DNA adduct was detected after 24 h of 6 μM PM exposure, while the more cytotoxic G-NOR-G DNA adduct was formed after 48 h by exposure to both PM concentrations. Phosphorylated H2AX (γH2AX), a marker of DNA double stranded break occurrence, was also increased by PM exposure, coincident with DNA adduct formation. Additionally, induction of genes (Atm, Parp1, Prkdc, Xrcc6, and Brca1) and proteins (ATM, γH2AX, PARP-1, PRKDC, XRCC6, and BRCA1) involved in DNA repair were observed in both a time- and dose-dependent manner. These data support that PM induces DNA adduct formation in ovarian granulosa cells, induces DNA damage and elicits the ovarian DNA repair response. - Highlights: • PM forms ovarian DNA adducts. • DNA damage marker γH2AX increased by PM exposure. • PM induces ovarian DNA double strand break repair.

Isoprene emission response to drought and the impact on global atmospheric chemistry

Science.gov (United States)

Jiang, Xiaoyan; Guenther, Alex; Potosnak, Mark; Geron, Chris; Seco, Roger; Karl, Thomas; Kim, Saewung; Gu, Lianhong; Pallardy, Stephen

2018-06-01

Biogenic isoprene emissions play a very important role in atmospheric chemistry. These emissions are strongly dependent on various environmental conditions, such as temperature, solar radiation, plant water stress, ambient ozone and CO2 concentrations, and soil moisture. Current biogenic emission models (i.e., Model of Emissions of Gases and Aerosols from Nature, MEGAN) can simulate emission responses to some of the major driving variables, such as short-term variations in temperature and solar radiation, but the other factors are either missing or poorly represented. In this paper, we propose a new modelling approach that considers the physiological effects of drought stress on plant photosynthesis and isoprene emissions for use in the MEGAN3 biogenic emission model. We test the MEGAN3 approach by integrating the algorithm into the existing MEGAN2.1 biogenic emission model framework embedded into the global Community Land Model of the Community Earth System Model (CLM4.5/CESM1.2). Single-point simulations are compared against available field measurements at the Missouri Ozarks AmeriFlux (MOFLUX) field site. The modelling results show that the MEGAN3 approach of using of a photosynthesis parameter (Vcmax) and soil wetness factor (βt) to determine the drought activity factor leads to better simulated isoprene emissions in non-drought and drought periods. The global simulation with the MEGAN3 approach predicts a 17% reduction in global annual isoprene emissions, in comparison to the value predicted using the default CLM4.5/MEGAN2.1 without any drought effect. This reduction leads to changes in surface ozone and oxidants in the areas where the reduction of isoprene emissions is observed. Based on the results presented in this study, we conclude that it is important to simulate the drought-induced response of biogenic isoprene emission accurately in the coupled Earth System model.

Ground-based intercomparison of two isoprene measurement techniques

Directory of Open Access Journals (Sweden)

E. Leibrock

2003-01-01

Full Text Available An informal intercomparison of two isoprene (C5H8 measurement techniques was carried out during Fall of 1998 at a field site located approximately 3 km west of Boulder, Colorado, USA. A new chemical ionization mass spectrometric technique (CIMS was compared to a well-established gas chromatographic technique (GC. The CIMS technique utilized benzene cation chemistry to ionize isoprene. The isoprene levels measured by the CIMS were often larger than those obtained with the GC. The results indicate that the CIMS technique suffered from an anthropogenic interference associated with air masses from the Denver, CO metropolitan area as well as an additional interference occurring in clean conditions. However, the CIMS technique is also demonstrated to be sensitive and fast. Especially after introduction of a tandem mass spectrometric technique, it is therefore a candidate for isoprene measurements in remote environments near isoprene sources.

Influence of isoprene chemical mechanism on modelled changes in tropospheric ozone due to climate and land use over the 21st century

Science.gov (United States)

Squire, O. J.; Archibald, A. T.; Griffiths, P. T.; Jenkin, M. E.; Smith, D.; Pyle, J. A.

2015-05-01

Isoprene is a~precursor to tropospheric ozone, a key pollutant and greenhouse gas. Anthropogenic activity over the coming century is likely to cause large changes in atmospheric CO2 levels, climate and land use, all of which will alter the global vegetation distribution leading to changes in isoprene emissions. Previous studies have used global chemistry-climate models to assess how possible changes in climate and land use could affect isoprene emissions and hence tropospheric ozone. The chemistry of isoprene oxidation, which can alter the concentration of ozone, is highly complex, therefore it must be parameterised in these models. In this work, we compare the effect of four different reduced isoprene chemical mechanisms, all currently used in Earth system models, on tropospheric ozone. Using a box model we compare ozone in these reduced schemes to that in a more explicit scheme (the Master Chemical Mechanism) over a range of NOx and isoprene emissions, through the use of O3 isopleths. We find that there is some variability, especially at high isoprene emissions, caused by differences in isoprene-derived NOx reservoir species. A global model is then used to examine how the different reduced schemes respond to potential future changes in climate, isoprene emissions, anthropogenic emissions and land use change. We find that, particularly in isoprene-rich regions, the response of the schemes varies considerably. The wide-ranging response is due to differences in the model descriptions of the peroxy radical chemistry, particularly their relative rates of reaction towards NO, leading to ozone formation, or HO2, leading to termination. Also important is the yield of isoprene nitrates and peroxyacyl nitrate precursors from isoprene oxidation. Those schemes that produce less of these NOx reservoir species, tend to produce more ozone locally and less away from the source region. We also note changes in other key oxidants such as NO3 and OH (due to the inclusion of

Isoprene biosynthesis in hybrid poplar impacts ozone tolerance

Science.gov (United States)

Behnke, K.; Kleist, E.; Uerlings, R.; Wildt, J.; Rennenberg, H.; Schnitzler, J. P.

2009-04-01

Isoprene is the most abundant volatile compound emitted by vegetation. It influences air chemistry and is thought to take part in plant defense reactions against abiotic stress such as high temperature or ozone. However, whether or not isoprene emission interacts with ozone tolerance of plants is still in discussion. We exploited transgenic non-isoprene emitting Grey poplar (Populus x canescens) in a biochemical and physiological model study to investigate the effect of acute ozone stress on the elicitation of defense-related emissions of plant volatiles, photosynthesis and the antioxidative system. We recorded that non-isoprene emitting poplars are more resistant to ozone as indicated by less damaged leaf area and higher assimilation rates compared to ozone-exposed wild type plants. The integral of green leaf volatile (GLV) emissions was different between the two poplar phenotypes and a reliable early marker for subsequent leaf damage. For other stress-induced volatiles like mono-, homo-, and sesquiterpenes, and methyl salicylate similar time profiles, pattern and emission intensities were observed in both transgenic and wild type plants. However, un-stressed non-isoprene emitting poplars are characterized by elevated levels of ascorbate and α-tocopherol as well as a more effective de-epoxidation ratio of xanthophylls than in wild type plants. Since ozone quenching properties of ascorbate are much higher than those of isoprene and furthermore α-tocopherol also is an essential antioxidant, non-isoprene emitting poplars might benefit from changes within the antioxidative system by providing them with enhanced ozone tolerance.

Sensitivities in global scale modeling of isoprene

Directory of Open Access Journals (Sweden)

R. von Kuhlmann

2004-01-01

Full Text Available A sensitivity study of the treatment of isoprene and related parameters in 3D atmospheric models was conducted using the global model of tropospheric chemistry MATCH-MPIC. A total of twelve sensitivity scenarios which can be grouped into four thematic categories were performed. These four categories consist of simulations with different chemical mechanisms, different assumptions concerning the deposition characteristics of intermediate products, assumptions concerning the nitrates from the oxidation of isoprene and variations of the source strengths. The largest differences in ozone compared to the reference simulation occured when a different isoprene oxidation scheme was used (up to 30-60% or about 10 nmol/mol. The largest differences in the abundance of peroxyacetylnitrate (PAN were found when the isoprene emission strength was reduced by 50% and in tests with increased or decreased efficiency of the deposition of intermediates. The deposition assumptions were also found to have a significant effect on the upper tropospheric HOx production. Different implicit assumptions about the loss of intermediate products were identified as a major reason for the deviations among the tested isoprene oxidation schemes. The total tropospheric burden of O3 calculated in the sensitivity runs is increased compared to the background methane chemistry by 26±9  Tg( O3 from 273 to an average from the sensitivity runs of 299 Tg(O3. % revised Thus, there is a spread of ± 35% of the overall effect of isoprene in the model among the tested scenarios. This range of uncertainty and the much larger local deviations found in the test runs suggest that the treatment of isoprene in global models can only be seen as a first order estimate at present, and points towards specific processes in need of focused future work.

Overview of the Ozark Isoprene Experiment (OZIE)

Energy Technology Data Exchange (ETDEWEB)

Pierce, T.; Koerber, M,; Guenther, A.; King, S.; Lingerich, S.; Turner, J.

1999-07-01

Ozone modeling studies, such as those performed for the Ozone Transport Advisory Group (OTAG), have raised concerns about extremely high isoprene concentrations ({gt} 50 ppbv) that have been predicted over the Ozark Plateau in southern Missouri. In response to these concerns, a collaborative study was undertaken involving participants from AMEREN, US Department of Army at Fort Leonard Wood, Lake Michigan Air Directors Consortium, National Center for Atmospheric Research, Purdue University, US Environmental Protection Agency, Washington State University, Washington University (St. Louis), and the states of Illinois, Indiana, and Missouri. The Ozark Isoprene Experiment (OZIE) took place during July 1998 and included measurements of isoprene from the surface and aloft at several locations stretching from northeastern Oklahoma to southern Indiana. Measurements were made along a balloon tethered to nearly 1,000 m, surface footprint sites at five locations upwind of the balloon, surface sites in Illinois and Indiana, and from an aircraft flying at heights ranging from 300 to 1,000 m over southern Illinois, southern Indiana, and southern Missouri. Preliminary analysis of the data indicates that daytime surface isoprene concentrations ranged from 1 to 36 ppbv, and isoprene concentrations measured at 600 m ranged from 0.4 to 6 ppbv. Conditions were favorable for the emission of isoprene, with daytime maximum temperatures exceeding 32 C on at least four days during the two-week study period. This paper provides an overview of the study design and describes measurements taken during the experiment.

Formation pathways of DMSO(2) in the addition channel of the OH-initiated DMS oxidation: A theoretical study.

Science.gov (United States)

Ramírez-Anguita, Juan M; González-Lafont, Angels; Lluch, José M

2009-07-15

The production of dimethyl sulfoxide (DMSO) and dimethyl sulfone (DMSO(2)) in the dimethyl sulfide (DMS) degradation scheme initiated by the hydroxyl (OH) radical has been shown to be very sensitive to nitrogen oxides (NO(x)) levels. In the present work we have explored the potential energy surfaces corresponding to several reaction pathways which yield DMSO(2) from the CH(3)S(O)(OH)CH(3) adduct [including the formation of CH(3)S(O)(OH)CH(3) from the reaction of DMSO with OH] and the reaction channels that yield DMSO or/and DMSO(2) from the CH(3)S(O(2))(OH)CH(3) adduct are also studied. The formation of the CH(3)S(O(2))(OH)CH(3) adduct from CH(3)S(OH)CH(3) (DMS-OH) and O(2) was analyzed in our previous work. All these pathways due to the presence of NO(x) (NO and NO(2)) and also due to the reactions with O(2), OH and HO(2) are compared with the objective of inferring their kinetic relevance in the laboratory experiments that measure DMSO(2) (and DMSO) formation yields. In particular, our theoretical results clearly show the existence of NO(x)-dependent pathways leading to the formation of DMSO(2), which could explain some of these experimental results in comparison with experimental measurements carried out in NO(x)-free conditions. Our results indicate that the relative importance of the addition channel in the DMS oxidation process can be dependent on the NO(x) content of chamber experiments and of atmospheric conditions. (c) 2008 Wiley Periodicals, Inc.

Diurnal Variation in the Basal Emission Rate of Isoprene

Science.gov (United States)

Jennifer Funk; Clive G. Jones; Christine J. Baker; Heather M. Fuller; Christian P. Giardina; Manuel T. Lerdua

2003-01-01

Isoprene is emitted from numerous plant species and profoundly influences tropospheric chemistry. Due to the short lifetime of isoprene in the atmosphere, developing an understanding of emission patterns at small time scales is essential for modeling regional atmospheric chemistry processes. Previous studies suggest that diurnal fluctuations in isoprene emission may be...

Measurements of total OH reactivity during PROPHET-AMOS 2016

Science.gov (United States)

Rickly, P.; Sakowski, J.; Bottorff, B.; Lew, M.; Stevens, P. S.; Sklaveniti, S.; Locoge, N.; Dusanter, S.

2017-12-01

As one of the main oxidant in the atmosphere, the hydroxyl radical (OH) initiates the oxidation of volatile organic compounds that can lead to the formation of ozone and secondary organic aerosols. Understanding both the sources and sinks of OH is therefore important to address issues related to air quality and climate change. Measurements of total OH reactivity can provide an important test of our understanding of the OH radical budget. Recent measurements of total reactivity in many environments have been greater than calculated based on the measured concentration of VOCs, suggesting that important OH sinks in these environments are not well characterized. Measurements of total OH reactivity were performed in a forested environment during the PROPHET - AMOS field campaign (Program for Research on Oxidants: PHotochemisty, Emissions, and Transport - Atmospheric Measurements of Oxidants in Summer) using the Comparative Reactivity Method (CRM) and the Total OH Loss Rate Method (TOHLM). The site is characterized by large emissions of isoprene and monoterpenes and low anthropogenic influence. Measurements of total OH reactivity using these two techniques agree to within their respective uncertainties, giving confidence in the measured OH reactivity. In addition, measurements of trace gases (VOCs, NOx, O3) were used to perform a comprehensive apportionment of OH sinks. These measurements are used in a chemical model using the Master Chemical Mechanism to calculate the expected OH reactivity. The results will be compared to previous measurements of total OH reactivity at this site.

Observations and Modeling of the Green Ocean Amazon 2014/15: Hydroxyl Radical (OH) Chemical Ionization Mass Spectrometer (CIMS) Field Campaign Report

Energy Technology Data Exchange (ETDEWEB)

Kim, Saewung [Univ. of California, Irvine, CA (United States)

2016-05-01

The University of California, Irvine, science team (Dr. Saewung Kim, Dr. Roger Seco, Dr. Alex Guenther, and Dr. Jim Smith) deployed a chemical ionization mass spectrometer system for hydroxyl radical (OH) and sulfuric acid quantifications. As part of the GoAmazon 2014/15 field campaign. Hydroxyl radical determines tropospheric oxidation capacity and had been expected to be very low in the pristine rain forest region such as the Brazilian Amazon because of the presence of significant levels of highly reactive biogenic volatile organic compounds and very low levels of NO, which is an OH recycling agent. However, several recent in situ OH observations provided by a laser-induced fluorescence system reported unaccountably high OH concentrations. To address this discrepancy, a series of laboratory and theoretical studies has postulated chemical reaction mechanisms of isoprene that may regenerate OH in photo-oxidation processes. Along with these efforts, potential artifacts on the laser induced fluorescence system from isoprene and its oxidation products also have been explored. Therefore, the first chemical ionization mass spectrometer observations at the U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Climate Research Facility’s T3 site in Manacapuru, Brazil, are expected to provide a critical experimental constraint to address uncertainty in constraining oxidation capacity over pristine rain forest environments. In addition, we deployed a National Center for Atmospheric Research (NCAR) proton transfer reaction time-of-flight mass spectrometer to characterize atmospheric volatile organic compound levels, especially isoprene and its oxidation products, which are critical input parameters for box modeling to simulate OH with different isoprene photo-oxidation schemes. As there has been no report on noticeable new particle formation events, our first in situ sulfuric acid observations in the Amazon rain forest were expected to constrain the

Circadian control of isoprene emissions from oil palm (Elaeis guineensis).

Science.gov (United States)

Wilkinson, Michael J; Owen, Susan M; Possell, Malcolm; Hartwell, James; Gould, Peter; Hall, Anthony; Vickers, Claudia; Nicholas Hewitt, C

2006-09-01

The emission of isoprene from the biosphere to the atmosphere has a profound effect on the Earth's atmospheric system. Until now, it has been assumed that the primary short-term controls on isoprene emission are photosynthetically active radiation and temperature. Here we show that isoprene emissions from a tropical tree (oil palm, Elaeis guineensis) are under strong circadian control, and that the circadian clock is potentially able to gate light-induced isoprene emissions. These rhythms are robustly temperature compensated with isoprene emissions still under circadian control at 38 degrees C. This is well beyond the acknowledged temperature range of all previously described circadian phenomena in plants. Furthermore, rhythmic expression of LHY/CCA1, a genetic component of the central clock in Arabidopsis thaliana, is still maintained at these elevated temperatures in oil palm. Maintenance of the CCA1/LHY-TOC1 molecular oscillator at these temperatures in oil palm allows for the possibility that this system is involved in the control of isoprene emission rhythms. This study contradicts the accepted theory that isoprene emissions are primarily light-induced.

Effect of temperature on postillumination isoprene emission in oak and poplar.

Science.gov (United States)

Li, Ziru; Ratliff, Ellen A; Sharkey, Thomas D

2011-02-01

Isoprene emission from broadleaf trees is highly temperature dependent, accounts for much of the hydrocarbon emission from plants, and has a profound effect on atmospheric chemistry. We studied the temperature response of postillumination isoprene emission in oak (Quercus robur) and poplar (Populus deltoides) leaves in order to understand the regulation of isoprene emission. Upon darkening a leaf, isoprene emission fell nearly to zero but then increased for several minutes before falling back to nearly zero. Time of appearance of this burst of isoprene was highly temperature dependent, occurring sooner at higher temperatures. We hypothesize that this burst represents an intermediate pool of metabolites, probably early metabolites in the methylerythritol 4-phosphate pathway, accumulated upstream of dimethylallyl diphosphate (DMADP). The amount of this early metabolite(s) averaged 2.9 times the amount of plastidic DMADP. DMADP increased with temperature up to 35°C before starting to decrease; in contrast, the isoprene synthase rate constant increased up to 40°C, the highest temperature at which it could be assessed. During a rapid temperature switch from 30°C to 40°C, isoprene emission increased transiently. It was found that an increase in isoprene synthase activity is primarily responsible for this transient increase in emission levels, while DMADP level stayed constant during the switch. One hour after switching to 40°C, the amount of DMADP fell but the rate constant for isoprene synthase remained constant, indicating that the high temperature falloff in isoprene emission results from a reduction in the supply of DMADP rather than from changes in isoprene synthase activity.

Quantification of 3-nitrobenzanthrone-DNA adducts using online column-switching HPLC-electrospray tandem mass spectrometry.

Science.gov (United States)

Gamboa da Costa, Gonçalo; Singh, Rajinder; Arlt, Volker M; Mirza, Amin; Richards, Meirion; Takamura-Enya, Takeji; Schmeiser, Heinz H; Farmer, Peter B; Phillips, David H

2009-11-01

The aromatic nitroketone 3-nitrobenzanthrone (3-nitro-7H-benz[de]anthracen-7-one; 3-NBA) is an extremely potent mutagen and a suspected human carcinogen detected in the exhaust of diesel engines and in airborne particulate matter. 3-NBA is metabolically activated via reduction of the nitro group to the hydroxylamine (N-OH-3-ABA) to form covalent DNA adducts. Thus far, the detection and quantification of covalent 3-NBA-DNA adducts has relied solely on (32)P-postlabeling methodologies. In order to expand the range of available techniques for the detection and improved quantification of 3-NBA-DNA adducts, we have developed a method based upon online column-switching HPLC coupled to electrospray tandem mass spectrometry, with isotopic dilution of (15)N-labeled internal standards. This methodology was applied to the determination of three 3-NBA-derived adducts: 2-(2'-deoxyguanosin-N(2)-yl)-3-aminobenzanthrone (dG-N(2)-3-ABA), N-(2'-deoxyguanosin-8-yl)-3-aminobenzanthrone (dG-C8-N-3-ABA) and 2-(2'-deoxyguanosine-8-yl)-3-aminobenzanthrone (dG-C8-C2-3-ABA). Dose-dependent increases were observed for all three adducts when salmon testis DNA was reacted with N-acetoxy-3-aminobenzanthrone (N-AcO-3-ABA). dG-C8-C2-3-ABA was detected at much lower levels (overall 1%) than the other two adducts. DNA samples isolated from tissues of rats treated either intratracheally with 3-NBA or intraperitoneally with N-OH-3-ABA were analyzed by mass spectrometry, and the results compared to those obtained by (32)P-postlabeling. The method required 50 microg of hydrolyzed animal DNA on column and the limit of detection was 2.0 fmol for each adduct. dG-C8-C2-3-ABA was not observed in any of the samples providing confirmation that it is not formed in vivo. Linear regression analysis of the levels of dG-N(2)-3-ABA and dG-C8-N-3-ABA in the rat DNA showed a reasonable correlation between the two methods (R(2) = 0.88 and 0.93, respectively). In summary, the mass spectrometric method is a faster, more

Potential controls of isoprene in the surface ocean

Science.gov (United States)

Hackenberg, S. C.; Andrews, S. J.; Airs, R.; Arnold, S. R.; Bouman, H. A.; Brewin, R. J. W.; Chance, R. J.; Cummings, D.; Dall'Olmo, G.; Lewis, A. C.; Minaeian, J. K.; Reifel, K. M.; Small, A.; Tarran, G. A.; Tilstone, G. H.; Carpenter, L. J.

2017-04-01

Isoprene surface ocean concentrations and vertical distribution, atmospheric mixing ratios, and calculated sea-to-air fluxes spanning approximately 125° of latitude (80°N-45°S) over the Arctic and Atlantic Oceans are reported. Oceanic isoprene concentrations were associated with a number of concurrently monitored biological variables including chlorophyll a (Chl a), photoprotective pigments, integrated primary production (intPP), and cyanobacterial cell counts, with higher isoprene concentrations relative to all respective variables found at sea surface temperatures greater than 20°C. The correlation between isoprene and the sum of photoprotective carotenoids, which is reported here for the first time, was the most consistent across all cruises. Parameterizations based on linear regression analyses of these relationships perform well for Arctic and Atlantic data, producing a better fit to observations than an existing Chl a-based parameterization. Global extrapolation of isoprene surface water concentrations using satellite-derived Chl a and intPP reproduced general trends in the in situ data and absolute values within a factor of 2 between 60% and 85%, depending on the data set and algorithm used.

Progress Report: DE-FG03-97ER20274, ''Microbial Production of Isoprene''

International Nuclear Information System (INIS)

Ray Fall

2002-01-01

We have discovered that microorganisms produce and emit the hydrocarbon isoprene (2-methyl-1,3-butadiene), and have suggested that if isoprene-producing enzymes and their genes can be harnessed, useful hydrocarbon-producing systems might be constructed. The main goal of the proposed work is to establish the biochemical mechanism and regulation of isoprene formation in the bacterial system, Bacillus subtilis. Specific objectives of the proposed work are the following: (A) to characterize the physiological regulation of isoprene formation in B. subtilis; (B) to characterize mutations in B. subtilis 168 that suppress isoprene formation, clone these genes, and determine how isoprene and isoprenoid carbon flow are regulated; and (C) to test ''overflow'' and ''signaling'' models for Bacillus isoprene formation. We are also pursuing the isolation and cloning of B. subtilis isoprene synthase, which we believe may be a regulatory enzyme

Direct Observations of Isoprene Secondary Organic Aerosol Formation in Ambient Cloud Droplets

Science.gov (United States)

Zelenyuk, A.; Bell, D.; Thornton, J. A.; Fast, J. D.; Shrivastava, M. B.; Berg, L. K.; Imre, D. G.; Mei, F.; Shilling, J.; Suski, K. J.; Liu, J.; Tomlinson, J. M.; Wang, J.

2017-12-01

Multiphase chemistry of isoprene photooxidation products has been shown to be one of the major sources of secondary organic aerosol (SOA) in the atmosphere. A number of recent studies indicate that aqueous aerosol phase provides a medium for reactive uptake of isoprene photooxidation products, and in particular, isomeric isoprene epoxydiols (IEPOX), with reaction rates and yields being dependent on aerosol acidity, water content, sulfate concentration, and organic coatings. However, very few studies focused on chemistry occurring within actual cloud droplets. We will present data acquired during recent Holistic Interactions of Shallow Clouds, Aerosols, and Land Ecosystems (HI-SCALE) Campaign, which provide direct evidence for IEPOX-SOA formation in cloud droplets. Single particle mass spectrometer, miniSPLAT, and a high-resolution, time-of-flight aerosol mass spectrometer were used to characterize the composition of aerosol particles and cloud droplet residuals, while a high-resolution, time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) was used to characterize gas-phase compounds. We find that the composition of cloud droplet residuals was markedly different than that of aerosol particles sampled outside the cloud. Cloud droplet residuals were comprised of individual particles with high relative fractions of sulfate and nitrate and significant fraction of particles with mass spectra that are nearly identical to those of laboratory-generated IEPOX-SOA particles. The observed cloud-induced formation of IEPOX-SOA was accompanied by simultaneous decrease in measured concentrations of IEPOX and other gas-phase isoprene photooxidation products. Ultimately, the combined cloud, aerosol, and gas-phase measurements conducted during HI-SCALE will be used to develop and evaluate model treatments of aqueous-phase isoprene SOA formation.

Reconciling functions and evolution of isoprene emission in higher plants.

Science.gov (United States)

Loreto, Francesco; Fineschi, Silvia

2015-04-01

Compilation and analysis of existing inventories reveal that isoprene is emitted by c. 20% of the perennial vegetation of tropical and temperate regions of the world. Isoprene emitters are found across different plant families without any clear phylogenetic thread. However, by critically appraising information in inventories, several ecological patterns of isoprene emission can be highlighted, including absence of emission from C4 and annual plants, and widespread emission from perennial and deciduous plants of temperate environments. Based on this analysis, and on available information on biochemistry, ecology and functional roles of isoprene, it is suggested that isoprene may not have evolved to help plants face heavy or prolonged stresses, but rather assists C3 plants to run efficient photosynthesis and to overcome transient and mild stresses, especially during periods of active plant growth in warm seasons. When the stress status persists, or when evergreen leaves cope with multiple and repeated stresses, isoprene biosynthesis is replaced by the synthesis of less volatile secondary compounds, in part produced by the same biochemical pathway, thus indicating causal determinism in the evolution of isoprene-emitting plants in response to the environment. © 2014 The Authors. New Phytologist © 2014 New Phytologist Trust.

Increased levels of etheno-DNA adducts and genotoxicity biomarkers of long-term exposure to pure diesel engine exhaust.

Science.gov (United States)

Shen, Meili; Bin, Ping; Li, Haibin; Zhang, Xiao; Sun, Xin; Duan, Huawei; Niu, Yong; Meng, Tao; Dai, Yufei; Gao, Weimin; Yu, Shanfa; Gu, Guizhen; Zheng, Yuxin

2016-02-01

Etheno-DNA adducts are biomarkers for assessing oxidative stress. In this study, the aim was to detect the level of etheno-DNA adducts and explore the relationship between the etheno-DNA adducts and genotoxicity biomarkers of the diesel engine exhaust (DEE)-exposed workers. We recruited 86 diesel engine testing workers with long-term exposure to DEE and 99 non-DEE-exposed workers. The urinary mono-hydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) and etheno-DNA adducts (εdA and εdC) were detected by HPLC-MS/MS and UPLC-MS/MS, respectively. Genotoxicity biomarkers were also evaluated by comet assay and cytokinesis-block micronucleus assay. The results showed that urinary εdA was significantly higher in the DEE-exposed workers (p<0.001), exhibited 2.1-fold increase compared with the non-DEE-exposed workers. The levels of urinary OH-PAHs were positively correlated with the level of εdA among all the study subjects (p<0.001). Moreover, we found that the increasing level of εdA was significantly associated with the increased olive tail moment, percentage of tail DNA, or frequency of micronucleus in the study subjects (p<0.01). No significant association was observed between the εdC level and any measured genotoxicity biomarkers. In summary, εdA could serve as an indicator for DEE exposure in the human population. Copyright © 2015 Elsevier B.V. All rights reserved.

Ochratoxin A: In Utero Exposure in Mice Induces Adducts in Testicular DNA

Directory of Open Access Journals (Sweden)

Jamie E. Jennings-Gee

2010-06-01

Full Text Available Ochratoxin A (OTA is a nephrotoxin and carcinogen that is associated with Balkan endemic nephropathy and urinary tract tumors. OTA crosses the placenta and causes adducts in the liver and kidney DNA of newborns. Because the testis and kidney develop from the same embryonic tissue, we reasoned that OTA also may cause adducts transplacentally in the testis. We tested the hypothesis that acute exposure to OTA, via food and via exposure in utero, causes adducts in testicular DNA and that these lesions are identical to those that can be produced in the kidney and testis by the consumption of OTA. Adult mice received a single dose of OTA (from 0–1,056 µg/kg by gavage. Pregnant mice received a single i.p. injection of OTA (2.5 mg/kg at gestation day 17. DNA adducts were determined by 32P-postlabeling. Gavage-fed animals sacrificed after 48 hours accumulated OTA in kidney and testis and showed DNA adducts in kidney and testis. Some OTA metabolites isolated from the tissues were similar in both organs (kidney and testis. The litters of mice exposed prenatally to OTA showed no signs of overt toxicity. However, newborn and 1-month old males had DNA adducts in kidney and testis that were chromatographically similar to DNA adducts observed in the kidney and testis of gavage-fed adults. One adduct was identified previously as C8-dG-OTA adduct by LC MS/MS. No adducts were observed in males from dams not exposed to OTA. Our findings that in utero exposure to OTA causes adducts in the testicular DNA of male offspring support a possible role for OTA in testicular cancer.

Isoprene emission and photosynthesis during heatwaves and drought in black locust

Science.gov (United States)

Bamberger, Ines; Ruehr, Nadine K.; Schmitt, Michael; Gast, Andreas; Wohlfahrt, Georg; Arneth, Almut

2017-08-01

Extreme weather conditions like heatwaves and drought can substantially affect tree physiology and the emissions of isoprene. To date, however, there is only limited understanding of isoprene emission patterns during prolonged heat stress and next to no data on emission patterns during coupled heat-drought stress or during post-stress recovery. We studied gas exchange and isoprene emissions of black locust trees under episodic heat stress and in combination with drought. Heatwaves were simulated in a controlled greenhouse facility by exposing trees to outside temperatures +10 °C, and trees in the heat-drought treatment were supplied with half of the irrigation water given to heat and control trees. Leaf gas exchange of isoprene, CO2 and H2O was quantified using self-constructed, automatically operating chambers, which were permanently installed on leaves (n = 3 per treatment). Heat and combined heat-drought stress resulted in a sharp decline of net photosynthesis (Anet) and stomatal conductance. Simultaneously, isoprene emissions increased 6- to 8-fold in the heat and heat-drought treatment, which resulted in a carbon loss that was equivalent to 12 and 20 % of assimilated carbon at the time of measurement. Once temperature stress was released at the end of two 15-day-long heatwaves, stomatal conductance remained reduced, while isoprene emissions and Anet recovered quickly to values of the control trees. Further, we found that isoprene emissions covaried with Anet during nonstress conditions, while during the heatwaves, isoprene emissions were not related to Anet but to light and temperature. Under standard air temperature and light conditions (here 30 °C and photosynthetically active radiation of 500 µmol m-2 s-1), isoprene emissions of the heat trees were by 45 % and the heat-drought trees were by 27 % lower than in control trees. Moreover, temperature response curves showed that not only the isoprene emission factor changed during both heat and heat

Isoprene emission and photosynthesis during heatwaves and drought in black locust

Directory of Open Access Journals (Sweden)

I. Bamberger

2017-08-01

Full Text Available Extreme weather conditions like heatwaves and drought can substantially affect tree physiology and the emissions of isoprene. To date, however, there is only limited understanding of isoprene emission patterns during prolonged heat stress and next to no data on emission patterns during coupled heat–drought stress or during post-stress recovery. We studied gas exchange and isoprene emissions of black locust trees under episodic heat stress and in combination with drought. Heatwaves were simulated in a controlled greenhouse facility by exposing trees to outside temperatures +10 °C, and trees in the heat–drought treatment were supplied with half of the irrigation water given to heat and control trees. Leaf gas exchange of isoprene, CO2 and H2O was quantified using self-constructed, automatically operating chambers, which were permanently installed on leaves (n = 3 per treatment. Heat and combined heat–drought stress resulted in a sharp decline of net photosynthesis (Anet and stomatal conductance. Simultaneously, isoprene emissions increased 6- to 8-fold in the heat and heat–drought treatment, which resulted in a carbon loss that was equivalent to 12 and 20 % of assimilated carbon at the time of measurement. Once temperature stress was released at the end of two 15-day-long heatwaves, stomatal conductance remained reduced, while isoprene emissions and Anet recovered quickly to values of the control trees. Further, we found that isoprene emissions covaried with Anet during nonstress conditions, while during the heatwaves, isoprene emissions were not related to Anet but to light and temperature. Under standard air temperature and light conditions (here 30 °C and photosynthetically active radiation of 500 µmol m−2 s−1, isoprene emissions of the heat trees were by 45 % and the heat–drought trees were by 27 % lower than in control trees. Moreover, temperature response curves showed that not only the isoprene emission

Rate Coefficients for the OH + (CHO)2 (Glyoxal) Reaction Between 240 and 400 K

Science.gov (United States)

Feierabend, K. J.; Talukdar, R. K.; Zhu, L.; Ravishankara, A. R.; Burkholder, J. B.

2006-12-01

Glyoxal (CHO)2, the simplest dialdehyde, is an end product formed in the atmospheric oxidation of biogenic hydrocarbons, for example, isoprene. As such, glyoxal plays a role in regional air quality and ozone production in certain locations. Glyoxal is lost in the atmosphere via UV photolysis and reaction with OH. However, the currently available rate coefficient data for the OH + glyoxal reaction is limited to a single room- temperature measurement made using the relative rate method. A determination of the rate coefficient temperature dependence is therefore needed for a more complete interpretation of the atmospheric processing of glyoxal. This study reports the rate coefficient for the OH + (CHO)2 reaction measured under pseudo- first-order conditions in OH ([(CHO)2] > 1000 [OH]0). OH radicals were produced using 248 nm pulsed laser photolysis of H2O2 or HNO3 and detected by pulsed laser induced fluorescence. The concentration of glyoxal in the reactor was determined using three independent techniques; gas flow rates as well as in situ UV and IR absorption. The total pressure in the reactor was varied from 40 to 300 Torr (He), and the rate coefficient was found to be independent of pressure over the temperature range studied. The rate coefficient exhibits a negative temperature dependence between 240 and 400 K consistent with the dependence previously observed for many other aldehydes. Our room-temperature rate coefficient is smaller than the relative rate value that is currently recommended for use in atmospheric model calculations. Our measured rate coefficients are discussed with respect to those for other aldehydes. The atmospheric implications of our work will also be discussed.

The OH-initiated atmospheric oxidation of divinyl sulfoxide: A theoretical investigation on the reaction mechanism

Science.gov (United States)

Zhang, Weichao; Zhang, Dongju

2012-08-01

The potential energy surfaces for the OH + divinyl sulfoxide reaction in the presence of O2/NO are theoretically characterized at the CCSD(T)/6-311+G(d,p)//BH&HLYP/6-311++G(d,p)+ZPE level of theory. Various possible pathways including the direct hydrogen abstraction channels and the addition-elimination channels are considered. The calculations show that the exclusive feasible entrance channel is the formation of adduct CH2(OH)CHS(O)CHdbnd CH2 (IM1) in the initial reaction pathways. In the atmosphere, the newly formed adduct IM1 can further react with O2/NO to form the dominant products HCHO + C(O)HS(O)CHdbnd CH2 (P9). The calculated results confirm the experimental studies.

Translesion DNA synthesis and mutation induced in a plasmid with a single adduct of the environmental contaminant 3-nitrobenzanthrone in SOS-induced Escherichia coli

International Nuclear Information System (INIS)

Kawanishi, M.; Kanno, T.; Yagi, T.; Enya-Takamura, T.; Fuchs, R.P.

2003-01-01

Full text: 3-Nitrobenzanthrone (NBA) is a powerfully mutagenic nitrated aromatic hydrocarbon found in diesel exhaust and in airborne particulate matters. NBA forms an unusual DNA adduct in vitro that has a C-C bond between the C-8 position of deoxyguanosine and the C-2 position of NBA. We previously found that this adduct is also present in the human cells treated with NBA, and induces mutations in supF shuttle vector system. In this study, we analyzed translesion DNA synthesis (TLS) over a single adduct in lacZ' gene in a plasmid in uvrAmutS Escherichia coli. The result showed that the adduct blocked DNA replication and an observed TLS frequency was 5.4% in non-SOS-induced E. coli. All progenies after the TLS had no mutation. On the other hand, TLS increased to 11.3%, and 4.8% of them had mostly G to T mutations in SOS-induced E. coli. These results suggest that this unusual adduct would be one of causes of lung cancer that is increasing in the urban areas polluted with diesel exhaust. It must be interesting to reveal which DNA polymerase is involved in this TLS

Modulation of Protein S-Nitrosylation by Isoprene Emission in Poplar.

Science.gov (United States)

Vanzo, Elisa; Merl-Pham, Juliane; Velikova, Violeta; Ghirardo, Andrea; Lindermayr, Christian; Hauck, Stefanie M; Bernhardt, Jörg; Riedel, Katharina; Durner, Jörg; Schnitzler, Jörg-Peter

2016-04-01

Researchers have been examining the biological function(s) of isoprene in isoprene-emitting (IE) species for two decades. There is overwhelming evidence that leaf-internal isoprene increases the thermotolerance of plants and protects them against oxidative stress, thus mitigating a wide range of abiotic stresses. However, the mechanisms of abiotic stress mitigation by isoprene are still under debate. Here, we assessed the impact of isoprene on the emission of nitric oxide (NO) and the S-nitroso-proteome of IE and non-isoprene-emitting (NE) gray poplar (Populus × canescens) after acute ozone fumigation. The short-term oxidative stress induced a rapid and strong emission of NO in NE compared with IE genotypes. Whereas IE and NE plants exhibited under nonstressful conditions only slight differences in their S-nitrosylation pattern, the in vivo S-nitroso-proteome of the NE genotype was more susceptible to ozone-induced changes compared with the IE plants. The results suggest that the nitrosative pressure (NO burst) is higher in NE plants, underlining the proposed molecular dialogue between isoprene and the free radical NO Proteins belonging to the photosynthetic light and dark reactions, the tricarboxylic acid cycle, protein metabolism, and redox regulation exhibited increased S-nitrosylation in NE samples compared with IE plants upon oxidative stress. Because the posttranslational modification of proteins via S-nitrosylation often impacts enzymatic activities, our data suggest that isoprene indirectly regulates the production of reactive oxygen species (ROS) via the control of the S-nitrosylation level of ROS-metabolizing enzymes, thus modulating the extent and velocity at which the ROS and NO signaling molecules are generated within a plant cell. © 2016 American Society of Plant Biologists. All Rights Reserved.

Reactions of OH-radicals with hydroxylated and methoxylated benzoic acids and cinnamic acids. Radiation-induced chemical changes in mushrooms

International Nuclear Information System (INIS)

Gaisberger, B.

2001-05-01

In the first part of this work the radiation induced chemical changes of methoxylated and hydroxylated benzoic acids and cinnamic acids were investigated. Methoxylated compounds were also used as model components for acid derivatives with no free-OH groups. The latter are essentials parts of vegetable foodstuff. A comparison of the radiolytic behaviour of single substituted methoxy- and hydroxybenzoic acids was given at first, data of literature was included. The priority of the investigation was the hydroxylation process induced by OH-radicals. The OH-adduct distribution is generally the same for the hydroxy- as well as for the methoxybenzoic acid isomers. This could be proved by oxidation of these OH-adducts with K 3 Fe(CN) 6 . In the presence of air 68-77 % of the hydroxybenzoic acids are converted into hydroxylation products, whereas with the methoxylated acids this reaction leads only to about 10%. An explanation gives the different decay pathways of the intermediate peroxylradical. The multiple methoxy- and hydroxybenzoic acids show three different reaction possibilities: hydroxylation, replacement of -OCH 3 by -OH and -in case of the cinnamic acids-oxidative decomposition of the rest of the propenic acid under formation of the corresponding benzaldehydes. All these reactions can be expected when irradiating foodstuff, containing these acid compounds. The characteristic formation of these components and their linear dose/concentration relationship make these substrates very promising for the use as markers for irradiation treatment of foodstuff. The second part of this work deals with the gamma-radiation induced chemical changes in mushrooms. The irradiated and non-irradiated samples were freeze-dried and purified from matrix components chromatographically on polyamid columns. In case of the phenolic compounds for 4-hydroxybenzoic acid and three unknown components linear dose/concentration relationships could be obtained. Two of these unknown compounds seem

Modeling Global Biogenic Emission of Isoprene: Exploration of Model Drivers

Science.gov (United States)

Alexander, Susan E.; Potter, Christopher S.; Coughlan, Joseph C.; Klooster, Steven A.; Lerdau, Manuel T.; Chatfield, Robert B.; Peterson, David L. (Technical Monitor)

1996-01-01

Vegetation provides the major source of isoprene emission to the atmosphere. We present a modeling approach to estimate global biogenic isoprene emission. The isoprene flux model is linked to a process-based computer simulation model of biogenic trace-gas fluxes that operates on scales that link regional and global data sets and ecosystem nutrient transformations Isoprene emission estimates are determined from estimates of ecosystem specific biomass, emission factors, and algorithms based on light and temperature. Our approach differs from an existing modeling framework by including the process-based global model for terrestrial ecosystem production, satellite derived ecosystem classification, and isoprene emission measurements from a tropical deciduous forest. We explore the sensitivity of model estimates to input parameters. The resulting emission products from the global 1 degree x 1 degree coverage provided by the satellite datasets and the process model allow flux estimations across large spatial scales and enable direct linkage to atmospheric models of trace-gas transport and transformation.

Fullerene–Carbene Lewis Acid–Base Adducts

KAUST Repository

Li, Huaping; Risko, Chad; Seo, Jung Hwa; Campbell, Casey; Wu, Guang; Brédas, Jean-Luc; Bazan, Guillermo C.

2011-01-01

The reaction between a bulky N-heterocylic carbene (NHC) and C60 leads to the formation of a thermally stable zwitterionic Lewis acid-base adduct that is connected via a C-C single bond. Low-energy absorption bands with weak oscillator strengths

Variational transition-state theory study of the rate constant of the DMS·OH scavenging reaction by O2.

Science.gov (United States)

Ramírez-Anguita, Juan M; González-Lafont, Àngels; Lluch, José M

2011-07-30

The chemical tropospheric dimethyl sulfide (DMS, CH3SCH3) degradation involves several steps highly dependent on the environmental conditions. So, intensive efforts have been devoted during the last years to enhance the understanding of the DMS oxidation mechanism under different conditions. The reaction of DMS with OH is considered to be the most relevant process that initiates the whole oxidation process. The experimental observations have been explained by a two-channel mechanism consisting of a H-abstraction process leading to CH3S(O)CH3 and HO2 and an addition reaction leading to the DMS·OH adduct. In the presence of O2, the DMS·OH adduct is competitively scavenged increasing the contribution of the addition channel to the overall DMS oxidation. Recent experimental measurements have determined from a global fit that the rate constant of this scavenging process is independent of pressure and temperature but this rate constant cannot be directly measured. In this article, a variational transition-state theory calculation of the low- and high-pressure rate constants for the reaction between DMS·OH and O2 has been carried out as a function of temperature. Our proposal is that the slight temperature dependence of the scavenging rate constant can only be explained if the H-abstraction bottleneck is preceded by a dynamical bottleneck corresponding to the association process between the DMS·OH adduct and the O2 molecule. The agreement between the low-pressure and high-pressure rate constants confirms the experimental observations. Copyright © 2011 Wiley Periodicals, Inc.

OH, HO2, and HO2* Radical Chemistry During PROPHET-AMOS 2016: Measurements and Model Comparison

Science.gov (United States)

Bottorff, B.; Lew, M.; Rickly, P.; Stevens, P. S.

2017-12-01

The hydroxyl (OH) and peroxy radicals, both the hydroperoxy radical (HO2) and organic peroxy radicals (RO2), play an important role in atmospheric chemistry. In addition to controlling lifetimes of many trace gases important to issues of global climate change, reactions of these radicals can also lead to the production of ozone and secondary organic aerosols in the atmosphere. Previous measurements of these radicals in remote forest environments have shown serious discrepancies with modeled concentrations. These results bring into question our understanding of the atmospheric chemistry of isoprene and other biogenic VOCs under low NOX conditions. In the summer of 2016, OH, HO2 and HO2* (HO2 + αRO2) radicals were measured using the Indiana University Laser-Induced Fluorescence Fluorescence Assay by Gas Expansion (LIF-FAGE) technique as part of the Program for Research on Oxidants: PHtochemistry, Emissions, and Transport- Atmospheric Measurements of Oxidants in Summer (PROPHET-AMOS). This campaign took place in a forested area in northern Michigan characterized by high mixing ratios of isoprene and low mixing ratios of NOX. Ambient measurements from this campaign will be compared to previous measurements at this site and to modeled predictions using both the Regional Atmospheric Chemistry Mechanism (RACM2) and the Master Chemical Mechanism. Potential interferences associated with the OH measurements will also be examined.

OH, HO2 and RO2 Radical and OH Reactivity Observations during the Summertime in Beijing: High In-Situ Ozone Production and Evidence of a Missing OH Source.

Science.gov (United States)

Whalley, L.; Ye, C.; Slater, E.; Woodward-Massey, R.; Lee, J. D.; Squires, F. A.; Hopkins, J. R.; Dunmore, R.; Shaw, M.; Hamilton, J.; Lewis, A. C.; Crilley, L.; Kramer, L. J.; Bloss, W.; Heard, D. E.

2017-12-01

Despite substantial reductions in primary emissions of pollutants in China over the past decade, concentrations of the secondary pollutant, ozone, still frequently exceed air quality threshold limits in urban areas during the summertime. We will present measurements of OH, HO2 and RO2 radicals and OH reactivity made in central Beijing at the Institute of Atmospheric Physics of the Chinese Academy of Sciences, close to the North 4th ring road in May and June 2017 which formed the summer phase of `An Integrated Study of AIR Pollution PROcesses'. Elevated levels of O3 (>100 ppbv) were regularly observed. NO concentrations were elevated during the morning but often decreased to below the instrument limit of detection during the afternoon hours when the ozone concentrations peaked. Biogenic emissions influenced the chemistry at the site, with several ppbv of isoprene measured during the afternoons. The OH measurements were made using the FAGE technique, equipped with an inlet pre injector (IPI) which provides an alternative method to determine the instrument background signal by injecting a scavenger to remove ambient OH and ensures an artefact-free OH measurement. Elevated levels of OH were observed, with a mean peak OH concentration of 1.2×107 molecule cm-3 at noon; but with OH concentrations reaching up to 2.5×107 molecule cm-3 on some days. Mean peak HO2 concentrations of 3×108 molecule cm-3 and total RO2 of 1.2×109 molecule cm-3 were recorded, with maximum concentrations of 1.0×109 molecule cm-3 and 4×109 molecule cm-3 observed for HO2 and RO2 respectively, suggesting significant in situ ozone production. A comparison of the artefact-free OH observations with steady state calculations, constrained to the total OH reactivity measurement and known OH precursors that were measured alongside OH, highlights a significant missing daytime OH source under low [NO], with the steady state OH concentrations approximately a factor of two lower than the OH concentrations

Temperature Dependence of Factors Controlling Isoprene Emissions

Science.gov (United States)

Duncan, Bryan N.; Yoshida, Yasuko; Damon, Megan R.; Douglass, Anne R.; Witte, Jacquelyn C.

2009-01-01

We investigated the relationship of variability in the formaldehyde (HCHO) columns measured by the Aura Ozone Monitoring Instrument (OMI) to isoprene emissions in the southeastern United States for 2005-2007. The data show that the inferred, regional-average isoprene emissions varied by about 22% during summer and are well correlated with temperature, which is known to influence emissions. Part of the correlation with temperature is likely associated with other causal factors that are temperature-dependent. We show that the variations in HCHO are convolved with the temperature dependence of surface ozone, which influences isoprene emissions, and the dependence of the HCHO column to mixed layer height as OMI's sensitivity to HCHO increases with altitude. Furthermore, we show that while there is an association of drought with the variation in HCHO, drought in the southeastern U.S. is convolved with temperature.

The OH-initiated atmospheric chemical reactions of polyfluorinated dibenzofurans and polychlorinated dibenzofurans: A comparative theoretical study.

Science.gov (United States)

Zeng, Xiaolan; Chen, Jing; Qu, Ruijuan; Pan, Xiaoxue; Wang, Zunyao

2017-02-01

The atmospheric chemical reactions of some polyfluorinated dibenzofurans (PFDFs) and polychlorinated dibenzofurans (PCDFs), initiated by OH radical, were investigated by performing theoretical calculations using density functional theory (DFT) and B3LYP/6-311++G(2df,p) method. The obtained results indicate that OH addition reactions of PFDFs and PCDFs occurring at C 1∼4 and C A sites are thermodynamic spontaneous changes and the branching ratio of the PF(C)DF-OH adducts is decided primarily by kinetic factor. The OH addition reactions of PFDFs taking place at fluorinated C 1∼4 positions are kinetically comparable with those occurring at nonfluorinated C 1∼4 positions, while OH addition reactions of PCDFs occurring at chlorinated C 1∼4 sites are negligible. The total rate constants of the addition reactions of PFDFs or PCDFs become smaller with consecutive fluorination or chlorination, and substituting at C 1 position has more adverse effects than substitution at other sites. The succedent O 2 addition reactions of PF(C)DF-OH adducts are thermodynamic nonspontaneous processes under the atmospheric conditions, and have high Gibbs free energies of activation (Δ r G ≠ ). The substituted dibenzofuranols are the primary oxidation products for PCDFs under the atmospheric conditions. However, other oxidative products may also be available for PFDFs besides substituted dibenzofuranols. Copyright © 2016 Elsevier Ltd. All rights reserved.

North American isoprene influence on intercontinental ozone pollution

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A. M. Fiore

2011-02-01

Full Text Available Changing land-use and climate may alter emissions of biogenic isoprene, a key ozone (O₃ precursor. Isoprene is also a precursor to peroxy acetyl nitrate (PAN and thus affects partitioning among oxidized nitrogen (NO_y species, shifting the balance towards PAN, which more efficiently contributes to long-range transport relative to nitric acid (HNO₃ which rapidly deposits. With a suite of sensitivity simulations in the MOZART-2 global tropospheric chemistry model, we gauge the relative importance of the intercontinental influence of a 20% increase in North American (NA isoprene and a 20% decrease in NA anthropogenic emissions (nitrogen oxides (NO_x, non-methane volatile organic compounds (NMVOC and NO_x + NMVOC + carbon monoxide + aerosols. The surface O₃ response to NA isoprene emissions (ΔO₃_ISOP in surface air over NA is about one third of the response to all NA anthropogenic emissions (ΔO₃_ANTH; although with different signs. Over intercontinental distances, ΔO₃_ISOP is relatively larger; in summer and fall, ΔO₃_ISOP in surface air over Europe and North Africa (EU region is more than half of ΔO₃_ANTH. Future increases in NA isoprene emissions could thus offset decreases in EU surface O₃ resulting from controls on NA anthropogenic emissions. Over the EU region, ΔPAN_ISOP at 700 hPa is roughly the same magnitude as ΔPAN_ANTH (oppositely signed. Outside of the continental source region, the percentage changes in PAN are at least twice as large as for surface O₃, implying that long-term PAN measurements at high altitude sites may help to detect O₃ precursor emission changes. We find that neither the baseline level of isoprene emissions nor the fate of isoprene nitrates contributes to the large diversity in model estimates of the anthropogenic emission influence on intercontinental surface O

Formation of secondary organic aerosol from isoprene oxidation over Europe

Directory of Open Access Journals (Sweden)

M. Karl

2009-09-01

Full Text Available The role of isoprene as a precursor to secondary organic aerosol (SOA over Europe is studied with the two-way nested global chemistry transport model TM5. The inclusion of the formation of SOA from isoprene oxidation in our model almost doubles the atmospheric burden of SOA over Europe compared to SOA formation from terpenes and aromatics. The reference simulation, which considers SOA formation from isoprene, terpenes and aromatics, predicts a yearly European production rate of 1.0 Tg SOA yr⁻¹ and an annual averaged atmospheric burden of about 50 Gg SOA over Europe. A fraction of 35% of the SOA produced in the boundary layer over Europe is transported to higher altitudes or to other world regions. Summertime measurements of organic matter (OM during the extensive EMEP OC/EC campaign 2002/2003 are better reproduced when SOA formation from isoprene is taken into account, reflecting also the strong seasonality of isoprene and other biogenic volatile organic compounds (BVOC emissions from vegetation. However, during winter, our model strongly underestimates OM, likely caused by missing wood burning in the emission inventories. Uncertainties in the parameterisation of isoprene SOA formation have been investigated. Maximum SOA production is found for irreversible sticking (non-equilibrium partitioning of condensable vapours on particles, with tropospheric SOA production over Europe increased by a factor of 4 in summer compared to the reference case. Completely neglecting SOA formation from isoprene results in the lowest estimate (0.51 Tg SOA yr⁻¹. The amount and the nature of the absorbing matter are shown to be another key uncertainty when predicting SOA levels. Consequently, smog chamber experiments on SOA formation should be performed with different types of seed aerosols and without seed aerosols in order to derive an improved treatment of the absorption of SOA in the models. Consideration of a number of recent insights

Microbial cycling of isoprene, the most abundantly produced biological volatile organic compound on Earth.

Science.gov (United States)

McGenity, Terry J; Crombie, Andrew T; Murrell, J Colin

2018-04-01

Isoprene (2-methyl-1,3-butadiene), the most abundantly produced biogenic volatile organic compound (BVOC) on Earth, is highly reactive and can have diverse and often detrimental atmospheric effects, which impact on climate and health. Most isoprene is produced by terrestrial plants, but (micro)algal production is important in aquatic environments, and the relative bacterial contribution remains unknown. Soils are a sink for isoprene, and bacteria that can use isoprene as a carbon and energy source have been cultivated and also identified using cultivation-independent methods from soils, leaves and coastal/marine environments. Bacteria belonging to the Actinobacteria are most frequently isolated and identified, and Proteobacteria have also been shown to degrade isoprene. In the freshwater-sediment isolate, Rhodococcus strain AD45, initial oxidation of isoprene to 1,2-epoxy-isoprene is catalyzed by a multicomponent isoprene monooxygenase encoded by the genes isoABCDEF. The resultant epoxide is converted to a glutathione conjugate by a glutathione S-transferase encoded by isoI, and further degraded by enzymes encoded by isoGHJ. Genome sequence analysis of actinobacterial isolates belonging to the genera Rhodococcus, Mycobacterium and Gordonia has revealed that isoABCDEF and isoGHIJ are linked in an operon, either on a plasmid or the chromosome. In Rhodococcus strain AD45 both isoprene and epoxy-isoprene induce a high level of transcription of 22 contiguous genes, including isoABCDEF and isoGHIJ. Sequence analysis of the isoA gene, encoding the large subunit of the oxygenase component of isoprene monooxygenase, from isolates has facilitated the development of PCR primers that are proving valuable in investigating the ecology of uncultivated isoprene-degrading bacteria.

Modulation of Protein S-Nitrosylation by Isoprene Emission in Poplar1

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Vanzo, Elisa; Velikova, Violeta; Ghirardo, Andrea; Lindermayr, Christian; Hauck, Stefanie M.; Riedel, Katharina; Durner, Jörg

2016-01-01

Researchers have been examining the biological function(s) of isoprene in isoprene-emitting (IE) species for two decades. There is overwhelming evidence that leaf-internal isoprene increases the thermotolerance of plants and protects them against oxidative stress, thus mitigating a wide range of abiotic stresses. However, the mechanisms of abiotic stress mitigation by isoprene are still under debate. Here, we assessed the impact of isoprene on the emission of nitric oxide (NO) and the S-nitroso-proteome of IE and non-isoprene-emitting (NE) gray poplar (Populus × canescens) after acute ozone fumigation. The short-term oxidative stress induced a rapid and strong emission of NO in NE compared with IE genotypes. Whereas IE and NE plants exhibited under nonstressful conditions only slight differences in their S-nitrosylation pattern, the in vivo S-nitroso-proteome of the NE genotype was more susceptible to ozone-induced changes compared with the IE plants. The results suggest that the nitrosative pressure (NO burst) is higher in NE plants, underlining the proposed molecular dialogue between isoprene and the free radical NO. Proteins belonging to the photosynthetic light and dark reactions, the tricarboxylic acid cycle, protein metabolism, and redox regulation exhibited increased S-nitrosylation in NE samples compared with IE plants upon oxidative stress. Because the posttranslational modification of proteins via S-nitrosylation often impacts enzymatic activities, our data suggest that isoprene indirectly regulates the production of reactive oxygen species (ROS) via the control of the S-nitrosylation level of ROS-metabolizing enzymes, thus modulating the extent and velocity at which the ROS and NO signaling molecules are generated within a plant cell. PMID:26850277

Photochemistry of Fe:H2O Adducts in Argon Matrixes: A Combined Experimental and Theoretical Study in the Mid-IR and UV-Visible Regions.

Science.gov (United States)

Deguin, Vincent; Mascetti, Joëlle; Simon, Aude; Ben Amor, Nadia; Aupetit, Christian; Latournerie, Sandra; Noble, Jennifer A

2018-01-18

The photochemistry of Fe:H 2 O adducts is of interest in fields as diverse as catalysis and astrochemistry. Industrially, iron can be used as a catalyst to convert H 2 O to H 2 , whereas in the interstellar medium it may be an important component of dust grains, influencing the chemistry on their icy surfaces. This study consisted of the deposition and spectral characterization of binary systems of atomic iron with H 2 O in cryogenic argon matrixes. In this way, we were able to obtain information about the interaction of the two species; we observed the formation of adducts of iron monomers and dimers with water molecules in the mid-IR and UV-visible spectral domains. Upon irradiation with a UV radiation source, the iron species were inserted into the water molecules to form HFeOH and HFe 2 OH, leading in some cases to the formation of FeO possibly accompanied by the production of H 2 . DFT and correlated multireference wave function calculations confirmed our attributions. This combination of IR and UV-visible spectroscopy with theoretical calculations allowed us to determine, for the first time, the spectral characteristics of iron adducts and their photoproducts in the UV-visible and in the OH stretching region of the mid-IR domain.

Characterization of trypsin-derived peptides acrylamide-adducted hemoglobin

International Nuclear Information System (INIS)

Springer, D.L.; Goheen, S.C.; Edmonds, C.G.; McCulloch, M.; Sylvester, D.M.; Sander, C.; Bull, R.J.

1991-01-01

Even though there are a number of sources for human exposure to acrylamide, reliable biomarkers of exposure are not available. In an effort to develop such a biomarker, the authors are characterizing peptides derived from trypsin digests of acrylamide-adducted hemoglobin. For this, radiolabeled acrylamide was incubated with this, radiolabeled acrylamide was incubated with purified human hemoglobin (Ao) and decomposition products removed by dialysis. When the adducted hemoglobin was separated by reverse-phase HPLC, radioactivity eluted with the α and β subunits, suggesting covalent binding. Digestion of individual subunits with trypsin followed by reverse phase HPLC, indicated that most of the radioactivity associated with the α subunit co-eluted with a single peptide. Similar results were observed for the β subunit except that significant amounts of radioactivity eluted with the solvent front, suggesting that radioactivity was released by trypsin digestion. Currently, these preparation are under further characterization by electrospray ionization mass spectrometry. This approach will aid in the identification of the adducted will aid in the identification of the adducted peptide and subsequent preparation of an acrylamide-specific antibody

Contribution of vegetation and water table on isoprene emission from boreal peatland microcosms

DEFF Research Database (Denmark)

Tiiva, Päivi; Faubert, Patrick; Räty, Sanna

2009-01-01

emission in these naturally wet ecosystems, although water table is predicted to decline due to climate warming. We studied the relative contribution of mosses vs. vascular plants to isoprene emission in boreal peatland microcosms in growth chambers by removing either vascular vegetation or both vascular...... hollows with intact vegetation, 45 ± 6 µg m-2 h-1, was decreased by 25% under water table drawdown. However, water table drawdown reduced net ecosystem carbon dioxide (CO2) exchange more dramatically than isoprene emission. Isoprene emission strongly correlated with both CO2 exchange and methane emission......Boreal peatlands are substantial sources of isoprene, a reactive hydrocarbon. However, it is not known how much mosses, vascular plants and peat each contribute to isoprene emission from peatlands. Furthermore, there is no information on the effects of declining water table depth on isoprene...

Isoprene oxidation by nitrate radical: alkyl nitrate and secondary organic aerosol yields

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A. W. Rollins

2009-09-01

Full Text Available Alkyl nitrates and secondary organic aerosol (SOA produced during the oxidation of isoprene by nitrate radicals has been observed in the SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction Chamber chamber. A 16 h dark experiment was conducted with temperatures at 289–301 K, and maximum concentrations of 11 ppb isoprene, 62.4 ppb O₃ and 31.1 ppb NO_x. We find the yield of nitrates is 70±8% from the isoprene + NO₃ reaction, and the yield for secondary dinitrates produced in the reaction of primary isoprene nitrates with NO₃ is 40±20%. We find an effective rate constant for reaction of NO₃ with the group of first generation oxidation products to be 7×10⁻¹⁴ molecule⁻¹ cm³ s⁻¹. At the low total organic aerosol concentration in the chamber (max=0.52 μg m⁻³ we observed a mass yield (ΔSOA mass/Δisoprene mass of 2% for the entire 16 h experiment. However a comparison of the timing of the observed SOA production to a box model simulation of first and second generation oxidation products shows that the yield from the first generation products was <0.7% while the further oxidation of the initial products leads to a yield of 14% (defined as ΔSOA/Δisoprene^2x where Δisoprene^2x is the mass of isoprene which reacted twice with NO₃. The SOA yield of 14% is consistent with equilibrium partitioning of highly functionalized C₅ products of isoprene oxidation.

DNA adducts as molecular dosimeters

International Nuclear Information System (INIS)

Lucier, G.W.

1990-01-01

There is compelling evidence that DNA adducts play an important role in the actions of many pulmonary carcinogens. During the last ten years sensitive methods (antibodies and 32 P-postlabeling) have been developed that permit detection of DNA adducts in tissues of animals or humans exposed to low levels of some genotoxic carcinogens. This capability has led to approaches designed to more reliably estimate the shape of the dose-response curve in the low dose region for a few carcinogens. Moreover, dosimetry comparisions can, in some cases, be made between animals and humans which help in judging the adequacy of animal models for human risk assessments. There are several points that need to be considered in the evaluation of DNA adducts as a molecular dosimeter. For example, DNA adduct formation is only one of many events that are needed for tumor development and some potent carcinogens do not form DNA adducts; i.e., TCDD. Other issues that need to be considered are DNA adduct heterogeneity, DNA repair, relationship of DNA adducts to somatic mutation and cell specificity in DNA adduct formation and persistence. Molecular epidemiology studies often require quantitation of adducts in cells such as lymphocytes which may or may not be reliable surrogates for adduct concentrations in target issues. In summary, accurate quantitation of low levels of DNA adducts may provide data useful in species to species extrapolation of risk including the development of more meaningful human monitoring programs

A new physically-based quantification of marine isoprene and primary organic aerosol emissions

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N. Meskhidze

2009-07-01

Full Text Available The global marine sources of organic carbon (OC are estimated here using a physically-based parameterization for the emission of marine isoprene and primary organic matter. The marine isoprene emission model incorporates new physical parameters such as light sensitivity of phytoplankton isoprene production and dynamic euphotic depth to simulate hourly marine isoprene emissions totaling 0.92 Tg C yr⁻¹. Sensitivity studies using different schemes for the euphotic zone depth and ocean phytoplankton speciation produce the upper and the lower range of marine-isoprene emissions of 0.31 to 1.09 Tg C yr⁻¹, respectively. Established relationships between sea spray fractionation of water-insoluble organic carbon (WIOC and chlorophyll-a concentration are used to estimate the total primary sources of marine sub- and super-micron OC of 2.9 and 19.4 Tg C yr⁻¹, respectively. The consistent spatial and temporal resolution of the two emission types allow us, for the first time, to explore the relative contributions of sub- and super-micron organic matter and marine isoprene-derived secondary organic aerosol (SOA to the total OC fraction of marine aerosol. Using a fixed 3% mass yield for the conversion of isoprene to SOA, our emission simulations show minor (<0.2% contribution of marine isoprene to the total marine source of OC on a global scale. However, our model calculations also indicate that over the tropical oceanic regions (30° S to 30° N, marine isoprene SOA may contribute over 30% of the total monthly-averaged sub-micron OC fraction of marine aerosol. The estimated contribution of marine isoprene SOA to hourly-averaged sub-micron marine OC emission is even higher, approaching 50% over the vast regions of the oceans during the midday hours when isoprene emissions are highest. As it is widely believed that sub-micron OC has the potential to influence the cloud droplet activation of marine aerosols, our

Secondary organic aerosol from VOC mixtures in an oxidation flow reactor

Science.gov (United States)

Ahlberg, Erik; Falk, John; Eriksson, Axel; Holst, Thomas; Brune, William H.; Kristensson, Adam; Roldin, Pontus; Svenningsson, Birgitta

2017-07-01

The atmospheric organic aerosol is a tremendously complex system in terms of chemical content. Models generally treat the mixtures as ideal, something which has been questioned owing to model-measurement discrepancies. We used an oxidation flow reactor to produce secondary organic aerosol (SOA) mixtures containing oxidation products of biogenic (α-pinene, myrcene and isoprene) and anthropogenic (m-xylene) volatile organic compounds (VOCs). The resulting volume concentration and chemical composition was measured using a scanning mobility particle sizer (SMPS) and a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), respectively. The SOA mass yield of the mixtures was compared to a partitioning model constructed from single VOC experiments. The single VOC SOA mass yields with no wall-loss correction applied are comparable to previous experiments. In the mixtures containing myrcene a higher yield than expected was produced. We attribute this to an increased condensation sink, arising from myrcene producing a significantly higher number of nucleation particles compared to the other precursors. Isoprene did not produce much mass in single VOC experiments but contributed to the mass of the mixtures. The effect of high concentrations of isoprene on the OH exposure was found to be small, even at OH reactivities that previously have been reported to significantly suppress OH exposures in oxidation flow reactors. Furthermore, isoprene shifted the particle size distribution of mixtures towards larger sizes, which could be due to a change in oxidant dynamics inside the reactor.

Alcohol, Aldehydes, Adducts and Airways

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Muna Sapkota

2015-11-01

Full Text Available Drinking alcohol and smoking cigarettes results in the formation of reactive aldehydes in the lung, which are capable of forming adducts with several proteins and DNA. Acetaldehyde and malondialdehyde are the major aldehydes generated in high levels in the lung of subjects with alcohol use disorder who smoke cigarettes. In addition to the above aldehydes, several other aldehydes like 4-hydroxynonenal, formaldehyde and acrolein are also detected in the lung due to exposure to toxic gases, vapors and chemicals. These aldehydes react with nucleophilic targets in cells such as DNA, lipids and proteins to form both stable and unstable adducts. This adduction may disturb cellular functions as well as damage proteins, nucleic acids and lipids. Among several adducts formed in the lung, malondialdehyde DNA (MDA-DNA adduct and hybrid malondialdehyde-acetaldehyde (MAA protein adducts have been shown to initiate several pathological conditions in the lung. MDA-DNA adducts are pre-mutagenic in mammalian cells and induce frame shift and base-pair substitution mutations, whereas MAA protein adducts have been shown to induce inflammation and inhibit wound healing. This review provides an insight into different reactive aldehyde adducts and their role in the pathogenesis of lung disease.

Decay kinetics of nicotine/NNK-DNA adducts in vivo studied by accelerator mass spectrometry

International Nuclear Information System (INIS)

Sun, H.F.; He, L.; Liu, Y.F.; Liu, K.X.; Lu, X.Y.; Wang, J.J.; Ma, H.J.; Li, K.

2000-01-01

The decay kinetics of nicotine-DNA adducts and NNK-DNA adducts in mice liver after single dosing was studied by accelerator mass spectrometry (AMS). The decay is characterized by a two-stage process. The half-lives of nicotine-DNA adducts are 1.3 d (4-24 h) and 7.0 d (1-21 d), while for NNK-DNA adducts are 0.7 d (4-24 h) and 18.0 d (1-21 d). The relatively faster decay of nicotine-DNA adducts suggests that the genotoxicity of nicotine is weaker than that of NNK. The in vitro study shows that the metabolization of nicotine is necessary for the final formation of nicotine-DNA adducts, and nicotine Δ1'(5') iminium ion is a probable metabolite species that binds to DNA molecule covalently

Isoprene emission from wetland sedges

Directory of Open Access Journals (Sweden)

A. Ekberg

2009-04-01

Full Text Available High latitude wetlands play an important role for the surface-atmosphere exchange of carbon dioxide (CO₂ and methane (CH₄, but fluxes of biogenic volatile organic compounds (BVOC in these ecosystems have to date not been extensively studied. This is despite BVOC representing a measurable proportion of the total gaseous C fluxes at northern locations and in the face of the high temperature sensitivity of these systems that requires a much improved process understanding to interpret and project possible changes in response to climate warming. We measured emission of isoprene and photosynthetic gas exchange over two growing seasons (2005–2006 in a subarctic wetland in northern Sweden with the objective to identify the physiological and environmental controls of these fluxes on the leaf scale. The sedge species Eriophorum angustifolium and Carex rostrata were both emitters of isoprene. Springtime emissions were first detected after an accumulated diurnal mean temperature above 0^°C of about 100 degree days. Maximum measured growing season standardized (basal emission rates (20^°C, 1000 μmol m⁻² s⁻¹ were 1075 (2005 and 1118 (2006 μg C m⁻² (leaf area h⁻¹ in E. angustifolium, and 489 (2005 and 396 (2006 μg C m⁻² h⁻¹ in C. rostrata. Over the growing season, basal isoprene emission varied in response to the temperature history of the last 48 h. Seasonal basal isoprene emission rates decreased with leaf nitrogen (N, which may be explained by the typical growth and resource allocation pattern of clonal sedges as the leaves age. The observations were used to model emissions over the growing season, accounting for effects of temperature history, links to leaf assimilation rate and the light and temperature dependencies of the cold-adapted sedges.

Observations of biogenic isoprene emissions and atmospheric chemistry components at the Savé super site in Benin, West Africa, during the DACCIWA field campaign.

Science.gov (United States)

Jambert, Corinne; Pacifico, Federica; Delon, Claire; Lohou, Fabienne; Reinares Martinez, Irene; Brilouet, Pierre-Etienne; Derrien, Solene; Dione, Cheikh; Brosse, Fabien; Gabella, Omar; Pedruzzo Bagazgoitia, Xavier; Durand, Pierre

2017-04-01

Tropospheric oxidation of VOCs (Volatile Organic Compounds), including isoprene, in the presence of NOx and sunlight leads to the formation of O3 and Secondary Organic Aerosols (SOA). Changes in NO or VOCs sources will consequently modify their atmospheric concentrations and thus, the rate of O3 production and SOA formation. NOx have also an impact on the abundance of the hydroxyl radical (OH) which determines the lifetime of some pollutants and greenhouse gases. Anthropogenic emissions of pollutants from mega cities located on the Guinean coast in South West Africa are likely to increase in the next decades due to a strong anthropogenic pressure and to land use changes at the regional or continental scale. The consequences on regional air quality and on pollutant deposition onto surfaces may have some harmful effects on human and ecosystem health. Furthermore, the regional climate and water cycle are affected by changes in atmospheric chemistry. When transported northward on the African continent, polluted air masses meet biogenic emissions from rural areas which contributes to increase ozone and SOA production, in high temperature and solar radiation conditions, highly favourable to enhanced photochemistry. During the Dynamics-aerosol-chemistry-cloud interactions in West Africa (DACCIWA) field campaign, we measured the atmospheric chemical composition and the exchanges of trace components in a hinterland area of Benin, at the Savé super-site (8°02'03" N, 2°29'11″ E). The observations, monitored in June and July 2016, in a rural mixed agricultural area, include near surface concentrations of ozone (O3), carbon monoxide (CO), nitrogen oxides (NOx) and isoprene, isoprene fluxes and meteorological parameters. We observed hourly average concentrations of O3 up to 50 ppb, low NOx concentrations (ca. 1 ppb and CO concentrations between 75 and 300 ppb. An 8 m tower was equipped with a Fast Isoprene Sensor and sonic anemometer to measure isoprene concentrations and

Mass Spectrometric Characterization of Circulating Covalent Protein Adducts Derived from a Drug Acyl Glucuronide Metabolite: Multiple Albumin Adductions in Diclofenac Patients

Science.gov (United States)

Hammond, Thomas G.; Meng, Xiaoli; Jenkins, Rosalind E.; Maggs, James L.; Castelazo, Anahi Santoyo; Regan, Sophie L.; Bennett, Stuart N. L.; Earnshaw, Caroline J.; Aithal, Guruprasad P.; Pande, Ira; Kenna, J. Gerry; Stachulski, Andrew V.; Park, B. Kevin

2014-01-01

Covalent protein modifications by electrophilic acyl glucuronide (AG) metabolites are hypothetical causes of hypersensitivity reactions associated with certain carboxylate drugs. The complex rearrangements and reactivities of drug AG have been defined in great detail, and protein adducts of carboxylate drugs, such as diclofenac, have been found in liver and plasma of experimental animals and humans. However, in the absence of definitive molecular characterization, and specifically, identification of signature glycation conjugates retaining the glucuronyl and carboxyl residues, it cannot be assumed any of these adducts is derived uniquely or even fractionally from AG metabolites. We have therefore undertaken targeted mass spectrometric analyses of human serum albumin (HSA) isolated from diclofenac patients to characterize drug-derived structures and, thereby, for the first time, have deconstructed conclusively the pathways of adduct formation from a drug AG and its isomeric rearrangement products in vivo. These analyses were informed by a thorough understanding of the reactions of HSA with diclofenac AG in vitro. HSA from six patients without drug-related hypersensitivities had either a single drug-derived adduct or one of five combinations of 2–8 adducts from among seven diclofenac N-acylations and three AG glycations on seven of the protein’s 59 lysines. Only acylations were found in every patient. We present evidence that HSA modifications by diclofenac in vivo are complicated and variable, that at least a fraction of these modifications are derived from the drug’s AG metabolite, and that albumin adduction is not inevitably a causation of hypersensitivity to carboxylate drugs or a coincidental association. PMID:24902585

Morphological changes of calcite single crystals induced by graphene-biomolecule adducts

Science.gov (United States)

Calvaresi, Matteo; Di Giosia, Matteo; Ianiro, Alessandro; Valle, Francesco; Fermani, Simona; Polishchuk, Iryna; Pokroy, Boaz; Falini, Giuseppe

2017-01-01

Calcite has the capability to interact with a wide variety of molecules. This usually induces changes in shape and morphology of crystals. Here, this process was investigated using sheets of graphene-biomolecule adducts. They were prepared and made dispersible in water through the exfoliation of graphite by tip sonication in the presence tryptophan or N-acetyl-D-glucosamine. The crystallization of calcium carbonate in the presence of these additives was obtained by the vapor diffusion method and only calcite formed. The analysis of the microscopic observations showed that the graphene-biomolecule adducts affected shape and morphology of rhombohedral {10.4} faced calcite crystals, due to their stabilization of additional {hk.0} faces. The only presence of the biomolecule affected minimally shape and morphology of calcite crystals, highlighting the key role of the graphene sheets as 2D support for the adsorption of the biomolecules.

Ionic fragmentation of the isoprene molecule in the VUV energy range (12 to 310 eV)

Energy Technology Data Exchange (ETDEWEB)

Bernini, R.B., E-mail: rafael.bernini@ifrj.edu.br [Instituto Federal de Ciência e Tecnologia do Rio de Janeiro (IFRJ), 25050-100 Duque de Caxias, RJ (Brazil); Coutinho, L.H. [Instituto de Física, Universidade Federal do Rio De Janeiro (UFRJ), 21941-972 Rio de Janeiro, RJ (Brazil); Nunez, C.V. [Laboratório de Bioprospecção e Biotecnologia, Coordenação de Tecnologia e Inovação, Instituto Nacional de Pesquisas da Amazônia (INPA), 69060-001 Manaus, AM (Brazil); Castilho, R.B. de [Departamento de Química, Instituto de Ciências Exatas, Universidade Federal do Amazonas (UFAM), 69077-000 Manaus, AM (Brazil); Souza, G.G.B. de [Instituto de Química, Universidade Federal do Rio de Janeiro (UFRJ), 21949-900 Rio de Janeiro, RJ (Brazil)

2015-07-15

Highlights: • Ionic fragmentation of isoprene following valence-shell and C 1s excitation. • Experimental observation of single and double ionization processes. • Large increase in fragmentation following core excitation. • Similar dissociation pattern bellow (270 eV) and above (310 eV) core edge. • Stable molecular ion observed at all photon energies. - Abstract: Isoprene, C{sub 5}H{sub 8}, is a biogenic volatile compound emitted from plants and animals, playing an important role in atmospheric chemistry. In this work, we have studied the ionic fragmentation of the isoprene molecule induced by high energy photons (synchrotron radiation), both at the valence (12.0, 14.0, 16.0, 18.0, and 21.0 eV) and carbon 1s edge (270 and 310 eV, respectively, below and above edge) energies. The ionic fragments were mass-analyzed using a Wiley–McLaren time-of-flight spectrometer (TOF) and single (PEPICO) and double ionization coincidence (PEPIPICO) spectra were obtained. As expected, the fragmentation degree increases with increasing energy. Below and above the carbon 1s edge, the fragmentation patterns are quite similar, and basically the same fragments are observed as compared to the spectra following valence-shell ionization. Stable doubly-charged ions were not observed. A PEPIPICO spectrum has shown that the main dissociation route for doubly-ionized species corresponds to the [CH{sub 3}]{sup +}/[C{sub 4}H{sub 2–5}]{sup +} ion pair. Intense fragmentation of the isoprene molecule has been observed following valence shell and core electron ionization. The observance of basically the same fragments when moving from valence to inner-shell suggests that basically the same fragmentation routes are present in both cases. All doubly (or multiply)-charged cations are unstable, at least on a microsecond scale.

Effects of Drought Stress and Ozone Exposure on Isoprene Emissions from Oak Seedlings in Texas

Science.gov (United States)

Madronich, M. B.; Harte, A.; Schade, G. W.

2014-12-01

Isoprene is the dominant hydrocarbon emitted by plants to the atmosphere with an approximate global emission of 550 Tg C yr-1. Isoprene emission studies have elucidated plants' isoprene production capacity, and the controlling factors of instantaneous emissions. However, it is not yet well understood how long-term climatic factors such as drought and increasing ozone concentrations affect isoprene emission rates. Drought reduces photosynthetic activity and is thus expected to reduce isoprene emission rate, since isoprene production relies on photosynthates. On the other hand, ozone is also known to negatively affect photosynthesis rates, but can instead increase isoprene emissions. These apparent inconsistencies and a lack of experimental data make it difficult to accurately parameterize isoprene emission responses to changing environmental conditions. The objective of this work is to reduce some of these uncertainties, using oak seedlings as a study system. Our project focuses on isoprene emission responses of oak trees to typical summer drought and high ozone conditions in Texas. We report on experiments conducted using a laboratory whole-plant chamber and leaf-level data obtained from greenhouse-grown seedlings. The chamber experiment studied the effects of ozone and drought on isoprene emissions from >3 year old oak seedlings under controlled conditions of photosynthetically active radiation (PAR), temperature, soil-moisture and the chamber's air composition. Stress in plants was induced by manipulating potted soil-moisture and ozone concentration in the chamber. The greenhouse study focused on understanding the effects of drought under Texas climatic conditions. For this study we used two year old seedlings of water oak (Quercus nigra) and post oak (Quercus stellata). Temperature, humidity and light in the greenhouse followed local conditions. Leaf-level conductance, photosynthesis measurements and isoprene sampling were carried out under controlled leaf

Isoprene Production on Enzymatic Hydrolysate of Peanut Hull Using Different Pretreatment Methods

Directory of Open Access Journals (Sweden)

Sumeng Wang

2016-01-01

Full Text Available The present study is about the use of peanut hull for isoprene production. In this study, two pretreatment methods, hydrogen peroxide-acetic acid (HPAC and popping, were employed prior to enzymatic hydrolysis, which could destroy the lignocellulosic structure and accordingly improve the efficiency of enzymatic hydrolysis. It is proven that the isoprene production on enzymatic hydrolysate with HPAC pretreatment is about 1.9-fold higher than that of popping pretreatment. Moreover, through High Performance Liquid Chromatography (HPLC analysis, the amount and category of inhibitors such as formic acid, acetic acid, and HMF were assayed and were varied in different enzymatic hydrolysates, which may be the reason leading to a decrease in isoprene production during fermentation. To further increase the isoprene yield, the enzymatic hydrolysate of HPAC was detoxified by activated carbon. As a result, using the detoxified enzymatic hydrolysate as the carbon source, the engineered strain YJM21 could accumulate 297.5 mg/L isoprene, which accounted for about 90% of isoprene production by YJM21 fermented on pure glucose (338.6 mg/L. This work is thought to be the first attempt on isoprene production by E. coli using peanut hull as the feedstock. More importantly, it also shows the prospect of peanut hull to be considered as an alternative feedstock for bio-based chemicals or biofuels production due to its easy access and high polysaccharide content.

Progress Report: DE-FG03-97ER20274, ''Microbial Production of Isoprene''

Energy Technology Data Exchange (ETDEWEB)

Ray Fall

2002-03-13

We have discovered that microorganisms produce and emit the hydrocarbon isoprene (2-methyl-1,3-butadiene), and have suggested that if isoprene-producing enzymes and their genes can be harnessed, useful hydrocarbon-producing systems might be constructed. The main goal of the proposed work is to establish the biochemical mechanism and regulation of isoprene formation in the bacterial system, Bacillus subtilis. Specific objectives of the proposed work are the following: (A) to characterize the physiological regulation of isoprene formation in B. subtilis; (B) to characterize mutations in B. subtilis 168 that suppress isoprene formation, clone these genes, and determine how isoprene and isoprenoid carbon flow are regulated; and (C) to test ''overflow'' and ''signaling'' models for Bacillus isoprene formation. We are also pursuing the isolation and cloning of B. subtilis isoprene synthase, which we believe may be a regulatory enzyme.

Detection of Riddelliine-Derived DNA Adducts in Blood of Rats Fed Riddelliine

Directory of Open Access Journals (Sweden)

Ming W. Chou

2002-09-01

Full Text Available Abstract: We have previously shown that riddelliine, a naturally occurring genotoxic pyrrolizidine alkaloid, induces liver tumors in rats and mice through a genotoxic mechanism mediated by the formation of a set of eight 6,7-dihydro-7-hydroxy-1-hydroxymethyl-5Hpyrrolizine ( DHP-derived DNA adducts. In this study we report the formation of these DHP-derived DNA adducts in blood DNA of rats fed riddelliine. In an adduct formation and removal experiment, male and female F344 rats (8 weeks of age were administered riddelliine by gavage at a single dose of 10.0 mg/kg body weight in 0.1 M phosphate buffer. At 8, 24, 48, and 168 hrs after dosing, the levels of DHP-derived DNA adduct in blood and liver were determined by 32P-postlabeling/HPLC. Maximum DNA adduct formation occurred at 48 hr after treatment. From 48 to 168 hours, the adduct levels in female rat blood were 4-fold greater than those in male rats. In a dose response experiment, female rats were gavaged 0.1 and 1.0 mg/kg doses of riddelliine for three consecutive days and the DHPderived DNA adducts in blood DNA were assayed. The levels of the DHP-derived DNA adducts in blood of rats receiving 0.1 and 1.0 mg/kg doses were 12.9 and 51.8 adducts/107 nucleotides. These results suggest that: (i leucocyte DNA can bind with DHP to form a set of DHP-derived DNA adducts generated in liver; (ii DHP-derived DNA adducts in blood can serve as a potential non-invasive biomarkers for assessing the exposure to riddelliine.

Airborne measurements of isoprene and monoterpene emissions from southeastern U.S. forests

Energy Technology Data Exchange (ETDEWEB)

Yu, Haofei; Guenther, Alex; Gu, Dasa; Warneke, Carsten; Geron, Chris; Goldstein, Allen; Graus, Martin; Karl, Thomas; Kaser, Lisa; Misztal, Pawel; Yuan, Bin

2017-10-01

Isoprene and monoterpene emission rates are essential inputs for atmospheric chemistry models that simulate atmospheric oxidant and particle distributions. Process studies of the biochemical and physiological mechanisms controlling these emissions are advancing our understanding and the accuracy of model predictions but efforts to quantify regional emissions have been limited by a lack of constraints on regional distributions of ecosystem emission capacities. We used an airborne wavelet-based eddy covariance measurement technique to characterize isoprene and monoterpene fluxes with high spatial resolution during the 2013 SAS (Southeast Atmosphere Study) in the southeastern United States. The fluxes measured by direct eddy covariance were comparable to emissions independently estimated using an indirect inverse modeling approach. Isoprene emission factors based on the aircraft wavelet flux estimates for high isoprene chemotypes (e.g., oaks) were similar to the MEGAN2.1 biogenic emission model estimates for landscapes dominated by oaks. Aircraft flux measurement estimates for landscapes with fewer isoprene emitting trees (e.g., pine plantations), were about a factor of two lower than MEGAN2.1 model estimates. The tendency for high isoprene emitters in these landscapes to occur in the shaded understory, where light dependent isoprene emissions are diminished, may explain the lower than expected emissions. This result demonstrates the importance of accurately representing the vertical profile of isoprene emitting biomass in biogenic emission models. Airborne measurement-based emission factors for high monoterpene chemotypes agreed with MEGAN2.1 in landscapes dominated by pine (high monoterpene chemotype) trees but were more than a factor of three higher than model estimates for landscapes dominated by oak (relatively low monoterpene emitting) trees. This results suggests that unaccounted processes, such as floral emissions or light dependent monoterpene emissions, or

Tamoxifen Forms DNA Adducts In Human Colon After Administration Of A Single [14C]-Labeled Therapeutic Dose.

Energy Technology Data Exchange (ETDEWEB)

Brown, K; Tompkins, E M; Boocock, D J; Martin, E A; Farmer, P B; Turteltaub, K W; Ubick, E; Hemingway, D; Horner-Glister, E; White, I H

2007-05-23

Tamoxifen is widely prescribed for the treatment of breast cancer and is also licensed in the U.S. for the prevention of this disease. However, tamoxifen therapy is associated with an increased occurrence of endometrial cancer in women and there is also evidence that it may elevate the risk of colorectal cancer. The underlying mechanisms responsible for tamoxifen-induced carcinogenesis in women have not yet been elucidated but much interest has focussed on the role of DNA adduct formation. We investigated the propensity of tamoxifen to bind irreversibly to colorectal DNA when given to ten women as a single [{sup 14}C]-labeled therapeutic (20 mg) dose, {approx}18 h prior to undergoing colon resections. Using the sensitive technique of accelerator mass spectrometry, coupled with HPLC separation of enzymatically digested DNA, a peak corresponding to authentic dG-N{sup 2}-tamoxifen adduct was detected in samples from three patients, at levels ranging from 1-7 adducts/10{sup 9} nucleotides. No [{sup 14}C]-radiolabel associated with tamoxifen or its major metabolites was detected. The presence of detectable CYP3A4 protein in all colon samples suggests this tissue has the potential to activate tamoxifen to {alpha}-hydroxytamoxifen, in addition to that occurring in the systemic circulation, and direct interaction of this metabolite with DNA could account for the binding observed. Although the level of tamoxifeninduced damage displayed a degree of inter-individual variability, when present it was {approx}10-100 times higher than that reported for other suspect human colon carcinogens such as PhIP. These findings provide a mechanistic basis through which tamoxifen could increase the incidence of colon cancers in women.

Photofragment imaging study of the CH2CCH2OH radical intermediate of the OH+allene reaction

International Nuclear Information System (INIS)

Raman, Arjun S.; Justine Bell, M.; Lau, K.-C.; Butler, Laurie J.

2007-01-01

These velocity map imaging experiments characterize the photolytic generation of one of the two radical intermediates formed when OH reacts via an addition mechanism with allene. The CH 2 CCH 2 OH radical intermediate is generated photolytically from the photodissociation of 2-chloro-2-propen-1-ol at 193 nm. Detecting the Cl atoms using [2+1] resonance-enhanced multiphoton ionization evidences an isotropic angular distribution for the Cl+CH 2 CCH 2 OH photofragments, a spin-orbit branching ratio for Cl( 2 P 1/2 ):Cl( 2 P 3/2 ) of 0.28, and a bimodal recoil kinetic energy distribution. Conservation of momentum and energy allows us to determine from this data the internal energy distribution of the nascent CH 2 CCH 2 OH radical cofragment. To assess the possible subsequent decomposition pathways of this highly vibrationally excited radical intermediate, we include electronic structure calculations at the G3//B3LYP level of theory. They predict the isomerization and dissociation transition states en route from the initial CH 2 CCH 2 OH radical intermediate to the three most important product channels for the OH+allene reaction expected from this radical intermediate: formaldehyde+C 2 H 3 , H+acrolein, and ethene+CHO. We also calculate the intermediates and transition states en route from the other radical adduct, formed by addition of the OH to the center carbon of allene, to the ketene+CH 3 product channel. We compare our results to a previous theoretical study of the O+allyl reaction conducted at the CBS-QB3 level of theory, as the two reactions include several common intermediates

Photofragment imaging study of the CH2CCH2OH radical intermediate of the OH +allene reaction

Science.gov (United States)

Raman, Arjun S.; Justine Bell, M.; Lau, Kai-Chung; Butler, Laurie J.

2007-10-01

These velocity map imaging experiments characterize the photolytic generation of one of the two radical intermediates formed when OH reacts via an addition mechanism with allene. The CH2CCH2OH radical intermediate is generated photolytically from the photodissociation of 2-chloro-2-propen-1-ol at 193nm. Detecting the Cl atoms using [2+1] resonance-enhanced multiphoton ionization evidences an isotropic angular distribution for the Cl +CH2CCH2OH photofragments, a spin-orbit branching ratio for Cl(P1/22):Cl(P3/22) of 0.28, and a bimodal recoil kinetic energy distribution. Conservation of momentum and energy allows us to determine from this data the internal energy distribution of the nascent CH2CCH2OH radical cofragment. To assess the possible subsequent decomposition pathways of this highly vibrationally excited radical intermediate, we include electronic structure calculations at the G3//B3LYP level of theory. They predict the isomerization and dissociation transition states en route from the initial CH2CCH2OH radical intermediate to the three most important product channels for the OH +allene reaction expected from this radical intermediate: formaldehyde+C2H3, H +acrolein, and ethene+CHO. We also calculate the intermediates and transition states en route from the other radical adduct, formed by addition of the OH to the center carbon of allene, to the ketene+CH3 product channel. We compare our results to a previous theoretical study of the O +allyl reaction conducted at the CBS-QB3 level of theory, as the two reactions include several common intermediates.

Understanding the impact of recent advances in isoprene photooxidation on simulations of regional air quality

OpenAIRE

Xie, Y; Paulot, F; Carter, WPL; Nolte, CG; Luecken, DJ; Hutzell, WT; Wennberg, PO; Cohen, RC; Pinder, RW

2013-01-01

The CMAQ (Community Multiscale Air Quality) us model in combination with observations for INTEX-NA/ICARTT (Intercontinental Chemical Transport Experiment–North America/International Consortium for Atmospheric Research on Transport and Transformation) 2004 are used to evaluate recent advances in isoprene oxidation chemistry and provide constraints on isoprene nitrate yields, isoprene nitrate lifetimes, and NOx recycling rates. We incorporate recent advances in isoprene oxidation ch...

Understanding the impact of recent advances in isoprene photooxidation on simulations of regional air quality

OpenAIRE

Xie, Y.; Carter, W. P. L.; Nolte, C. G.; Luecken, D. J.; Hutzell, W. T.; Wennberg, P. O.; Cohen, R. C.; Pinder, R. W.

2013-01-01

The CMAQ (Community Multiscale Air Quality) us model in combination with observations for INTEX-NA/ICARTT (Intercontinental Chemical Transport Experiment–North America/International Consortium for Atmospheric Research on Transport and Transformation) 2004 are used to evaluate recent advances in isoprene oxidation chemistry and provide constraints on isoprene nitrate yields, isoprene nitrate lifetimes, and NO_x recycling rates. We incorporate recent advances in isoprene oxidation chemistry int...

Isoprene emission by poplar is not important for the feeding behaviour of poplar leaf beetles

OpenAIRE

M?ller, Anna; Kaling, Moritz; Faubert, Patrick; Gort, Gerrit; Smid, Hans M; Van Loon, Joop JA; Dicke, Marcel; Kanawati, Basem; Schmitt-Kopplin, Philippe; Polle, Andrea; Schnitzler, J?rg-Peter; Rosenkranz, Maaria

2015-01-01

Background Chrysomela populi (poplar leaf beetle) is a common herbivore in poplar plantations whose infestation causes major economic losses. Because plant volatiles act as infochemicals, we tested whether isoprene, the main volatile organic compound (VOC) produced by poplars (Populus x canescens), affects the performance of C. populi employing isoprene emitting (IE) and transgenic isoprene non-emitting (NE) plants. Our hypothesis was that isoprene is sensed and affects beetle orientation or ...

Line narrowing spectroscopic studies of DNA-carcinogen adducts and DNA-dye complexes

International Nuclear Information System (INIS)

Suh, Myungkoo.

1995-01-01

Laser-induced fluorescence line narrowing and non-line narrowing spectroscopic methods were applied to conformational studies of stable DNA adducts of the 7β, 8α-dihydoxy-9α, l0α-epoxy-7,8,9, 10-tetrahydrobenzo[α]pyrene (anti-BPDE). Stereochemically distinct (+)-trans-, (-)-trans-, (+)-cis- and (-)-cis adducts of anti-BPDE bound to exocyclic amino group of the central guanine in an 11-mer oligonucleotide, exist in a mixture of conformations in frozen aqueous buffer matrices. The (+)-trans adduct adopts primarily an external conformation with a smaller fraction ( ∼ 25 %) exists in a partially base-stacked conformation. Both cis adducts were found to be intercalated with significant π-π stacking interactions between the pyrenyl residues and the bases. Conformations of the trans-adduct of (+)-anti -BPDE in 11-mer oligonucleotides were studied as a function of flanking bases. In single stranded form the adduct at G 2 or G 3 (5 ft-flanking, base guanine) adopts a conformation with strong, interaction with the bases. In contrast, the adduct with a 5ft-flanking, thymine exists in a primarily helixexternal conformation. Similar differences were observed in the double stranded oligonucleotides. The nature of the 3ft-flanking base has little influence on the conformational equilibrium of the (+)-trans-anti BPDE-dG adduct. The formation and repair of BPDE-N 2 -dG in DNA isolated from the skin of mice treated topically with benzo[α]pyrene (BP) was studied. Low-temperature fluorescence spectroscopy of the intact DNA identified the major adduct as (+)-trans-anti-BPDE-N-dG, and the minor adduct fraction consisted mainly of (+)-cis-anti-BPDE-N 2 -dG

Reactivity of OH radicals with chlorobenzoic acids-A pulse radiolysis and steady-state radiolysis study

Energy Technology Data Exchange (ETDEWEB)

Zona, Robert [University of Vienna, Department of Nutritional Sciences, Section Radiation Biology, UZAII, Althanstrasse 14, A-1090 Vienna (Austria); Solar, Sonja, E-mail: sonja.solar@univie.ac.a [University of Vienna, Department of Nutritional Sciences, Section Radiation Biology, UZAII, Althanstrasse 14, A-1090 Vienna (Austria); Getoff, Nikola [University of Vienna, Department of Nutritional Sciences, Section Radiation Biology, UZAII, Althanstrasse 14, A-1090 Vienna (Austria); Sehested, Knud; Holcman, Jerzy [RISO National Laboratory Environmental Science and Technology Department, DK-4000, Roskilde (Denmark)

2010-05-15

The reactions of OH radicals with 2-, 3-, 4-chlorobenzoic acids (ClBzA) and chlorobenzene (ClBz), k({sup c}entre dotOH+substrates)=(4.5-6.2)x10{sup 9} dm{sup 3} mol{sup -1} s{sup -1}, have been studied by pulse radiolysis in N{sub 2}O saturated solutions. The absorption maxima of the OH-adducts were in the range of 320-340 nm. Their decay was according to a second-order reaction, 2k=(1-9)x10{sup 8} dm{sup 3} mol{sup -1} s{sup -1}. In the presence of N{sub 2}O/O{sub 2} the formation of peroxyl radicals was detectable for 2-, 4-ClBzA and ClBz, k(OH-adduct+O{sub 2})=(2-4)x10{sup 7} dm{sup 3} mol{sup -1} s{sup -1}, while this reaction for 3-ClBzA was too slow to be registered. In the presence of N{sub 2}O the degradation rates induced by gamma radiation were very similar for all chlorobenzoic acids, yet the chloride formation was distinctly higher for 3-ClBzA. In the presence of oxygen the initial degradation of 2-and 4-ClBzA equaled the OH-radical concentration, whereas in case of 3-ClBzA only approx60% of {sup c}entre dotOH led to degradation. The order for the efficiency of dehalogenation was 4->2->3-ClBzA. Several primary radiolytic products could be detected by HPLC. To evaluate the toxicity of final products a bacterial bioluminescence test was carried out.

Separation and identification of DNA-carcinogen adduct conformers by polyacrylamide gel electrophoresis with laser-induced fluorescence detection

Energy Technology Data Exchange (ETDEWEB)

Marsch, G.A.; Jankowiak, R.; Farhat, J.H.; Small, G.J. (Ames Lab., IA (United States) Iowa State Univ., Ames (United States))

1992-12-01

The authors have developed a separation protocol utilizing high-resolution polyacrylamide gel electrophoresis (PAGE) to isolate stable anti-benzo[a]pyrene diol epoxide adducts of oligodeoxynucleotides. Both enantiomers produced multiple adduct species. The distribution of adduct types could be quantitated by densitometry of autoradiograms or Cerenkov counting of eluted oligomers modified by anti-BPDE isomers. Laser-induced fluorescence (LIF) spectra of eluted adducts at 4.2 K (fluorescence line-narrowing spectroscopy) and 77 K revealed that bands corresponded to pure conformers of pyrene chromophore. Carcinogen-modified oligodeoxynucleotides were single-stranded, but there were often considerable stacking interactions between the pyrenyl residues and the oligonucleotide bases, indicating that electrophoresed oligomers were single-stranded but in a native, versus random-coil conformation. The ability to identify and quantitate adducts by PAGE-LIF, coupled with the high resolution and sensitivity of both techniques, makes PAGE and LIF in tandem a potentially powerful tool in the study of chemical carcinogenesis or other ligand-DNA interactions. 43 refs., 7 figs., 1 tab.

Mechanisms of the different DNA adduct forming potentials of the urban air pollutants 2-nitrobenzanthrone and carcinogenic 3-nitrobenzanthrone.

Science.gov (United States)

Stiborová, Marie; Martínek, Václav; Svobodová, Martina; Sístková, Jana; Dvorák, Zdenek; Ulrichová, Jitka; Simánek, Vilím; Frei, Eva; Schmeiser, Heinz H; Phillips, David H; Arlt, Volker M

2010-07-19

2-Nitrobenzanthrone (2-NBA) has recently been detected in ambient air particulate matter. Its isomer 3-nitrobenzanthrone (3-NBA) is a potent mutagen and suspected human carcinogen identified in diesel exhaust. We compared the efficiencies of human enzymatic systems [hepatic microsomes and cytosols, NAD(P)H:quinone oxidoreductase 1 (NQO1), xanthine oxidase, NADPH:cytochrome P450 reductase, N,O-acetyltransferases, and sulfotransferases] and human primary hepatocytes to activate 2-NBA and its isomer 3-NBA to species forming DNA adducts. In contrast to 3-NBA, 2-NBA was not metabolized at detectable levels by the tested human enzymatic systems and enzymes expressed in human hepatocytes, and no DNA adducts detectable by (32)P-postlabeling were generated by 2-NBA. Even NQO1, the most efficient human enzyme to bioactive 3-NBA, did not activate 2-NBA. Molecular docking of 2-NBA and 3-NBA to the active site of NQO1 showed similar binding affinities; however, the binding orientation of 2-NBA does not favor the reduction of the nitro group. This was in line with the inhibition of 3-NBA-DNA adduct formation by 2-NBA, indicating that 2-NBA can compete with 3-NBA for binding to NQO1, thereby decreasing the metabolic activation of 3-NBA. In addition, the predicted equilibrium conditions favor a 3 orders of magnitude higher dissociation of N-OH-3-ABA in comparison to N-OH-2-ABA. These findings explain the very different genotoxicity, mutagenicity, and DNA adduct forming potential of the two compounds. Collectively, our results suggest that 2-NBA possesses a relatively lower risk to humans than 3-NBA.

Photosynthesis-dependent isoprene emission from leaf to planet in a global carbon-chemistry-climate model

Science.gov (United States)

Unger, N.; Harper, K.; Zheng, Y.; Kiang, N. Y.; Aleinov, I.; Arneth, A.; Schurgers, G.; Amelynck, C.; Goldstein, A.; Guenther, A.; Heinesch, B.; Hewitt, C. N.; Karl, T.; Laffineur, Q.; Langford, B.; McKinney, K. A.; Misztal, P.; Potosnak, M.; Rinne, J.; Pressley, S.; Schoon, N.; Serça, D.

2013-10-01

We describe the implementation of a biochemical model of isoprene emission that depends on the electron requirement for isoprene synthesis into the Farquhar-Ball-Berry leaf model of photosynthesis and stomatal conductance that is embedded within a global chemistry-climate simulation framework. The isoprene production is calculated as a function of electron transport-limited photosynthesis, intercellular and atmospheric carbon dioxide concentration, and canopy temperature. The vegetation biophysics module computes the photosynthetic uptake of carbon dioxide coupled with the transpiration of water vapor and the isoprene emission rate at the 30 min physical integration time step of the global chemistry-climate model. In the model, the rate of carbon assimilation provides the dominant control on isoprene emission variability over canopy temperature. A control simulation representative of the present-day climatic state that uses 8 plant functional types (PFTs), prescribed phenology and generic PFT-specific isoprene emission potentials (fraction of electrons available for isoprene synthesis) reproduces 50% of the variability across different ecosystems and seasons in a global database of 28 measured campaign-average fluxes. Compared to time-varying isoprene flux measurements at 9 select sites, the model authentically captures the observed variability in the 30 min average diurnal cycle (R2 = 64-96%) and simulates the flux magnitude to within a factor of 2. The control run yields a global isoprene source strength of 451 TgC yr-1 that increases by 30% in the artificial absence of plant water stress and by 55% for potential natural vegetation.

Photosynthesis-dependent Isoprene Emission from Leaf to Planet in a Global Carbon-chemistry-climate Model

Science.gov (United States)

Unger, N.; Harper, K.; Zeng, Y.; Kiang, N. Y.; Alienov, I.; Arneth, A.; Schurgers, G.; Amelynck, C.; Goldstein, A.; Guenther, A.;

Photosynthesis-dependent isoprene emission from leaf to planet in a global carbon-chemistry-climate model

Energy Technology Data Exchange (ETDEWEB)

Unger, N.; Harper, K.; Zheng, Y.; Kiang, N. Y.; Aleinov, I.; Arneth, Almut; Schurgers, G.; Amelynck, C.; Goldstein, Allen H.; Guenther, Alex B.; Heinesch, B.; Hewitt, C. N.; Karl, T.; Laffineur, Q.; Langford, B.; McKinney, Karena A.; Misztal, P.; Potosnak, M.; Rinne, J.; Pressley, S.; Schoon, N.; Serca, D.

2013-10-22

We describe the implementation of a biochemical model of isoprene emission that depends on the electron requirement for isoprene synthesis into the Farquhar/Ball- Berry leaf model of photosynthesis and stomatal conductance that is embedded within a global chemistry-climate simulation framework. The isoprene production is calculated as a function of electron transport-limited photosynthesis, intercellular carbon dioxide concentration, and canopy temperature. The vegetation biophysics module computes the photosynthetic uptake of carbon dioxide coupled with the transpiration of water vapor and the isoprene emission rate at the 30 min physical integration time step of the global chemistry-climate model. In the model, the rate of carbon assimilation provides the dominant control on isoprene emission variability over canopy temperature. A control simulation representative of the present day climatic state that uses plant functional types (PFTs), prescribed phenology and generic PFT-specific isoprene emission potentials (fraction of electrons available for isoprene synthesis) reproduces 50% of the variability across different ecosystems and seasons in a global database of measured campaign-average fluxes. Compared to time-varying isoprene flux measurements at select sites, the model authentically captures the observed variability in the 30 min average diurnal cycle (R² = 64-96 %) and simulates the flux magnitude to within a factor of 2. The control run yields a global isoprene source strength of 451 TgC yr^-1 that increases by 30% in the artificial absence of plant water stress and by 55% for potential natural vegetation.

Reactivity of OH radicals with chlorobenzoic acids-A pulse radiolysis and steady-state radiolysis study

DEFF Research Database (Denmark)

Zona, Robert; Solar, Sonja; Getoff, Nikola

2010-01-01

The reactions of OH radicals with 2-, 3-, 4-chlorobenzoic acids (ClBzA) and chlorobenzene (ClBz), k(OH+substrates)=(4.5−6.2)×109 dm3 mol−1 s−1, have been studied by pulse radiolysis in N2O saturated solutions. The absorption maxima of the OH-adducts were in the range of 320−340 nm. Their decay wa...... to degradation. The order for the efficiency of dehalogenation was 4->2->3-ClBzA. Several primary radiolytic products could be detected by HPLC. To evaluate the toxicity of final products a bacterial bioluminescence test was carried out....

Isoprene Emission Factors for Subtropical Street Trees for Regional Air Quality Modeling.

Science.gov (United States)

Dunn-Johnston, Kristina A; Kreuzwieser, Jürgen; Hirabayashi, Satoshi; Plant, Lyndal; Rennenberg, Heinz; Schmidt, Susanne

2016-01-01

Evaluating the environmental benefits and consequences of urban trees supports their sustainable management in cities. Models such as i-Tree Eco enable decision-making by quantifying effects associated with particular tree species. Of specific concern are emissions of biogenic volatile organic compounds, particularly isoprene, that contribute to the formation of photochemical smog and ground level ozone. Few studies have quantified these potential disservices of urban trees, and current models predominantly use emissions data from trees that differ from those in our target region of subtropical Australia. The present study aimed (i) to quantify isoprene emission rates of three tree species that together represent 16% of the inventoried street trees in the target region; (ii) to evaluate outputs of the i-Tree Eco model using species-specific versus currently used, generic isoprene emission rates; and (iii) to evaluate the findings in the context of regional air quality. Isoprene emission rates of (Myrtaceae) and (Proteaceae) were 2.61 and 2.06 µg g dry leaf weight h, respectively, whereas (Sapindaceae) was a nonisoprene emitter. We substituted the generic isoprene emission rates with these three empirical values in i-Tree Eco, resulting in a 182 kg yr (97%) reduction in isoprene emissions, totaling 6284 kg yr when extrapolated to the target region. From these results we conclude that care has to be taken when using generic isoprene emission factors for urban tree models. We recommend that emissions be quantified for commonly planted trees, allowing decision-makers to select tree species with the greatest overall benefit for the urban environment. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Airborne measurements of isoprene and monoterpene emissions from southeastern U.S. forests.

Science.gov (United States)

Yu, Haofei; Guenther, Alex; Gu, Dasa; Warneke, Carsten; Geron, Chris; Goldstein, Allen; Graus, Martin; Karl, Thomas; Kaser, Lisa; Misztal, Pawel; Yuan, Bin

2017-10-01

Isoprene and monoterpene emission rates are essential inputs for atmospheric chemistry models that simulate atmospheric oxidant and particle distributions. Process studies of the biochemical and physiological mechanisms controlling these emissions are advancing our understanding and the accuracy of model predictions but efforts to quantify regional emissions have been limited by a lack of constraints on regional distributions of ecosystem emission capacities. We used an airborne wavelet-based eddy covariance measurement technique to characterize isoprene and monoterpene fluxes with high spatial resolution during the 2013 SAS (Southeast Atmosphere Study) in the southeastern United States. The fluxes measured by direct eddy covariance were comparable to emissions independently estimated using an indirect inverse modeling approach. Isoprene emission factors based on the aircraft wavelet flux estimates for high isoprene chemotypes (e.g., oaks) were similar to the MEGAN2.1 biogenic emission model estimates for landscapes dominated by oaks. Aircraft flux measurement estimates for landscapes with fewer isoprene emitting trees (e.g., pine plantations), were about a factor of two lower than MEGAN2.1 model estimates. The tendency for high isoprene emitters in these landscapes to occur in the shaded understory, where light dependent isoprene emissions are diminished, may explain the lower than expected emissions. This result demonstrates the importance of accurately representing the vertical profile of isoprene emitting biomass in biogenic emission models. Airborne measurement-based emission factors for high monoterpene chemotypes agreed with MEGAN2.1 in landscapes dominated by pine (high monoterpene chemotype) trees but were more than a factor of three higher than model estimates for landscapes dominated by oak (relatively low monoterpene emitting) trees. This results suggests that unaccounted processes, such as floral emissions or light dependent monoterpene emissions, or

How light, temperature, and measurement and growth [CO2] interactively control isoprene emission in hybrid aspen.

Science.gov (United States)

Niinemets, Ülo; Sun, Zhihong

2015-02-01

Plant isoprene emissions have been modelled assuming independent controls by light, temperature and atmospheric [CO2]. However, the isoprene emission rate is ultimately controlled by the pool size of its immediate substrate, dimethylallyl diphosphate (DMADP), and isoprene synthase activity, implying that the environmental controls might interact. In addition, acclimation to growth [CO2] can shift the share of the control by DMADP pool size and isoprene synthase activity, and thereby alter the environmental sensitivity. Environmental controls of isoprene emission were studied in hybrid aspen (Populus tremula × Populus tremuloides) saplings acclimated either to ambient [CO2] of 380 μmol mol(-1) or elevated [CO2] of 780 μmol mol(-1). The data demonstrated strong interactive effects of environmental drivers and growth [CO2] on isoprene emissions. Light enhancement of isoprene emission was the greatest at intermediate temperatures and was greater in elevated-[CO2]-grown plants, indicating greater enhancement of the DMADP supply. The optimum temperature for isoprene emission was higher at lower light, suggesting activation of alternative DMADP sinks at higher light. In addition, [CO2] inhibition of isoprene emission was lost at a higher temperature with particularly strong effects in elevated-[CO2]-grown plants. Nevertheless, DMADP pool size was still predicted to more strongly control isoprene emission at higher temperatures in elevated-[CO2]-grown plants. We argue that interactive environmental controls and acclimation to growth [CO2] should be incorporated in future isoprene emission models at the level of DMADP pool size. © The Author 2014. Published by Oxford University Press on behalf of the Society for Experimental Biology.

Enhanced Oxidation of Isoprene and Monoterpenes in High and Low NOx Conditions

Science.gov (United States)

Tokarek, T. W.; Gilman, J.; Lerner, B. M.; Koss, A.; Yuan, B.; Taha, Y. M.; Osthoff, H. D.; Warneke, C.; De Gouw, J. A.

2015-12-01

In the troposphere, the photochemical oxidation of volatile organic compounds (VOCs) is primarily initiated by their reactions with the hydroxyl radical (OH) which yields peroxy radicals (HO2 and RO2). Concentrations of OH and the rates of VOC oxidation depend on the efficiency of peroxy radical recycling to OH. Radical recycling mainly occurs through reaction of HO2 with NO to produce NO2 and, ultimately, ozone (O3). Hence, the rate of VOC oxidation is dependent on NOx (=NO+NO2) concentration. The Shale Oil and Natural Gas Nexus (SONGNEX) campaign was conducted from March 17 to April 29, 2015 with the main goal of identifying and quantifying industrial sources of pollutants throughout the United States, in particular those associated with the production of oil and natural gas. In this work, a case study of biogenic VOC oxidation within and outside a power plant plume in the Haynesville basin near the border of Texas and Louisiana is presented. Isoprene, monoterpenes and their oxides were measured by H3O+ chemical ionization mass spectrometry (H3O+ CIMS) in high time resolution (1 s). Further, an improved Whole Air Sampler (iWAS) was used to collect samples for post-flight analysis by gas chromatography mass spectrometric detection (GC-MS) and yielded speciated quantification of biogenic VOCs. The monoterpene oxide to monoterpene ratio follows the spatial extent of the plume as judged by another tracer (NOx), tracking the enhancement of oxidation rates by NOx. The observations are rationalized with the aid of box modeling using the Master Chemical Mechanism (MCM).

Assessing the impact of anthropogenic pollution on isoprene-derived secondary organic aerosol formation in PM2.5 collected from the Birmingham, Alabama, ground site during the 2013 Southern Oxidant and Aerosol Study

Directory of Open Access Journals (Sweden)

W. Rattanavaraha

2016-04-01

Full Text Available In the southeastern US, substantial emissions of isoprene from deciduous trees undergo atmospheric oxidation to form secondary organic aerosol (SOA that contributes to fine particulate matter (PM2.5. Laboratory studies have revealed that anthropogenic pollutants, such as sulfur dioxide (SO2, oxides of nitrogen (NOx, and aerosol acidity, can enhance SOA formation from the hydroxyl radical (OH-initiated oxidation of isoprene; however, the mechanisms by which specific pollutants enhance isoprene SOA in ambient PM2.5 remain unclear. As one aspect of an investigation to examine how anthropogenic pollutants influence isoprene-derived SOA formation, high-volume PM2.5 filter samples were collected at the Birmingham, Alabama (BHM, ground site during the 2013 Southern Oxidant and Aerosol Study (SOAS. Sample extracts were analyzed by gas chromatography–electron ionization-mass spectrometry (GC/EI-MS with prior trimethylsilylation and ultra performance liquid chromatography coupled to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-QTOFMS to identify known isoprene SOA tracers. Tracers quantified using both surrogate and authentic standards were compared with collocated gas- and particle-phase data as well as meteorological data provided by the Southeastern Aerosol Research and Characterization (SEARCH network to assess the impact of anthropogenic pollution on isoprene-derived SOA formation. Results of this study reveal that isoprene-derived SOA tracers contribute a substantial mass fraction of organic matter (OM ( ∼  7 to  ∼  20 %. Isoprene-derived SOA tracers correlated with sulfate (SO42− (r2 = 0.34, n = 117 but not with NOx. Moderate correlations between methacrylic acid epoxide and hydroxymethyl-methyl-α-lactone (together abbreviated MAE/HMML-derived SOA tracers with nitrate radical production (P[NO3] (r2 = 0.57, n = 40 were observed during nighttime, suggesting a

Processes Controlling CH2O Over the Baltimore/Washington DC Metropolitan Region: A Box Model Analysis Using Data from DISCOVER-AQ

Science.gov (United States)

Olson, J. R.; Crawford, J. H.; Fried, A.; Wisthaler, A.; Weinheimer, A. J.; Barrick, J. D.; Diskin, G. S.; Duncan, B. N.; Mikoviny, T.

2012-12-01

The first deployment for NASA's Earth Venture campaign DISCOVER-AQ (Deriving Information on Surface conditions from Column and Vertically Resolved Observations Relevant to Air Quality) took place over the Baltimore/Washington DC region during July of 2011. Observations of CH2O in the lowest kilometer (pressure-altitude) indicate that median concentrations can vary day to day by as much as 5 ppbv. Further, variability within a single day can correlate with a number of species, including H2O, temperature, isoprene, and/or CO. The NASA Langley photochemical box model is used to examine the dominant budget terms for CH2O during DISCOVER-AQ and to diagnose the drivers of the CH2O variability. Modeling results show that the source of CH2O is largely dominated by isoprene. However, the variability of CH2O within single flight days is rarely directly correlated to isoprene. Rather, most often, CH2O variability is correlated to the oxidative capacity of the atmosphere, defined by OH and driven by OH precursors such as H2O, O3 photolysis rates, and NO. Sensitivity model runs where isoprene is held constant to daily medians show excellent ability to predict both the overall CH2O concentration (dominated by isoprene) and the variability of CH2O throughout a day (driven by variations in oxidative capacity).

Photosynthesis-dependent isoprene emission from leaf to planet in a global carbon-chemistry-climate model

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N. Unger

2013-10-01

Full Text Available We describe the implementation of a biochemical model of isoprene emission that depends on the electron requirement for isoprene synthesis into the Farquhar–Ball–Berry leaf model of photosynthesis and stomatal conductance that is embedded within a global chemistry-climate simulation framework. The isoprene production is calculated as a function of electron transport-limited photosynthesis, intercellular and atmospheric carbon dioxide concentration, and canopy temperature. The vegetation biophysics module computes the photosynthetic uptake of carbon dioxide coupled with the transpiration of water vapor and the isoprene emission rate at the 30 min physical integration time step of the global chemistry-climate model. In the model, the rate of carbon assimilation provides the dominant control on isoprene emission variability over canopy temperature. A control simulation representative of the present-day climatic state that uses 8 plant functional types (PFTs, prescribed phenology and generic PFT-specific isoprene emission potentials (fraction of electrons available for isoprene synthesis reproduces 50% of the variability across different ecosystems and seasons in a global database of 28 measured campaign-average fluxes. Compared to time-varying isoprene flux measurements at 9 select sites, the model authentically captures the observed variability in the 30 min average diurnal cycle (R2 = 64–96% and simulates the flux magnitude to within a factor of 2. The control run yields a global isoprene source strength of 451 TgC yr−1 that increases by 30% in the artificial absence of plant water stress and by 55% for potential natural vegetation.

Line narrowing spectroscopic studies of DNA-carcinogen adducts and DNA-dye complexes

Energy Technology Data Exchange (ETDEWEB)

Suh, Myungkoo [Iowa State Univ., Ames, IA (United States)

1995-12-06

Laser-induced fluorescence line narrowing and non-line narrowing spectroscopic methods were applied to conformational studies of stable DNA adducts of the 7β, 8α-dihydoxy-9α, l0α-epoxy-7,8,9, 10-tetrahydrobenzo[α]pyrene (anti-BPDE). Stereochemically distinct (+)-trans-, (-)-trans-, (+)-cis- and (-)-cis adducts of anti-BPDE bound to exocyclic amino group of the central guanine in an 11-mer oligonucleotide, exist in a mixture of conformations in frozen aqueous buffer matrices. The (+)-trans adduct adopts primarily an external conformation with a smaller fraction ( ~25 %) exists in a partially base-stacked conformation. Both cis adducts were found to be intercalated with significant π-π stacking interactions between the pyrenyl residues and the bases. Conformations of the trans-adduct of (+)-anti -BPDE in 11-mer oligonucleotides were studied as a function of flanking bases. In single stranded form the adduct at G₂ or G₃ (5 ft-flanking, base guanine) adopts a conformation with strong, interaction with the bases. In contrast, the adduct with a 5ft-flanking, thymine exists in a primarily helixexternal conformation. Similar differences were observed in the double stranded oligonucleotides. The nature of the 3ft-flanking base has little influence on the conformational equilibrium of the (+)-trans-anti BPDE-dG adduct. The formation and repair of BPDE-N²-dG in DNA isolated from the skin of mice treated topically with benzo[α]pyrene (BP) was studied. Low-temperature fluorescence spectroscopy of the intact DNA identified the major adduct as (+)-trans-anti-BPDE-N-dG, and the minor adduct fraction consisted mainly of (+)-cis-anti-BPDE-N²-dG.

Repair of O6-methylguanine adducts in human telomeric G-quadruplex DNA by O6-alkylguanine-DNA alkyltransferase

Science.gov (United States)

Hellman, Lance M.; Spear, Tyler J.; Koontz, Colton J.; Melikishvili, Manana; Fried, Michael G.

2014-01-01

O6-alkylguanine-DNA alkyltransferase (AGT) is a single-cycle DNA repair enzyme that removes pro-mutagenic O6-alkylguanine adducts from DNA. Its functions with short single-stranded and duplex substrates have been characterized, but its ability to act on other DNA structures remains poorly understood. Here, we examine the functions of this enzyme on O6-methylguanine (6mG) adducts in the four-stranded structure of the human telomeric G-quadruplex. On a folded 22-nt G-quadruplex substrate, binding saturated at 2 AGT:DNA, significantly less than the ∼5 AGT:DNA found with linear single-stranded DNAs of similar length, and less than the value found with the telomere sequence under conditions that inhibit quadruplex formation (4 AGT:DNA). Despite these differences, AGT repaired 6mG adducts located within folded G-quadruplexes, at rates that were comparable to those found for a duplex DNA substrate under analogous conditions. Repair was kinetically biphasic with the amplitudes of rapid and slow phases dependent on the position of the adduct within the G-quadruplex: in general, adducts located in the top or bottom tetrads of a quadruplex stack exhibited more rapid-phase repair than did adducts located in the inner tetrad. This distinction may reflect differences in the conformational dynamics of 6mG residues in G-quadruplex DNAs. PMID:25080506

Challenges in modelling isoprene and monoterpene emission dynamics of Arctic plants

DEFF Research Database (Denmark)

Tang, Jing; Schurgers, Guy; Valolahti, Hanna Maritta

2016-01-01

test. The model showed reasonable agreement to the observed vegetation CO2 fluxes in the main growing season as well as day-to-day variability of isoprene and monoterpene emissions. The observed relatively high WRs were better captured by the adjusted T response curve than by the common one. During...... 1999-2012, the modelled annual mean isoprene and monoterpene emissions were 20 and 8 mg C mg-2 yrg-1, with an increase by 55 and 57 % for 2 °C summertime warming, respectively. Warming by 4 and 8 °C for the same period further elevated isoprene emission for all years, but the impacts on monoterpene...

Single-Cycle Terahertz Pulse Generation from OH1 Crystal via Cherenkov Phase Matching

Science.gov (United States)

Uchida, Hirohisa; Oota, Kengo; Okimura, Koutarou; Kawase, Kodo; Takeya, Kei

2018-06-01

OH1 crystal is an organic nonlinear optical crystal with a large nonlinear optical constant. However, it has dispersion of refractive indices in the terahertz (THz) frequency. This limits the frequencies that satisfy the phase matching conditions for THz wave generation. In this study, we addressed the phase matching conditions for THz wave generation by combining an OH1 crystal with prism-coupled Cherenkov phase matching. We observed the generation of single-cycle THz pulses with a spectrum covering a frequency range of 3 THz. These results prove that combining prism-coupled Cherenkov phase matching with nonlinear optical crystals yields a THz wave generation method that is insusceptible to crystal dispersion.

Evidence for a significant proportion of Secondary Organic Aerosol from isoprene above a maritime tropical forest

Directory of Open Access Journals (Sweden)

N. H. Robinson

2011-02-01

Full Text Available Isoprene is the most abundant non-methane biogenic volatile organic compound (BVOC, but the processes governing secondary organic aerosol (SOA formation from isoprene oxidation are only beginning to become understood and selective quantification of the atmospheric particulate burden remains difficult. Organic aerosol above a tropical rainforest located in Danum Valley, Borneo, Malaysia, a high isoprene emission region, was studied during Summer 2008 using Aerosol Mass Spectrometry and offline detailed characterisation using comprehensive two dimensional gas chromatography. Observations indicate that a substantial fraction (up to 15% by mass of atmospheric sub-micron organic aerosol was observed as methylfuran (MF after thermal desorption. This observation was associated with the simultaneous measurements of established gas-phase isoprene oxidation products methylvinylketone (MVK and methacrolein (MACR. Observations of MF were also made during experimental chamber oxidation of isoprene. Positive matrix factorisation of the AMS organic mass spectral time series produced a robust factor which accounts for an average of 23% (0.18 μg m⁻³, reaching as much as 53% (0.50 μg m⁻³ of the total oraganic loading, identified by (and highly correlated with a strong MF signal. Assuming that this factor is generally representative of isoprene SOA, isoprene derived aerosol plays a significant role in the region. Comparisons with measurements from other studies suggest this type of isoprene SOA plays a role in other isoprene dominated environments, albeit with varying significance.

DNA adducts in senescent cells

International Nuclear Information System (INIS)

Gaubatz, J.W.

1987-01-01

Perturbations in DNA repair and other metabolic processes during development and aging might affect the steady-state level of genomic damage. The persistence or accumulation of DNA lesions in postmitotic cells could have a significant impact on proper cellular function, interfering with gene regulation for example. To test the notion that DNA damage increases as a function of age in non-dividing cells, DNA was purified from heart tissue of C57BL/6Nia mice at different ages and analyzed by post labeling techniques to detect DNA adducts. In the present experiments, four-dimensional, thin-layer chromatography was used to isolate aromatic adducts that were labeled with carrier-free (γ- 32 P) ATP under DNA-P excess conditions. The complexity and frequency of aromatic adducts varied between DNA samples. Several adducts were present in all preparations and were clearly more abundant in nucleotide maps of mature and old heart DNA. However, a direct correlation with age was not observed. In contrast, experiments in which aromatic adducts were first isolated by phase-transfer to 1-butanol, then labeled with excess (γ- 32 P)ATP indicated that there was an age-related increase in these adducts. The results are consistent with their earlier studies that showed alkyl adducts increased during aging of mouse myocardium and suggest that a common repair pathway might be involved

Global isoprene and monoterpene emissions under changing climate, vegetation, CO2 and land use

DEFF Research Database (Denmark)

Hantson, Stijn; Knorr, Wolfgang; Schurgers, Guy

2017-01-01

Plants emit large quantities of isoprene and monoterpenes, the main components of global biogenic volatile organic compound (BVOC) emissions. BVOCs have an important impact on the atmospheric composition of methane, and of short-lived radiative forcing agents (e.g. ozone, aerosols etc.). It is th......Plants emit large quantities of isoprene and monoterpenes, the main components of global biogenic volatile organic compound (BVOC) emissions. BVOCs have an important impact on the atmospheric composition of methane, and of short-lived radiative forcing agents (e.g. ozone, aerosols etc.......). It is therefore necessary to know how isoprene and monoterpene emissions have changed over the past and how future changes in climate, land-use and other factors will impact them. Here we present emission estimates of isoprene and monoterpenes over the period 1901–2 100 based on the dynamic global vegetation...... model LPJ-GUESS, including the effects of all known important drivers. We find that both isoprene and monoterpene emissions at the beginning of the 20th century were higher than at present. While anthropogenic land-use change largely drives the global decreasing trend for isoprene over the 20th century...

Different roles of water in secondary organic aerosol formation from toluene and isoprene

Science.gov (United States)

Jia, Long; Xu, YongFu

2018-06-01

Roles of water in the formation of secondary organic aerosol (SOA) from the irradiations of toluene-NO2 and isoprene-NO2 were investigated in a smog chamber. Experimental results show that the yield of SOA from toluene almost doubled as relative humidity increased from 5 to 85 %, whereas the yield of SOA from isoprene under humid conditions decreased by 2.6 times as compared to that under dry conditions. The distinct difference of RH effects on SOA formation from toluene and isoprene is well explained with our experiments and model simulations. The increased SOA from humid toluene-NO2 irradiations is mainly contributed by O-H-containing products such as polyalcohols formed from aqueous reactions. The major chemical components of SOA in isoprene-NO2 irradiations are oligomers formed from the gas phase. SOA formation from isoprene-NO2 irradiations is controlled by stable Criegee intermediates (SCIs) that are greatly influenced by water. As a result, high RH can obstruct the oligomerization reaction of SCIs to form SOA.

Isoprene emissions over Asia 1979-2012 : impact of climate and land use changes

Science.gov (United States)

Stavrakou, Trissevgeni; Müller, Jean-Francois; Bauwens, Maite; Guenther, Alex; De Smedt, Isabelle; Van Roozendael, Michel

2014-05-01

Due to the scarcity of observational contraints and the rapidly changing environment in East and Southeast Asia, isoprene emissions predicted by models are expected to bear substantial uncertainties. This study aims at improving upon current bottom-up estimates, and investigate the temporal evolution of isoprene fluxes in Asia over 1979-2012. For that, we use the MEGAN model and incorporate (i) changes in land use, including the rapid expansion of oil palms, (ii) meteorological variability, (iii) long-term changes in solar radiation constrained by surface network measurements, and (iv) recent experimental evidence that South Asian forests are much weaker isoprene emitters than previously assumed. These effects lead to a significant reduction of the total isoprene fluxes over the studied domain compared to the standard simulation. The bottom-up emissions are evaluated using satellite-based emission estimates derived from inverse modelling constrained by GOME-2/MetOp-A formaldehyde columns through 2007-2012. The top-down estimates support our assumptions and confirm the lower isoprene emission rate in tropical forests of Indonesia and Malaysia.

Synthesis of Mesoporous Single Crystal Co(OH)2 Nanoplate and Its Topotactic Conversion to Dual-Pore Mesoporous Single Crystal Co3O4.

Science.gov (United States)

Jia, Bao-Rui; Qin, Ming-Li; Li, Shu-Mei; Zhang, Zi-Li; Lu, Hui-Feng; Chen, Peng-Qi; Wu, Hao-Yang; Lu, Xin; Zhang, Lin; Qu, Xuan-Hui

2016-06-22

A new class of mesoporous single crystalline (MSC) material, Co(OH)2 nanoplates, is synthesized by a soft template method, and it is topotactically converted to dual-pore MSC Co3O4. Most mesoporous materials derived from the soft template method are reported to be amorphous or polycrystallined; however, in our synthesis, Co(OH)2 seeds grow to form single crystals, with amphiphilic block copolymer F127 colloids as the pore producer. The single-crystalline nature of material can be kept during the conversion from Co(OH)2 to Co3O4, and special dual-pore MSC Co3O4 nanoplates can be obtained. As the anode of lithium-ion batteries, such dual-pore MSC Co3O4 nanoplates possess exceedingly high capacity as well as long cyclic performance (730 mAh g(-1) at 1 A g(-1) after the 350th cycle). The superior performance is because of the unique hierarchical mesoporous structure, which could significantly improve Li(+) diffusion kinetics, and the exposed highly active (111) crystal planes are in favor of the conversion reaction in the charge/discharge cycles.

Coregulation of terpenoid pathway genes and prediction of isoprene production in Bacillus subtilis using transcriptomics

Energy Technology Data Exchange (ETDEWEB)

Hess, Becky M.; Xue, Junfeng; Markillie, Lye Meng; Taylor, Ronald C.; Wiley, H. S.; Ahring, Birgitte K.; Linggi, Bryan E.

2013-06-19

The isoprenoid pathway converts pyruvate to isoprene and related isoprenoid compounds in plants and some bacteria. Currently, this pathway is of great interest because of the critical role that isoprenoids play in basic cellular processes as well as the industrial value of metabolites such as isoprene. Although the regulation of several pathway genes has been described, there is a paucity of information regarding the system level regulation and control of the pathway. To address this limitation, we examined Bacillus subtilis grown under multiple conditions and then determined the relationship between altered isoprene production and the pattern of gene expression. We found that terpenoid genes appeared to fall into two distinct subsets with opposing correlations with respect to the amount of isoprene produced. The group whose expression levels positively correlated with isoprene production included dxs, the gene responsible for the commitment step in the pathway, as well as ispD, and two genes that participate in the mevalonate pathway, yhfS and pksG. The subset of terpenoid genes that inversely correlated with isoprene production included ispH, ispF, hepS, uppS, ispE, and dxr. A genome wide partial least squares regression model was created to identify other genes or pathways that contribute to isoprene production. This analysis showed that a subset of 213 regulated genes was sufficient to create a predictive model of isoprene production under different conditions and showed correlations at the transcriptional level. We conclude that gene expression levels alone are sufficiently informative about the metabolic state of a cell that produces increased isoprene and can be used to build a model which accurately predicts production of this secondary metabolite across many simulated environmental conditions.

Effect of humidity on the composition of isoprene photooxidation secondary organic aerosol

Directory of Open Access Journals (Sweden)

T. B. Nguyen

2011-07-01

Full Text Available The effect of relative humidity (RH on the composition and concentrations of gas-phase products and secondary organic aerosol (SOA generated from the photooxidation of isoprene under high-NO_x conditions was investigated. Experiments were performed with hydrogen peroxide as the OH precursor and in the absence of seed aerosol. The relative yields of most gas-phase products were the same regardless of initial water vapor concentration with exception of hydroxyacetone and glycolaldehyde, which were considerably affected by RH. A significant change was observed in the SOA composition, with many unique condensed-phase products formed under humid (90 % RH vs. dry (<2 % RH conditions, without any detectable effect on the rate and extent of the SOA mass growth. There is a 40 % reduction in the number and relative abundance of distinct particle-phase nitrogen-containing organic compounds (NOC detected by high resolution mass spectrometry. The suppression of condensation reactions, which produce water as a product, is the most important chemical effect of the increased RH. For example, the total signal from oligomeric esters of 2-methylglyceric acid was reduced by about 60 % under humid conditions and the maximum oligomer chain lengths were reduced by 7–11 carbons. Oligomers formed by addition mechanisms, without direct involvement of water, also decreased at elevated RH but to a much smaller extent. The observed reduction in the extent of condensation-type oligomerization at high RH may have substantial impact on the phase characteristics and hygroscopicity of the isoprene aerosol. The reduction in the amount of organic nitrates in the particle phase has implications for understanding the budget of NOC compounds.

Measurements of the Weak UV Absorptions of Isoprene and Acetone at 261–275 nm Using Cavity Ringdown Spectroscopy for Evaluation of a Potential Portable Ringdown Breath Analyzer

Science.gov (United States)

Sahay, Peeyush; Scherrer, Susan T.; Wang, Chuji

2013-01-01

The weak absorption spectra of isoprene and acetone have been measured in the wavelength range of 261–275 nm using cavity ringdown spectroscopy. The measured absorption cross-sections of isoprene in the wavelength region of 261–266 nm range from 3.65 × 10−21 cm2·molecule−1 at 261 nm to 1.42 × 10−21 cm2·molecule−1 at 266 nm; these numbers are in good agreement with the values reported in the literature. In the longer wavelength range of 270–275 nm, however, where attractive applications using a single wavelength compact diode laser operating at 274 nm is located, isoprene has been reported in the literature to have no absorption (too weak to be detected). Small absorption cross-sections of isoprene in this longer wavelength region are measured using cavity ringdown spectroscopy for the first time in this work, i.e., 6.20 × 10−23 cm2·molecule−1 at 275 nm. With the same experimental system, wavelength-dependent absorption cross-sections of acetone have also been measured. Theoretical detection limits of isoprene and comparisons of absorbance of isoprene, acetone, and healthy breath gas in this wavelength region are also discussed. PMID:23803787

Quantifying the causes of differences in tropospheric OH within global models

Science.gov (United States)

Nicely, Julie M.; Salawitch, Ross J.; Canty, Timothy; Anderson, Daniel C.; Arnold, Steve R.; Chipperfield, Martyn P.; Emmons, Louisa K.; Flemming, Johannes; Huijnen, Vincent; Kinnison, Douglas E.; Lamarque, Jean-François; Mao, Jingqiu; Monks, Sarah A.; Steenrod, Stephen D.; Tilmes, Simone; Turquety, Solene

2017-02-01

The hydroxyl radical (OH) is the primary daytime oxidant in the troposphere and provides the main loss mechanism for many pollutants and greenhouse gases, including methane (CH4). Global mean tropospheric OH differs by as much as 80% among various global models, for reasons that are not well understood. We use neural networks (NNs), trained using archived output from eight chemical transport models (CTMs) that participated in the Polar Study using Aircraft, Remote Sensing, Surface Measurements and Models, of Climate, Chemistry, Aerosols and Transport Model Intercomparison Project (POLMIP), to quantify the factors responsible for differences in tropospheric OH and resulting CH4 lifetime (τCH4) between these models. Annual average τCH4, for loss by OH only, ranges from 8.0 to 11.6 years for the eight POLMIP CTMs. The factors driving these differences were quantified by inputting 3-D chemical fields from one CTM into the trained NN of another CTM. Across all CTMs, the largest mean differences in τCH4 (ΔτCH4) result from variations in chemical mechanisms (ΔτCH4 = 0.46 years), the photolysis frequency (J) of O3 → O(1D) (0.31 years), local O3 (0.30 years), and CO (0.23 years). The ΔτCH4 due to CTM differences in NOx (NO + NO2) is relatively low (0.17 years), although large regional variation in OH between the CTMs is attributed to NOx. Differences in isoprene and J(NO2) have negligible overall effect on globally averaged tropospheric OH, although the extent of OH variations due to each factor depends on the model being examined. This study demonstrates that NNs can serve as a useful tool for quantifying why tropospheric OH varies between global models, provided that essential chemical fields are archived.

Isoprene emissions at the canopy scale: measurements in the Escompte program

Science.gov (United States)

Serça, D.; Fotiadi, A.; Bouchou, P.; Cortinovis, J.

2003-04-01

Concentrations of biogenic volatile organic compounds (BVOCs) play a crucial role in the atmospheric chemistry through their role in the production-destruction cycle of tropospheric O3. Half of these BVOCs would be made of isoprene (C5H8), a compound predominantly emitted by ligneous species. Measurements presented here were collected during the ESCOMPTE campaign carried out in the Marseille region, South-West of France. Meteorological parameters, microclimate and fluxes were measured at the canopy scale of a Quercus pubescens forest. Latent and sensible heat, CO2 and isoprene fluxes were calculated using the eddy covariance method. Isoprene fluxes followed the expected diurnal evolution, with maximum emissions at noon reaching about 5 to 10 mgC m-2 h-1. Significant regression coefficient (r2 between 0.61 and 0.76) were found between isoprene emission and PAR, isoprene concentrations and energy fluxes (latent and sensible). The strongest correlation (r2 = 0.8) was found between mean emission and temperature averaged each day between 6 am and 6pm. A cumulative effect of temperature was observed with a constant flux increase (max from 5 to 15 mgCm-2h-1) along a one week period corresponding to an increase in maximum temperature from 24°C to 30°C. The calculated mean emission factor (37.2 µg g-1dw h-1) is in the order of values found in the literature for oak Mediterranean forests.

Secondary organic aerosols over oceans via oxidation of isoprene and monoterpenes from Arctic to Antarctic.

Science.gov (United States)

Hu, Qi-Hou; Xie, Zhou-Qing; Wang, Xin-Ming; Kang, Hui; He, Quan-Fu; Zhang, Pengfei

2013-01-01

Isoprene and monoterpenes are important precursors of secondary organic aerosols (SOA) in continents. However, their contributions to aerosols over oceans are still inconclusive. Here we analyzed SOA tracers from isoprene and monoterpenes in aerosol samples collected over oceans during the Chinese Arctic and Antarctic Research Expeditions. Combined with literature reports elsewhere, we found that the dominant tracers are the oxidation products of isoprene. The concentrations of tracers varied considerably. The mean average values were approximately one order of magnitude higher in the Northern Hemisphere than in the Southern Hemisphere. High values were generally observed in coastal regions. This phenomenon was ascribed to the outflow influence from continental sources. High levels of isoprene could emit from oceans and consequently have a significant impact on marine SOA as inferred from isoprene SOA during phytoplankton blooms, which may abruptly increase up to 95 ng/m³ in the boundary layer over remote oceans.

Measurement of endogenous acetone and isoprene in exhaled breath during sleep

International Nuclear Information System (INIS)

King, Julian; Kupferthaler, Alexander; Unterkofler, Karl; Amann, Anton; Frauscher, Birgit; Hackner, Heinz; Högl, Birgit; Teschl, Gerald; Hinterhuber, Hartmann

2012-01-01

This explorative study aims at characterizing the breath behavior of two prototypic volatile organic compounds, acetone and isoprene, during normal human sleep and to possibly relate changes in the respective concentration time courses to the underlying sleep architecture. For this purpose, six normal healthy volunteers (two females, four males, age 20–29 years) were monitored over two consecutive nights (the first one being an adaption night) by combining real-time proton-transfer-reaction mass spectrometry measurements from end-tidal exhalation segments with laboratory-based polysomnographic data. Breath acetone concentrations increased overnight in all measurements, with an average relative change by a factor of up to 4 (median 2.5). Nighttime concentration maxima were usually recorded 2–3 h before lights on. For breath isoprene, a nocturnal increase in baseline concentrations of about 74% was observed, with individual changes ranging from 36–110%. Isoprene profiles exhibited pronounced concentration peaks, which were highly specific for leg movements as scored by tibial electromyography. Furthermore, relative to a linear trend, baseline isoprene concentrations decreased during the transition from the NREM to the REM phase of a complete sleep cycle. (paper)

32P-postlabeling DNA adduct assay: cigarette smoke-induced dna adducts in the respiratory and nonrespiratory rat tissues. Book chapter

International Nuclear Information System (INIS)

Gupta, R.C.; Gairola, C.G.

1990-01-01

An analysis of the tissue DNA adducts in rats by the sensitive (32)p-postlabeling assay showed one to eight detectable DNA adducts in lung, trachea, larynx, heart and bladder of the sham controls. Chronic exposure of animals to mainstream cigarette smoke showed a remarkable enhancement of most adducts in the lung and heart DNA. Since cigarette smoke contains several thousand chemicals and a few dozen of them are known or potential carcinogens, the difference between the DNA adducts of nasal and the other tissues may reflect the diversity of reactive constituents and their differential absorption in different tissues. In comparison to the lung DNA adducts, the adducts in nasal DNA were less hydrophobic. Identity of the predominant adducts was further investigated by comparison with several reference DNA adducts from 10 PAH and aromatic amines. Since some of these chemicals are present in cigarette smoke, the results suggest that these constituents of cigarette smoke may not be directly responsible for formation of DNA adducts in the lung and heart of the smoke-exposed animals

High-resolution photoelectron spectroscopy of TiO3H2-: Probing the TiO2- + H2O dissociative adduct

Science.gov (United States)

DeVine, Jessalyn A.; Abou Taka, Ali; Babin, Mark C.; Weichman, Marissa L.; Hratchian, Hrant P.; Neumark, Daniel M.

2018-06-01

Slow electron velocity-map imaging spectroscopy of cryogenically cooled TiO3H2- anions is used to probe the simplest titania/water reaction, TiO20/- + H2O. The resultant spectra show vibrationally resolved structure assigned to detachment from the cis-dihydroxide TiO(OH)2- geometry based on density functional theory calculations, demonstrating that for the reaction of the anionic TiO2- monomer with a single water molecule, the dissociative adduct (where the water is split) is energetically preferred over a molecularly adsorbed geometry. This work represents a significant improvement in resolution over previous measurements, yielding an electron affinity of 1.2529(4) eV as well as several vibrational frequencies for neutral TiO(OH)2. The energy resolution of the current results combined with photoelectron angular distributions reveals Herzberg-Teller coupling-induced transitions to Franck-Condon forbidden vibrational levels of the neutral ground state. A comparison to the previously measured spectrum of bare TiO2- indicates that reaction with water stabilizes neutral TiO2 more than the anion, providing insight into the fundamental chemical interactions between titania and water.

Photosynthesis-dependent isoprene emission from leaf to planet in a global carbon-chemistry-climate model

OpenAIRE

Unger, N.; Harper, K.; Zheng, Y.; Kiang, N. Y.; Aleinov, I.; Arneth, A.; Schurgers, G.; Amelynyck, C.; Goldstein, A.; Guenther, A.; Heinesch, B.; Hewitt, C. N.; Karl, T.; Laffineur, Q.; Langford, B.

2013-01-01

We describe the implementation of a biochemical model of isoprene emission that depends on the electron requirement for isoprene synthesis into the Farquhar–Ball–Berry leaf model of photosynthesis and stomatal conductance that is embedded within a global chemistry-climate simulation framework. The isoprene production is calculated as a function of electron transport-limited photosynthesis, intercellular and atmospheric carbon dioxide concentration, and canopy temperature. Th...

Understanding isoprene photooxidation using observations and modeling over a subtropical forest in the southeastern US

Directory of Open Access Journals (Sweden)

L. Su

2016-06-01

Full Text Available The emission, dispersion, and photochemistry of isoprene (C5H8 and related chemical species in the convective boundary layer (CBL during sunlit daytime were studied over a mixed forest in the southeastern United States by combining ground-based and aircraft observations. Fluxes of isoprene and monoterpenes were quantified at the top of the forest canopy using a high-resolution proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS. Snapshot (∼  2 min sampling duration vertical profiles of isoprene, methyl vinyl ketone (MVK + methacrolein (MACR, and monoterpenes were collected from aircraft every hour in the CBL (100–1000 m. Both ground-based and airborne collected volatile organic compound (VOC data are used to constrain the initial conditions of a mixed-layer chemistry model (MXLCH, which is applied to examine the chemical evolution of the O3–NOx–HOx–VOC system and how it is affected by boundary layer dynamics in the CBL. The chemical loss rate of isoprene (∼  1 h is similar to the turbulent mixing timescale (0.1–0.5 h, which indicates that isoprene concentrations are equally dependent on both photooxidation and boundary layer dynamics. Analysis of a model-derived concentration budget suggests that diurnal evolution of isoprene inside the CBL is mainly controlled by surface emissions and chemical loss; the diurnal evolution of O3 is dominated by entrainment. The NO to HO2 ratio (NO : HO2 is used as an indicator of anthropogenic impact on the CBL chemical composition and spans a wide range (1–163. The fate of hydroxyl-substituted isoprene peroxyl radical (HOC5H8OO·; ISOPOO is strongly affected by NO : HO2, shifting from NO-dominant to NO–HO2-balanced conditions from early morning to noontime. This chemical regime change is reflected in the diurnal evolution of isoprene hydroxynitrates (ISOPN and isoprene hydroxy hydroperoxides (ISOPOOH.

Aflatoxin B1-lysine adduct in dried blood spot samples of animals and humans.

Science.gov (United States)

Xue, Kathy S; Cai, Wenjie; Tang, Lili; Wang, Jia-Sheng

2016-12-01

Dried blood spots (DBS) were proposed as potentially viable method for exposure assessment of environmental toxicants in infant and young children. For this study, we validated an experimental protocol to quantify AFB 1 -lysine adduct in DBS samples of AFB 1 -treated F344 rats, as well as samples from human field study. Significant dose-response relationships in AFB 1 -lysine adduct formation were found in DBS samples of rats treated with single- and repeated-dose AFB 1 . AFB 1 -lysine levels in DBS samples were highly correlated with corresponding serum sample levels. The Person coefficients were 0.997 for the single-dose exposure, and 0.996 for the repeated-dose exposure. Levels of AFB 1 -lysine adduct had also good agreement between DBS and serum samples as shown by Bland-Altman plot analysis. For human field study samples (n = 36), a Pearson correlation coefficient of 0.784 was found between AFB 1 -lysine adduct levels of DBS and corresponding serum samples. Bland-Altman plots showed the distribution of the log differences between DBS and serum AFB 1 -lysine levels are within 95% confidence intervals. These results showed AFB 1 -lysine adduct levels in DBS cards and serum samples from animals and human samples are comparable, and the DBS technique and analytical protocol is a good means to assess AFB 1 exposure in infant and children populations. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effect of turmeric and curcumin on BP-DNA adducts.

Science.gov (United States)

Mukundan, M A; Chacko, M C; Annapurna, V V; Krishnaswamy, K

1993-03-01

Many human cancers that are widely prevalent today can be prevented through modifications in life-styles, of which diet appears to be an important agent. Several dietary constituents modulate the process of carcinogenesis and prevent genotoxicity. Many plant constituents including turmeric appear to be potent antimutagens and antioxidants. Therefore the modulatory effects of turmeric and curcumin on the levels of benzo[a]pyrene induced DNA adducts in the livers of rats were studied by the newly developed 32P-postlabelling assay method. Turmeric when fed at 0.1, 0.5 and 3% and the active principle of turmeric (curcumin) when fed at a level of 0.03% in the diet for 4 weeks significantly reduced the level of BP-DNA adducts including the major adduct dG-N2-BP, formed within 24 h in response to a single i.p. injection of benzo[a]pyrene. The significance of these effects in terms of the potential anticarcinogenic effects of turmeric is discussed. Further, these results strengthen the various other biological effects of turmeric which have direct relevance to anticarcinogenesis and chemoprevention.

Two-year concurrent observation of isoprene at 20 sites over China: comparison with MEGAN-REAM model simulation

Science.gov (United States)

Zhang, Y.; Yang, W.; Zhang, R.; Zhang, Z.; Lyu, S.; Yu, J.; Wang, Y.; Wang, G.; Wang, X.

2017-12-01

Isoprene, the most abundant non-methane hydrocarbon emitted from plants, directly and indirectly affects atmospheric photochemistry and radiative forcing, yet narrowing its emission uncertainties is a continuous challenge. Comparison of observed and modelled isoprene on large spatiotemporal scales would help recognize factors that control isoprene variability, systematic field observation data are however quite lacking. Here we collected ambient air samples with 1 L silonite-treated stainless steel canisters simultaneously at 20 sites over China on every Wednesday at approximately 14:00 pm Beijing time from 2012 to 2014, and analyzed isoprene mixing ratios by preconcentrator-GC-MSD/FID. Observed isoprene mixing ratios were also compared with that simulated by coupling MEGAN 2.0 (Guenther et al., 2006) with a 3-D Regional chEmical trAnsport Model (REAM) (Zhang et al., 2017). Similar seasonal variations between observation and model simulation were obtained for most of sampling sites, but overall the average isoprene mixing ratios during growing months (May to October) was 0.37 ± 0.08 ppbv from model simulation, about 32% lower than that of 0.54 ± 0.20 ppbv based on ground-based observation, and this discrepancy was particularly significant in north China during wintertime. Further investigation demonstrated that emission of biogenic isoprene in northwest China might be underestimated and non-biogenic emission, such burning biomass/biofuel, might contribute to the elevated levels of isoprene during winter time. The observation-based empirical formulas for changing isoprene emission with solar radiation and temperature were also derived for different regions of China.

Analysis of the isoprene chemistry observed during the New England Air Quality Study (NEAQS) 2002 intensive experiment

Science.gov (United States)

Roberts, James M.; Marchewka, Mathew; Bertman, Steven B.; Goldan, Paul; Kuster, William; de Gouw, Joost; Warneke, Carsten; Williams, Eric; Lerner, Brian; Murphy, Paul; Apel, Eric; Fehsenfeld, Fred C.

2006-12-01

Isoprene and its first and second generation photochemical products, methyl vinyl ketone (MVK), methacrolein (MACR), and peroxymethacrylic nitric anhydride (MPAN), were measured off the coast of New England during the 2002 New England Air Quality Study (NEAQS) on board the NOAA Research Vessel Ronald H. Brown. The results of these measurements were analyzed using a simple sequential reaction model that has been used previously to examine regional oxidant chemistry. The highest isoprene impact was observed in air masses that had passed over an area of high isoprene emission WSW of Boston. The relative concentrations of isoprene and its first generation products show that the photochemistry is consistently "older" than the isoprene photochemistry observed at continental sites. The sequential reaction model was also applied to the aldehyde-PANs (Peroxycarboxylic nitric anhydride) system, and the resulting PPN (peroxypropionic nitric anhydride)/propanal and PAN (peroxyacetic nitric anhydride)/acetaldehyde relationships were consistent with additional sources of PAN in this environment, e.g., isoprene photochemistry. This isoprene source was estimated to result in approximately 1.6 to 4 times more PAN in this environment relative to that produced from anthropogenic VOCs (volatile organic compounds) alone.

UV spectra and OH-oxidation kinetics of gaseous phase morpholinic compounds

KAUST Repository

Rachidi, Mariam El

2014-05-01

This paper presents an experimental study of the UV spectra as well as the kinetics of gaseous phase OH-oxidation of morpholine, N-formylmorpholine (NFM) and N-acetlymorpholine (NAM). The spectra recorded using a UV spectrometer in the spectral range 200-280nm show that the analytes mainly absorb at wavelengths less than 280nm. This indicates that their photolysis potential in the troposphere is insignificant. Meanwhile, the OH-reactivity of these analytes was studied using a triple-jacket 2m long reactor equipped with a multi-reflection system and coupled to an FTIR spectrometer. The experiments were carried out at 295 and 313K for the amine and amides, respectively. The study was conducted in the relative mode using isoprene and benzaldehyde as reference compounds. The rate constants obtained are 14.0±1.9, 4.0±1.1 and 3.8±1.0 (in units of 10-11cm3molecule-1s-1) for morpholine, NFM and NAM respectively. These results are discussed in terms of reactivity and compared to those obtained for other oxy-nitrogenated species. In addition, the determined rate constants are used to estimate effective atmospheric lifetimes of the investigated morpholinic compounds with respect to reaction with OH radicals. © 2014 Elsevier Ltd.

UV spectra and OH-oxidation kinetics of gaseous phase morpholinic compounds

KAUST Repository

Rachidi, Mariam El; El Masri, A.; Roth, E.; Chakir, A.

2014-01-01

This paper presents an experimental study of the UV spectra as well as the kinetics of gaseous phase OH-oxidation of morpholine, N-formylmorpholine (NFM) and N-acetlymorpholine (NAM). The spectra recorded using a UV spectrometer in the spectral range 200-280nm show that the analytes mainly absorb at wavelengths less than 280nm. This indicates that their photolysis potential in the troposphere is insignificant. Meanwhile, the OH-reactivity of these analytes was studied using a triple-jacket 2m long reactor equipped with a multi-reflection system and coupled to an FTIR spectrometer. The experiments were carried out at 295 and 313K for the amine and amides, respectively. The study was conducted in the relative mode using isoprene and benzaldehyde as reference compounds. The rate constants obtained are 14.0±1.9, 4.0±1.1 and 3.8±1.0 (in units of 10-11cm3molecule-1s-1) for morpholine, NFM and NAM respectively. These results are discussed in terms of reactivity and compared to those obtained for other oxy-nitrogenated species. In addition, the determined rate constants are used to estimate effective atmospheric lifetimes of the investigated morpholinic compounds with respect to reaction with OH radicals. © 2014 Elsevier Ltd.

Contribution of various carbon sources toward isoprene biosynthesis in poplar leaves mediated by altered atmospheric CO2 concentrations.

Directory of Open Access Journals (Sweden)

Amy M Trowbridge

Full Text Available Biogenically released isoprene plays important roles in both tropospheric photochemistry and plant metabolism. We performed a (13CO(2-labeling study using proton-transfer-reaction mass spectrometry (PTR-MS to examine the kinetics of recently assimilated photosynthate into isoprene emitted from poplar (Populus × canescens trees grown and measured at different atmospheric CO(2 concentrations. This is the first study to explicitly consider the effects of altered atmospheric CO(2 concentration on carbon partitioning to isoprene biosynthesis. We studied changes in the proportion of labeled carbon as a function of time in two mass fragments, M41(+, which represents, in part, substrate derived from pyruvate, and M69(+, which represents the whole unlabeled isoprene molecule. We observed a trend of slower (13C incorporation into isoprene carbon derived from pyruvate, consistent with the previously hypothesized origin of chloroplastic pyruvate from cytosolic phosphenolpyruvate (PEP. Trees grown under sub-ambient CO(2 (190 ppmv had rates of isoprene emission and rates of labeling of M41(+ and M69(+ that were nearly twice those observed in trees grown under elevated CO(2 (590 ppmv. However, they also demonstrated the lowest proportion of completely labeled isoprene molecules. These results suggest that under reduced atmospheric CO(2 availability, more carbon from stored/older carbon sources is involved in isoprene biosynthesis, and this carbon most likely enters the isoprene biosynthesis pathway through the pyruvate substrate. We offer direct evidence that extra-chloroplastic rather than chloroplastic carbon sources are mobilized to increase the availability of pyruvate required to up-regulate the isoprene biosynthesis pathway when trees are grown under sub-ambient CO(2.

Distribution and sea-to-air flux of isoprene in the East China Sea and the South Yellow Sea during summer.

Science.gov (United States)

Li, Jian-Long; Zhang, Hong-Hai; Yang, Gui-Peng

2017-07-01

Spatial distribution and sea-to-air flux of isoprene in the East China Sea and the South Yellow Sea in July 2013 were investigated. This study is the first to report the concentrations of isoprene in the China marginal seas. Isoprene concentrations in the surface seawater during summer ranged from 32.46 to 173.5 pM, with an average of 83.62 ± 29.22 pM. Distribution of isoprene in the study area was influenced by the diluted water from the Yangtze River, which stimulated higher in-situ phytoplankton production of isoprene rather than direct freshwater input. Variations in isoprene concentrations were found to be diurnal, with high values observed during daytime. A significant correlation was observed between isoprene and chlorophyll a in the study area. Relatively higher isoprene concentrations were recorded at stations where the phytoplankton biomass was dominated by Chaetoceros, Skeletonema, Pennate-nitzschia, and Thalassiosira. Positive correlation was observed between isoprene and methyl iodide. In addition, sea-to-air fluxes of isoprene approximately ranged from 22.17 nmol m -2  d -1 -537.2 nmol m -2  d -1 , with an average of 161.5 ± 133.3 nmol m -2  d -1 . These results indicate that the coastal and shelf areas may be important sources of atmospheric isoprene. Copyright © 2017 Elsevier Ltd. All rights reserved.

Concentrations and fluxes of isoprene and oxygenated VOCs at a French Mediterranean oak forest

International Nuclear Information System (INIS)

Kalogridis, C.; Gros, V.; Sarda-Esteve, R.; Bonsang, B.; Bonnaire, N.; Boissard, C.; Baisnee, D.; Lathiere, J.

2014-01-01

The CANOPEE project aims to better understand the biosphere-atmosphere exchanges of biogenic volatile organic compounds (BVOCs) in the case of Mediterranean ecosystems and the impact of in-canopy processes on the atmospheric chemical composition above the canopy. Based on an intensive field campaign, the objective of our work was to determine the chemical composition of the air inside a canopy as well as the net fluxes of reactive species between the canopy and the boundary layer. Measurements were carried out during spring 2012 at the field site of the Oak Observatory of the Observatoire de Haute Provence (O3HP) located in the southeast of France. The site is a forest ecosystem dominated by downy oak, Quercus pubescens Willd., a typical Mediterranean species which features large isoprene emission rates. Mixing ratios of isoprene, its degradation products methylvinylketone (MVK) and methacrolein (MACR) and several other oxygenated VOC (OxVOC) were measured above the canopy using an online proton transfer reaction mass spectrometer (PTR-MS), and fluxes were calculated by the disjunct eddy covariance approach. The O3HP site was found to be a very significant source of isoprene emissions, with daily maximum ambient concentrations ranging between 2-16 ppbv inside and 2-5 ppbv just above the top of the forest canopy. Significant isoprene fluxes were observed only during daytime, following diurnal cycles with midday net emission fluxes from the canopy ranging between 2.0 and 9.7 mgm -2 h -1 . Net isoprene normalized flux (at 30 C, 1000 μmol quantam -2 s -1 ) was estimated at 7.4 mgm -2 h -1 . Evidence of direct emission of methanol was also found exhibiting maximum daytime fluxes ranging between 0.2 and 0.6 mgm -2 h -1 , whereas flux values for monoterpenes and others OxVOC such as acetone and acetaldehyde were below the detection limit. The MVK+MACR-to-isoprene ratio provided useful information on the oxidation of isoprene, and is in agreement with recent findings

Fullerene–Carbene Lewis Acid–Base Adducts

KAUST Repository

Li, Huaping

2011-08-17

The reaction between a bulky N-heterocylic carbene (NHC) and C60 leads to the formation of a thermally stable zwitterionic Lewis acid-base adduct that is connected via a C-C single bond. Low-energy absorption bands with weak oscillator strengths similar to those of n-doped fullerenes were observed for the product, consistent with a net transfer of electron density to the C60 core. Corroborating information was obtained using UV photoelectron spectroscopy, which revealed that the adduct has an ionization potential ∼1.5 eV lower than that of C60. Density functional theory calculations showed that the C-C bond is polarized, with a total charge of +0.84e located on the NHC framework and -0.84e delocalized on the C 60 cage. The combination of reactivity, characterization, and theoretical studies demonstrates that fullerenes can behave as Lewis acids that react with C-based Lewis bases and that the overall process describes n-doping via C-C bond formation. © 2011 American Chemical Society.

Seasonal cycles of isoprene concentrations in the Amazonian rainforest

Science.gov (United States)

Trostdorf, C. R.; Gatti, L. V.; Yamazaki, A.; Potosnak, M. J.; Guenther, A.; Martins, W. C.; Munger, J. W.

2004-03-01

Tropical forests are an important global source of volatile organic compounds (VOCs) and other atmospheric trace gases. The high biodiversity in tropical rainforests complicates the extrapolation of biogenic volatile organic compound (BVOC) emissions from leaf-level measurements to landscape and regional or global scales. In Amazónia, a significant fraction of the carbon emitted from the biosphere to the atmosphere is emitted in the form of BVOCs, and the knowledge of these emissions is important to our understanding of tropical and global atmospheric chemistry and carbon cycling. As part of the Large scale Biosphere-atmosphere experiment in Amazónia (LBA). VOC concentrations were measured at two sites near Santarém, Para State, Brazil. The two sites are located in the National Forest of Tapajós, the first corresponding to primary forest and the second to a forest, that was selectively logged. The samples were collected simultaneously at heights of 65 and 55 m (20 and 10 m above forest canopy, respectively). The average isoprene mixing ratio was 2.2-2.5 ppb at the two sites and the standard deviations within a site ranged from 1 to 1.2 ppb. A strong seasonality of isoprene mixing ratio was observed and associated with the wet and dry seasons. The lowest mixing ratios were found during the transition between the wet to dry season, while at the start of the biomass burning season the mixing ratios increase. A qualitative analysis of a one dimensional model demonstrates that the seasonal cycle in concentrations reflects changes in isoprene production by the ecosystem, not changes in boundary layer dynamics or chemistry. The magnitude of the cycle indicates that the physiological capacity of the ecosystem to emit isoprene may depend on water availability although phenological changes could also contribute to the observed variations. A simple 1-D model that assumes mean daytime isoprene fluxes of 1.5 mg m-2h-1 and 0.9 mg m-2h-1 scaled by an algorithm depending on

Drought impact on Quercus pubescens Willd. isoprene emissions over the Mediterranean area: what future?

Science.gov (United States)

Cyrielle Genard-Zielinski, Anne; Boissard, Christophe; Ormeño, Elena; Lathière, Juliette; Guenet, Bertrand; Gauquelin, Thierry; Fernandez, Catherine

2015-04-01

Biogenic Volatile Organic Compounds (BVOCs) released by plants mostly originate from their secondary metabolism. Their emissions are modulated, in terms of intensity and molecule diversity, by environmental conditions. Among BVOCs, isoprene has been especially studied due to its high emission fluxes and its contribution to tropospheric photochemistry, both in the gaseous and particulate phases. However, the way isoprene emissions are impacted by some abiotic factors, especially water stress, is still under debate. In a world facing climatic changes, global climate models expect air temperature and drought intensity to strengthen in the Mediterranean area by 2100. Our work focuses on the impact of water stress on isoprene emissions (ERiso) from Quercus pubescens Willd. This species covers large areas of the Mediterranean area where it appears to be the main isoprene emitter. An in situ experimentation was performed at the O3HP (Oak Observatory at OHP, southern France) in a pubescent oak forest with trees adapted to long lasting stress periods. We investigated during a whole seasonal cycle (from June 2012 to June 2013) the course of ERiso under both natural water stress (control treatment: C) and intensified water stress (stress treatment: S) by artificially reducing rain by 30% using a specific rain exclusion device. Restricted rain did not modify either the net CO2 assimilation or ERiso during the whole season. However, isoprene emission factors (Is) for trees under S were significantly higher (a factor of ˜ 2) than for trees growing under C in August (137.8 compared to 75.3 μgC.gDM-1.h-1 respectively) and September (75.3 compared to 40.2 μgC.gDM-1.h-1 respectively). Based on our experimental emission database, an appropriate isoprene emission algorithm (GZ2014) was developed using a statistic approach (an artificial neural network). Using ambient and edaphic environmental parameters integrated over up to 3 weeks, GZ2014 was found to represent more than 80% of

High-resolution inversion of OMI formaldehyde columns over the Southeast US to infer isoprene emissions

Science.gov (United States)

Kaiser, J.; Zhu, L.; Travis, K.; Jacob, D.

2017-12-01

In the South East United States, biogenic isoprene fuels tropospheric ozone formation, and its oxidation products contribute significantly to organic aerosol. Bottom-up emission inventories rely on very limited isoprene emission and land-cover data, yielding uncertainties of a factor of 2 or more. Here, we use formaldehyde columns from the Ozone Monitoring Instrument in a high-resolution (0.25 x 0.325o) adjoint-based inversion to constrain isoprene emissions over the SE US during Aug-Sept of 2013. We find that the MEGANv2.1 inventory is biased high over most of the SE US. Our derived scaling factors show significant spatial variability, with the largest corrections applied to Louisiana and the Edwards Plateau in Texas. We test our inversion results against a comprehensive set of isoprene oxidation product observations from the NASA SEAC4RS flight campaign. The SEAC4RS data provides new confidence in the satellite retrievals and in mechanism linking isoprene oxidation to formaldehyde production. Finally, we relate the posterior scaling factors to the underlying land-type, and examine potential sources of observed biases.

Isoprene emission inventory for the BOREAS southern study area

International Nuclear Information System (INIS)

Westberg, H.; Lamb, B.; Kempf, K.; Allwine, G.

2000-01-01

The Boreal Ecosystem-Atmosphere Study (BOREAS) was designed to measure trace gas fluxes, nutrient cycling, hydrologic budgets and other ecosystem features in order to establish relationships between ecosystem processes and various global climate change scenarios. During the 1994 BOREAS field study isoprene and terpene emissions have been measured at several sites in the Southern Study Area (SSA). Ambient measurements were also made to help establish the chemical importance of these biogenic species in boreal atmosphere. The data was used to test and improve algorithms for predicting emission rates as a function of species, environmental conditions and biomass dynamics and to provide an expanded database describing the relationship of volatile organic compounds emissions to ecosystem dynamics. The study also sought to provide the foundation for improved understanding of physical exchange processes, and define hydrocarbon reactivity in the boundary layer at high latitudes. Details of the biogenic emission rate measurements made in the SSA are also discussed, including the creation of an isoprene emission inventory for the area. The study has been helpful in eliminating major sources of uncertainty associated with estimates of carbon loss due to isoprene emission on the BOREAS SSA. 28 refs., 4 tabs., 5 figs

Hydrogen abstraction reactions by amide electron adducts

International Nuclear Information System (INIS)

Sevilla, M.D.; Sevilla, C.L.; Swarts, S.

1982-01-01

Electron reactions with a number of peptide model compounds (amides and N-acetylamino acids) in aqueous glasses at low temperature have been investigated using ESR spectroscopy. The radicals produced by electron attachment to amides, RC(OD)NDR', are found to act as hydrogen abstracting agents. For example, the propionamide electron adduct is found to abstract from its parent propionamide. Electron adducts of other amides investigated show similar behavior except for acetamide electron adduct which does not abstract from its parent compound, but does abstract from other amides. The tendency toward abstraction for amide electron adducts are compared to electron adducts of several carboxylic acids, ketones, aldehydes and esters. The comparison suggests the hydrogen abstraction tendency of the various deuterated electron adducts (DEAs) to be in the following order: aldehyde DEA > acid DEA = approximately ester DEA > ketone DEA > amide DEA. In basic glasses the hydrogen abstraction ability of the amide electron adducts is maintained until the concentration of base is increased sufficiently to convert the DEA to its anionic form, RC(O - )ND 2 . In this form the hydrogen abstracting ability of the radical is greatly diminished. Similar results were found for the ester and carboxylic acid DEA's tested. (author)

Adduction of DNA with MTBE and TBA in mice studied by accelerator mass spectrometry.

Science.gov (United States)

Yuan, Y; Wang, H F; Sun, H F; Du, H F; Xu, L H; Liu, Y F; Ding, X F; Fu, D P; Liu, K X

2007-12-01

Methyl tert-butyl ether (MTBE) is a currently worldwide used octane enhancer substituting for lead alkyls and gasoline oxygenate. Our previous study using doubly (14)C-labeled MTBE [(CH(3))(3) (14)CO(14)CH(3)] has shown that MTBE binds DNA to form DNA adducts at low dose levels in mice. To elucidate the mechanism of the binding reaction, in this study, the DNA adducts with singly (14)C-labeled MTBE, which was synthesized from (14)C-methanol and tert-butyl alcohol (TBA), or (14)C-labeled TBA in mice have been measured by ultra sensitive accelerator mass spectrometry. The results show that the methyl group of MTBE and tert-butyl alcohol definitely form adducts with DNA in mouse liver, lung, and kidney. The methyl group of MTBE is the predominant binding part in liver, while the methyl group and the tert-butyl group give comparable contributions to the adduct formation in lung and kidney.

Global terrestrial isoprene emission models: sensitivity to variability in climate and vegetation

Directory of Open Access Journals (Sweden)

A. Arneth

2011-08-01

Full Text Available Due to its effects on the atmospheric lifetime of methane, the burdens of tropospheric ozone and growth of secondary organic aerosol, isoprene is central among the biogenic compounds that need to be taken into account for assessment of anthropogenic air pollution-climate change interactions. Lack of process-understanding regarding leaf isoprene production as well as of suitable observations to constrain and evaluate regional or global simulation results add large uncertainties to past, present and future emissions estimates. Focusing on contemporary climate conditions, we compare three global isoprene models that differ in their representation of vegetation and isoprene emission algorithm. We specifically aim to investigate the between- and within model variation that is introduced by varying some of the models' main features, and to determine which spatial and/or temporal features are robust between models and different experimental set-ups. In their individual standard configurations, the models broadly agree with respect to the chief isoprene sources and emission seasonality, with maximum monthly emission rates around 20–25 Tg C, when averaged by 30-degree latitudinal bands. They also indicate relatively small (approximately 5 to 10 % around the mean interannual variability of total global emissions. The models are sensitive to changes in one or more of their main model components and drivers (e.g., underlying vegetation fields, climate input which can yield increases or decreases in total annual emissions of cumulatively by more than 30 %. Varying drivers also strongly alters the seasonal emission pattern. The variable response needs to be interpreted in view of the vegetation emission capacities, as well as diverging absolute and regional distribution of light, radiation and temperature, but the direction of the simulated emission changes was not as uniform as anticipated. Our results highlight the need for modellers to evaluate their

Isoprene emissions modelling for West Africa: MEGAN model evaluation and sensitivity analysis

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J. Ferreira

2010-09-01

Full Text Available Isoprene emissions are the largest source of reactive carbon to the atmosphere, with the tropics being a major source region. These natural emissions are expected to change with changing climate and human impact on land use. As part of the African Monsoon Multidisciplinary Analyses (AMMA project the Model of Emissions of Gases and Aerosols from Nature (MEGAN has been used to estimate the spatial and temporal distribution of isoprene emissions over the West African region. During the AMMA field campaign, carried out in July and August 2006, isoprene mixing ratios were measured on board the FAAM BAe-146 aircraft. These data have been used to make a qualitative evaluation of the model performance.

MEGAN was firstly applied to a large area covering much of West Africa from the Gulf of Guinea in the south to the desert in the north and was able to capture the large scale spatial distribution of isoprene emissions as inferred from the observed isoprene mixing ratios. In particular the model captures the transition from the forested area in the south to the bare soils in the north, but some discrepancies have been identified over the bare soil, mainly due to the emission factors used. Sensitivity analyses were performed to assess the model response to changes in driving parameters, namely Leaf Area Index (LAI, Emission Factors (EF, temperature and solar radiation.

A high resolution simulation was made of a limited area south of Niamey, Niger, where the higher concentrations of isoprene were observed. This is used to evaluate the model's ability to simulate smaller scale spatial features and to examine the influence of the driving parameters on an hourly basis through a case study of a flight on 17 August 2006.

This study highlights the complex interactions between land surface processes and the meteorological dynamics and chemical composition of the PBL. This has implications for quantifying the impact of biogenic emissions

Methanol and isoprene emissions from the fast growing tropical pioneer species Vismia guianensis (Aubl. Pers. (Hypericaceae in the central Amazon forest

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K. J. Jardine

2016-05-01

Full Text Available Isoprene (Is emissions by plants represent a loss of carbon and energy resources leading to the initial hypothesis that fast growing pioneer species in secondary tropical forests allocate carbon primarily to growth at the expense of isoprenoid defenses. In this study, we quantified leaf isoprene and methanol emissions from the abundant pantropical pioneer tree species Vismia guianensis and ambient isoprene concentrations above a diverse secondary forest in the central Amazon. As photosynthetically active radiation (PAR was varied (0 to 3000 µmol m−2 s−1 under standard leaf temperature (30 °C, isoprene emissions from V. guianensis increased without saturation up to 80 nmol m−2 s−1. A nonlinear increase in isoprene emissions with respect to net photosynthesis (Pn resulted in the fraction of Pn dedicated to isoprene emissions increasing with light intensity (up to 2 % of Pn. Emission responses to temperature under standard light conditions (PAR of 1000 µmol m−2 s−1 resulted in the classic uncoupling of isoprene emissions (Topt, iso > 40 °C from net photosynthesis (Topt, Pn = 30.0–32.5 °C with up to 7 % of Pn emitted as isoprene at 40 °C. Under standard environmental conditions of PAR and leaf temperature, young V. guianensis leaves showed high methanol emissions, low Pn, and low isoprene emissions. In contrast, mature leaves showed high Pn, high isoprene emissions, and low methanol emissions, highlighting the differential control of leaf phenology over methanol and isoprene emissions. High daytime ambient isoprene concentrations (11 ppbv were observed above a secondary Amazon rainforest, suggesting that isoprene emissions are common among neotropical pioneer species. The results are not consistent with the initial hypothesis and support a functional role of methanol during leaf expansion and the establishment of photosynthetic machinery and a protective role of isoprene for

An Investigation of Chemical Landscapes in Aqueous Electrosprays by Tracking Oligomerization of Isoprene

KAUST Repository

Junior, Adair Gallo

2017-12-01

Electrospray ionization mass spectrometry (ESIMS) is widely used to characterize neutral and ionic species in solvents. Typically, electrical, thermal, and pneumatic potentials are applied to create electrosprays from which charged ionic species are ejected for downstream analysis by mass spectrometry. Most recently, ESIMS has been exploited to investigate ambient proton transfer reactions at air-water interfaces in real time. We assessed the validity of these experiments via complementary laboratory experiments. Specifically, we characterized the products of two reaction scenarios via ESIMS and proton nuclear magnetic resonance (1H-NMR): (i) emulsions of pH-adjusted water and isoprene (C5H8) that were mechanically agitated, and (ii) electrosprays of pH-adjusted water that were collided with gas-phase isoprene. Our experiments unambiguously demonstrate that, while isoprene does not oligomerize in emulsions, it does undergo protonation and oligomerization in electrosprays, both with and without pH-adjusted water, confirming that C-C bonds form along myriad high-energy pathways during electrospray ionization. We also compared our experimental results with some quantum mechanics simulations of isoprene molecules interacting with hydronium at different hydration levels (gas versus liquid phase). In agreement with our experiments, the kinetic barriers to protonation and oligomerization of isoprene were inaccessible under ambient conditions. Rather, the gas-phase chemistries during electrospray ionization drove the oligomerization of isoprene. Therefore, we consider that ESIMS could induce artifacts in interfacial reactions. These findings warrant a reassessment of previous reports on tracking chemistries under ambient conditions at liquid-vapor interfaces via ESIMS. Further, we took some high-speed images of electrosprays where it was possible to observe the main characteristics of the phenomena, i.e. Taylor cone, charge separation, and Coulomb fission. Finally, we took

Above Canopy Emissions of Isoprene and Monoterpenes from a Southeast Asian Tropical Forest

Science.gov (United States)

Baker, B.; Johnson, C.; Cai, Z.; Guenther, A.; Greenberg, J.; Bai, J.; Li, Q.

2003-12-01

Fluxes of isoprene were measured using the eddy covariance technique and an ozone chemiluminescence isoprene sensor above a secondary tropical forest/rubber tree plantation located in the Xishuangbanna region of southern China during the wet and dry seasons. Fluxes of monoterpenes were inferred from ambient boundary layer concentrations (wet season) and from relaxed eddy accumulation measurements (dry season). Isoprene emissions were comparable to what has been observed from other tropical forests in Africa and South America. In this forest, monoterpene emissions were much higher during the wet season due to the senescence of the rubber trees during the dry season. These flux measurements represent the first ecosystem level flux measurements reported from Southeast Asian tropical forests.

Formation of adduct of cerium (4) thenoyltrifluoroacetonate

International Nuclear Information System (INIS)

Anyfrieva, S.I.; Polyakova, G.V.; Snezhko, N.I.; Pechurova, N.I.; Martynenko, L.I.; Spitsyn, V.I.

1981-01-01

Adduct formation of thenoyltrifluoroacetonate of Ce(4) [Ce(TTFA) 4 ] with seven nitrogen- and oxygen-containing donor additional ligands is studied using the methods of IR-spectroscopy, derivatography, X-ray phase analysis. The presence of formation of Ce(TTFA) 4 adducts with phosphorus-containing additional ligands tributyl phosphate (TBP), trioctylphosphine oxide (TOPO), triphenylphosphine oxide (TPPO); α, α'-dipyridyl (Dipy) and o-phenanthroline (Phen) is established. The adduct Ce(TTFA) 4 stable to reduction is formed with Dipy, and in the case of Phen, TBP, TOPO, TPPO in the process of adduct formation the reduction of Ce(4) to Ce(3) takes place [ru

Ozone, OH and NO3 sink terms at a coniferous forest site in Central Germany: Role of biogenic VOCs

Science.gov (United States)

Bonn, B.; Bourtsoukidis, S.; Haunold, W.; Sitals, R.; Jacobi, S.

2012-04-01

sink terms during daytime. The contributions of monoterpene and isoprene reactions strengthened towards the summer period, while sesquiterpene reactions slowed down. Hydroxyl radical: The picture becomes much more complex for OH. Besides the reaction with nitrogen dioxide, isoprene and monoterpenes were key destructing agents of OH with estimated contributions of about 50-60%, increasing towards the summertime. Contributions of their oxidation products to the total sink of OH are supposed to be less than 20% but showing more intense during summer and less towards cooler periods. Sesquiterpene OH-reactions only contributed to 10% with a maximum of about 20% at the early April. Nitrate radical: NO3 displayed a mixture of the sinks of OH and ozone. The dominant destruction takes place via NOx-reactions (about 50%) and the remainder primarily via monoterpene (36±20%), sesquiterpene (11±8%) and isoprene (2±1%) OH-reactions. From our observations at this particular site it is apparent that the spruce forest provides a quite efficient variety of pathways to compensate oxidation stress. This is essentially displayed in the variation of emission pattern of different compound classes with different reactivity for the three major oxidation agents. One needs to be aware of the fact that the sink is highly variable in space, too. Therefore we conclude: In order to understand and describe the oxidation tolerance of a certain ecosystem one needs to detect at least the reactive hydrocarbons. [1] Jenkin, M.E., Shallcross, D. E., and Harvey, J. N.: Development and application of a possible mechanism for the generation of cis-pinic acid form the ozonolysis of α- and β-pinene. Atmos.Environ., 34, 2837-2850, 2000.

Gas/particle partitioning of carbonyls in the photooxidation of isoprene and 1,3,5-trimethylbenzene

Directory of Open Access Journals (Sweden)

R. M. Healy

2008-06-01

Full Text Available A new denuder-filter sampling technique has been used to investigate the gas/particle partitioning behaviour of the carbonyl products from the photooxidation of isoprene and 1,3,5-trimethylbenzene. A series of experiments was performed in two atmospheric simulation chambers at atmospheric pressure and ambient temperature in the presence of NO_x and at a relative humidity of approximately 50%. The denuder and filter were both coated with the derivatizing agent O-(2,3,4,5,6-pentafluorobenzyl-hydroxylamine (PFBHA to enable the efficient collection of gas- and particle-phase carbonyls respectively. The tubes and filters were extracted and carbonyls identified as their oxime derivatives by GC-MS. The carbonyl products identified in the experiments accounted for around 5% and 10% of the mass of secondary organic aerosol formed from the photooxidation of isoprene and 1,3,5-trimethylbenzene respectively.

Experimental gas/particle partitioning coefficients were determined for a wide range of carbonyl products formed from the photooxidation of isoprene and 1,3,5-trimethylbenzene and compared with the theoretical values based on standard absorptive partitioning theory. Photooxidation products with a single carbonyl moiety were not observed in the particle phase, but dicarbonyls, and in particular, glyoxal and methylglyoxal, exhibited gas/particle partitioning coefficients several orders of magnitude higher than expected theoretically. These findings support the importance of heterogeneous and particle-phase chemical reactions for SOA formation and growth during the atmospheric degradation of anthropogenic and biogenic hydrocarbons.

Can the capacity for isoprene emission acclimate to environmental modifications during autumn senescence in temperate deciduous tree species Populus tremula?

Science.gov (United States)

Sun, Zhihong; Copolovici, Lucian; Niinemets, Ülo

2012-03-01

Changes in isoprene emission (Φ(isoprene)), and foliage photosynthetic (A) rates, isoprene precursor dimethylallyldiphosphate (DMADP), and nitrogen and carbon contents were studied from late summer to intensive leaf fall in Populus tremula to gain insight into the emission controls by temperature and endogenous, senescence-induced, modifications. Methanol emissions, characterizing degradation of cell wall pectins, were also measured. A rapid reduction in Φ(isoprene) and A of 60-70% of the initial value was observed in response to a rapid reduction of ambient temperature by ca. 15°C (cold stress). Later phases of senescence were associated with further reductions in Φ(isoprene) and A, with simultaneous major decrease in nitrogen content. However, during episodes of temperature increase, A and in particular, Φ(isoprene) partly recovered. Variation in Φ(isoprene) during senescence was correlated with average temperature of preceding days, with the highest degree of explained variance observed with average temperature of 6 days. Throughout the study, methanol emissions were small, but a large burst of methanol emission was associated with leaf yellowing and abscission. Overall, these data demonstrate that the capacity for isoprene emission can adjust to environmental conditions in senescing leaves as well, but the responsiveness is low compared with mid-season and is also affected by stress.

Synthesis, structure, and spectroscopic and magnetic characterization of [Mn12O12(O2CCH2But)16(MeOH)4]·MeOH, a Mn12 single-molecule magnet with true axial symmetry.

Science.gov (United States)

Lampropoulos, Christos; Murugesu, Muralee; Harter, Andrew G; Wernsdofer, Wolfgang; Hill, Stephen; Dalal, Naresh S; Reyes, Arneil P; Kuhns, Philip L; Abboud, Khalil A; Christou, George

2013-01-07

The synthesis and properties are reported of a rare example of a Mn(12) single-molecule magnet (SMM) in truly axial symmetry (tetragonal, I4). [Mn(12)O(12)(O(2)CCH(2)Bu(t))(16)(MeOH)(4)]·MeOH (3·MeOH) was synthesized by carboxylate substitution on [Mn(12)O(12)(O(2)CMe)(16)(H(2)O)(4)]·2MeCO(2)H·4H(2)O (1). The complex was found to possess an S = 10 ground state, as is typical for the Mn(12) family, and displayed both frequency-dependent out-of-phase AC susceptibility signals and hysteresis loops in single-crystal magnetization vs DC field sweeps. The loops also exhibited quantum tunneling of magnetization steps at periodic field values. Single-crystal, high-frequency electron paramagnetic resonance spectra on 3·MeOH using frequencies up to 360 GHz revealed perceptibly sharper signals than for 1. Moreover, careful studies as a function of the magnetic field orientation did not reveal any satellite peaks, as observed for 1, suggesting that the crystals of 3 are homogeneous and do not contain multiple Mn(12) environments. In the single-crystal (55)Mn NMR spectrum in zero applied field, three well-resolved peaks were observed, which yielded hyperfine and quadrupole splitting at three distinct sites. However, observation of a slight asymmetry in the Mn(4+) peak was detectable, suggesting a possible decrease in the local symmetry of the Mn(4+) site. Spin-lattice (T(1)) relaxation studies were performed on single crystals of 3·MeOH down to 400 mK in an effort to approach the quantum tunneling regime, and fitting of the data using multiple functions was employed. The present work and other recent studies continue to emphasize that the new generation of truly high-symmetry Mn(12) complexes are better models for thorough investigation of the physical properties of SMMs than their predecessors such as 1.

DNA adduct profiling of in vitro colonic meat digests to map red vs. white meat genotoxicity.

Science.gov (United States)

Hemeryck, Lieselot Y; Rombouts, Caroline; De Paepe, Ellen; Vanhaecke, Lynn

2018-05-01

The consumption of red meat has been linked to an increased colorectal cancer (CRC) risk. One of the major hypotheses states that heme iron (present in red meat) stimulates the formation of genotoxic N-nitroso compounds (NOCs) and lipid peroxidation products (LPOs). By means of DNA adductomics, chemically induced DNA adduct formation can be mapped in relation to e.g. dietary exposures. In this study, this state-of-the-art methodology was used to investigate alkylation and (lipid per)oxidation induced DNA adduct formation in in vitro red vs. white meat digests. In doing so, 90 alkylation and (lipid per)oxidation induced DNA adduct types could be (tentatively) identified. Overall, 12 NOC- and/or LPO-related DNA adduct types, i.e. dimethyl-T (or ethyl-T), hydroxymethyl-T, tetramethyl-T, methylguanine (MeG), guanidinohydantoin, hydroxybutyl-C, hydroxymethylhydantoin, malondialdehyde-x3-C, O 6 -carboxymethylguanine, hydroxyethyl-T, carboxyethyl-T and 3,N 4 -etheno-C were singled out as potential heme-rich meat digestion markers. The retrieval of these DNA adduct markers is in support of the heme, NOC and LPO hypotheses, suggesting that DNA adduct formation may indeed contribute to red meat related CRC risk. Copyright © 2018 Elsevier Ltd. All rights reserved.

Photochemistry of psoralen-DNA adducts, biological effects of psoralen-DNA adducts, applications of psoralen-DNA photochemistry

Energy Technology Data Exchange (ETDEWEB)

Shi, Yun-bo

1988-03-01

This thesis consists of three main parts and totally eight chapters. In Part I, The author will present studies on the photochemistry of psoralen-DNA adducts, specifically, the wavelength dependencies for the photoreversals of thymidine-HMT (4'-hydroxymethyl-4, 5', 8-trimenthylpsoralen) monoadducts and diadduct and the same adducts incorporated in DNA helices and the wavelength dependecies for the photocrossslinking of thymidine-HMT monoadducts in double-stranded helices. In Part II, The author will report some biological effects of psoralen-DNA adducts, i.e., the effects on double-stranded DNA stability, DNA structure, and transcription by E. coli and T7 RNA polymerases. Finally, The author will focus on the applications of psoralen-DNA photochemistry to investigation of protein-DNA interaction during transcription, which includes the interaction of E. coli and T7 RNA polymerases with DNA in elongation complexes arrested at specific psoralen-DNA adduct sites as revealed by DNase I footprinting experiments. 123 refs., 52 figs., 12 tabs.

Photochemistry of psoralen-DNA adducts, biological effects of psoralen-DNA adducts, applications of psoralen-DNA photochemistry

International Nuclear Information System (INIS)

Shi, Yun-bo.

1988-03-01

This thesis consists of three main parts and totally eight chapters. In Part I, The author will present studies on the photochemistry of psoralen-DNA adducts, specifically, the wavelength dependencies for the photoreversals of thymidine-HMT (4'-hydroxymethyl-4, 5', 8-trimenthylpsoralen) monoadducts and diadduct and the same adducts incorporated in DNA helices and the wavelength dependecies for the photocrossslinking of thymidine-HMT monoadducts in double-stranded helices. In Part II, The author will report some biological effects of psoralen-DNA adducts, i.e., the effects on double-stranded DNA stability, DNA structure, and transcription by E. coli and T7 RNA polymerases. Finally, The author will focus on the applications of psoralen-DNA photochemistry to investigation of protein-DNA interaction during transcription, which includes the interaction of E. coli and T7 RNA polymerases with DNA in elongation complexes arrested at specific psoralen-DNA adduct sites as revealed by DNase I footprinting experiments. 123 refs., 52 figs., 12 tabs

Hip adduction and abduction strength profiles in elite soccer players

DEFF Research Database (Denmark)

Thorborg, Kristian; Serner, Andreas; Petersen, Jesper

2011-01-01

An ipsilateral hip adduction/abduction strength ratio of more than 90%, and hip adduction strength equal to that of the contralateral side have been suggested to clinically represent adequate strength recovery of hip adduction strength in athletes after groin injury. However, to what extent side-......-to-side symmetry in isometric hip adduction and abduction strength can be assumed in soccer players remains uncertain.......An ipsilateral hip adduction/abduction strength ratio of more than 90%, and hip adduction strength equal to that of the contralateral side have been suggested to clinically represent adequate strength recovery of hip adduction strength in athletes after groin injury. However, to what extent side...

Determination of breath isoprene and acetone concentration with a needle-type extraction device in gas chromatography-mass spectrometry.

Science.gov (United States)

Ueta, Ikuo; Mizuguchi, Ayako; Okamoto, Mitsuyoshi; Sakamaki, Hiroyuki; Hosoe, Masahiko; Ishiguro, Motoyuki; Saito, Yoshihiro

2014-03-20

Isoprene in human breath is said to be related to cholesterol metabolism, and the possibility of the correlations with some clinical parameters has been studied. However, at this stage, no clear benefit of breath isoprene has been reported for clinical diagnosis. In this work, isoprene and acetone concentrations were measured in the breath of healthy and obese subjects using a needle-type extraction device for subsequent analysis in gas chromatography-mass spectrometry (GC-MS) to investigate the possibility of these compounds as an indicator of possible diseases. After measuring intraday and interday variations of isoprene and acetone concentrations in breath samples of healthy subjects, their concentrations were also determined in 80 healthy and 17 obese subjects. In addition, correlation between these breath concentrations and the blood tests result was studied for these healthy and obese subjects. The results indicated successful determination of breath isoprene and acetone in this work, however, no clear correlation was observed between these measured values and the blood test results. Breath isoprene concentration may not be a useful indicator for obesity or hypercholesterolemia. Copyright © 2014 Elsevier B.V. All rights reserved.

Aqueous-phase mechanism for secondary organic aerosol formation from isoprene: application to the southeast United States and co-benefit of SO2 emission controls

Directory of Open Access Journals (Sweden)

E. A. Marais

2016-02-01

Full Text Available Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA, but the mechanism and yields are uncertain. Aerosol is prevailingly aqueous under the humid conditions typical of isoprene-emitting regions. Here we develop an aqueous-phase mechanism for isoprene SOA formation coupled to a detailed gas-phase isoprene oxidation scheme. The mechanism is based on aerosol reactive uptake coefficients (γ for water-soluble isoprene oxidation products, including sensitivity to aerosol acidity and nucleophile concentrations. We apply this mechanism to simulation of aircraft (SEAC4RS and ground-based (SOAS observations over the southeast US in summer 2013 using the GEOS-Chem chemical transport model. Emissions of nitrogen oxides (NOx  ≡  NO + NO2 over the southeast US are such that the peroxy radicals produced from isoprene oxidation (ISOPO2 react significantly with both NO (high-NOx pathway and HO2 (low-NOx pathway, leading to different suites of isoprene SOA precursors. We find a mean SOA mass yield of 3.3 % from isoprene oxidation, consistent with the observed relationship of total fine organic aerosol (OA and formaldehyde (a product of isoprene oxidation. Isoprene SOA production is mainly contributed by two immediate gas-phase precursors, isoprene epoxydiols (IEPOX, 58 % of isoprene SOA from the low-NOx pathway and glyoxal (28 % from both low- and high-NOx pathways. This speciation is consistent with observations of IEPOX SOA from SOAS and SEAC4RS. Observations show a strong relationship between IEPOX SOA and sulfate aerosol that we explain as due to the effect of sulfate on aerosol acidity and volume. Isoprene SOA concentrations increase as NOx emissions decrease (favoring the low-NOx pathway for isoprene oxidation, but decrease more strongly as SO2 emissions decrease (due to the effect of sulfate on aerosol acidity and volume. The US Environmental Protection Agency (EPA projects 2013–2025 decreases in

Uniaxial-pressure dependence of the magnetization dynamics in the high-symmetry single-molecule magnet Mn12-MeOH

Science.gov (United States)

Atkinson, James H.; Bhaskaran, Lakshmi; Hill, Stephen; Myasoedov, Yuri; Zeldov, Eli; Del Barco, Enrique; Friedman, Jonathan; Fournet, Adeline; Christou, George

2015-03-01

The single-molecule magnet [Mn12O12(O2CCH3)16(CH3OH)4]CH3OH (``Mn12-MeOH'') is a high-symmetry sibling of the Mn12-Acetate SMM that offers a prime opportunity to explore the consequences of molecular symmetry. A previous study has shown that applied pressure induced changes in the Mn12-Acetate's anisotropy parameters. Here we present the results of a study in which uniaxial pressure was applied to a crystalline sample of Mn12-MeOH in order to examine how the pressure affects the quantum tunneling of magnetization at low temperature. We find that the pressure induces an increase in the resonant tunneling rate manifested as a change in the height of the tunneling steps in the magnetic hysteresis. These results suggest that pressure is altering symmetry-breaking terms in the molecule's spin Hamiltonian, giving rise to increased tunneling.

Interaction between isoprene and ozone fluxes at ecosystem level in a poplar plantation and its impact at European level

Science.gov (United States)

Zenone, T.; Hendriks, C.; Brilli, F.; Gioli, B.; Portillo Estrada, M.; Schaap, M.; Ceulemans, R.

2015-12-01

The emissions of Biogenic volatile organic compounds (BVOCs) from vegetation, mainly in form of isoprenoids, play an important role in the tropospheric ozone (O3) formation. The potential large expansion of isoprene emitter species (e.g. poplar) as biofuels feedstock might impact the ground level O3 formation. Here we report the simultaneous observations, using the eddy covariance (EC) technique, of isoprene, O3 and CO2 fluxes in a short rotation coppice (SRC) of poplar. The impact of current poplar plantations and associated isoprene emissions on ground level ozone concentrations for Europe was evaluated using a chemistry transport model (CTM) LOTOS-EUROS. The isoprene fluxes showed a well-defined seasonal and daily cycle that mirrored with the stomata O3 uptake. The isoprene emission and the stomata O3 uptake showed significant statistical relationship especially at elevated temperature. Isoprene was characterized by a remarkable peak of emissions (e.g. 38 nmol m-2s-1) occurring for few days as a consequence of the rapid variation of the air and surface temperature. During these days the photosynthetic apparatus (i.e. the CO2 fluxes) and transpiration rates did not show significant variation while we did observe a variation of the energy exchange and a reduction of the bowen ratio. The response of isoprene emissions to ambient O3 concentration follows the common form of the hormetic dose-response curve with a considerable reduction of the isoprene emissions at [O3] > 80 ppbv indicating a potential damping effect of the O3 levels on isoprene. Under the current condition the impact of SRC plantations on ozone concentrations / formation is very limited in Europe. Our findings indicate that, even with future scenarios with more SRC, or conventional poplar plantations, the impact on Ozone formation is negligible.

Marine isoprene production and consumption in the mixed layer of the surface ocean - a field study over two oceanic regions

Science.gov (United States)

Booge, Dennis; Schlundt, Cathleen; Bracher, Astrid; Endres, Sonja; Zäncker, Birthe; Marandino, Christa A.

2018-02-01

Parameterizations of surface ocean isoprene concentrations are numerous, despite the lack of source/sink process understanding. Here we present isoprene and related field measurements in the mixed layer from the Indian Ocean and the eastern Pacific Ocean to investigate the production and consumption rates in two contrasting regions, namely oligotrophic open ocean and the coastal upwelling region. Our data show that the ability of different phytoplankton functional types (PFTs) to produce isoprene seems to be mainly influenced by light, ocean temperature, and salinity. Our field measurements also demonstrate that nutrient availability seems to have a direct influence on the isoprene production. With the help of pigment data, we calculate in-field isoprene production rates for different PFTs under varying biogeochemical and physical conditions. Using these new calculated production rates, we demonstrate that an additional significant and variable loss, besides a known chemical loss and a loss due to air-sea gas exchange, is needed to explain the measured isoprene concentration. We hypothesize that this loss, with a lifetime for isoprene between 10 and 100 days depending on the ocean region, is potentially due to degradation or consumption by bacteria.

Heterogeneous processing of biomass burning aerosol proxies by OH radicals for a wide range of OH concentrations and detection of volatilization products

Science.gov (United States)

Slade, J. H.; Knopf, D. A.

2012-12-01

Biomass burning aerosol (BBA) constitutes the majority of primary organic aerosol found in the atmosphere, with emission rates comparable to fossil-fuel burning. BBA affects earth's radiative budget directly through absorption and scattering of radiation or indirectly by modifying cloud radiative properties, and impacts air quality. Quantifying BBA source strength and thus its effects on air quality, human health, and climate can be difficult since these organic particles can chemically transform during atmospheric transport, a process also termed aging, due to heterogeneous reactions with oxidants and radicals such as OH. In this work we investigate the reactive uptake of OH radicals by typical BBA compounds that also serve as molecular markers for source apportionment studies. Organic substrates of cellulose pyrolysis products such as levoglucosan (1,6-anhydro-β-glucopyranose, C6H10O5), resin acids such as abietic acid (1-phenanthrenecarboxylic acid, C20H30O2), and lignin decomposition products such as 5-nitroguaiacol (2-methoxy-5-nitrophenol, C7H7NO4) have been exposed to a wide range of OH concentrations (~107-1011 cm-3), in presence of O2 in a rotating wall flow reactor operated at 2-6 mbar coupled to a custom built chemical ionization mass spectrometer (CIMS). OH radicals were generated through H2 dissociation in an Evenson microwave resonant cavity operated at 2.45 GHz followed by reaction with O2 or NO2. In addition, potential volatilization of organic material due to heterogeneous oxidation by OH has been determined in-situ by monitoring the volatile organic compounds using a high resolution-proton transfer reaction-time of flight-mass spectrometer (HR-PTR-ToF-MS). The volatilization studies are conducted at 1 atm and OH is generated by O3 photolysis in the presence of H2O vapor and quantified using a photochemical box model as well as through reaction with a known concentration of isoprene (2-methyl-1,3-butadiene, C5H8). Reactive uptake validation

The effects of isoprene and NOx on secondary organic aerosols formed through reversible and irreversible uptake to aerosol water

Science.gov (United States)

El-Sayed, Marwa M. H.; Ortiz-Montalvo, Diana L.; Hennigan, Christopher J.

2018-01-01

Isoprene oxidation produces water-soluble organic gases capable of partitioning to aerosol liquid water. The formation of secondary organic aerosols through such aqueous pathways (aqSOA) can take place either reversibly or irreversibly; however, the split between these fractions in the atmosphere is highly uncertain. The aim of this study was to characterize the reversibility of aqSOA formed from isoprene at a location in the eastern United States under substantial influence from both anthropogenic and biogenic emissions. The reversible and irreversible uptake of water-soluble organic gases to aerosol water was characterized in Baltimore, Maryland, USA, using measurements of particulate water-soluble organic carbon (WSOCp) in alternating dry and ambient configurations. WSOCp evaporation with drying was observed systematically throughout the late spring and summer, indicating reversible aqSOA formation during these times. We show through time lag analyses that WSOCp concentrations, including the WSOCp that evaporates with drying, peak 6 to 11 h after isoprene concentrations, with maxima at a time lag of 9 h. The absolute reversible aqSOA concentrations, as well as the relative amount of reversible aqSOA, increased with decreasing NOx / isoprene ratios, suggesting that isoprene epoxydiol (IEPOX) or other low-NOx oxidation products may be responsible for these effects. The observed relationships with NOx and isoprene suggest that this process occurs widely in the atmosphere, and is likely more important in other locations characterized by higher isoprene and/or lower NOx levels. This work underscores the importance of accounting for both reversible and irreversible uptake of isoprene oxidation products to aqueous particles.

Structure and Oxidation of Pyrrole Adducts Formed between Aflatoxin B2a and Biological Amines.

Science.gov (United States)

Rushing, Blake R; Selim, Mustafa I

2017-06-19

Aflatoxin B 2a has been shown to bind to proteins through a dialdehyde intermediate under physiological conditions. The proposed structure of this adduct has been published showing a Schiff base interaction, but adequate verification using structural elucidation instrumental techniques has not been performed. In this work, we synthesized the aflatoxin B 2a amino acid adduct under alkaline conditions, and the formation of a new product was determined using high performance liquid chromatography-time-of-flight mass spectrometry. The resulting accurate mass was used to generate a novel proposed chemical structure of the adduct in which the dialdehyde forms a pyrrole ring with primary amines rather than the previously proposed Schiff base interaction. The pyrrole structure was confirmed using 1 H, 13 C, correlation spectroscopy, heteronuclear single quantum correlation, and heteronuclear multiple bond correlation NMR and tandem mass spectrometry. Reaction kinetics show that the reaction is overall second order and that the rate increases as pH increases. Additionally, this study shows for the first time that aflatoxin B 2a dialdehyde forms adducts with phosphatidylethanolamines and does so through pyrrole ring formation, which makes it the first aflatoxin-lipid adduct to be structurally identified. Furthermore, oxidation of the pyrrole adduct produced a product that was 16 m/z heavier. When the aflatoxin B 2a -lysine (ε) adduct was oxidized, it gave a product with an accurate mass, mass fragmentation pattern, and 1 H NMR spectrum that match aflatoxin B 1 -lysine, which suggest the transformation of the pyrrole ring to a pyrrolin-2-one ring. These data give new insight into the fate and chemical properties of biological adducts formed from aflatoxin B 2a as well as possible interferences with known aflatoxin B 1 exposure biomarkers.

Recognition and repair of 2-aminofluorene- and 2-(acetylamino)fluorene-DNA adducts by UVRABC nuclease

International Nuclear Information System (INIS)

Pierce, J.R.; Case, R.; Tang, Moonshong

1989-01-01

Recognition of damage induced by N-hydroxy-2-aminofluorene (N-OH-AF) and N-acetoxy-2-(acetylamino)fluorene (NAAAF) in both φX174 RFI supercoiled DNA and a linear DNA fragment by purified UVRA, UVRB, and UVRC proteins was investigated. The authors have previously demonstrated that N-OH-AF and NAAAF treatments produce N-(deoxyguanosin-8-yl)-2-aminofluorene (dG-C8-AF) and N-(deoxyguanosin-8-yl)-2-(acetylamino)fluorene (dG-C8-AAF), respectively, in DNA. Using a piperidine cleavage method and DNA sequence analysis, they have found that all guanine residues can be modified by N-OH-AF and NAAAF. These two kinds of adducts have different impacts on the DNA helix structure; while dG-C8-AF maintains the anti configuration, dG-C8-AAF is in the syn form. φX174 RF DNA-Escherichia coli transfection results indicate that while the uvrA, uvrB, and uvrC gene products are needed to repair dG-C8-AAF, the uvrC, but not the uvrA or uvrB gene products, is needed for repair of dG-C8-Af. However, they have found that in vitro the UVRA, UVRB, and UVRC proteins must work in concert to nick both dG-C8-AF and dG-C8-AAF. In general, the reactions of UVRABC nuclease toward dG-C8-AF are similar to those toward dG-C8-AAF; it incises seven to eight nucleotides from the 5' side and three to four nucleotides from the 3' side of the DNA adduct. Evidence is presented to suggest that hydrolysis on the 3' and 5' sides of the damaged base by UVRABC nuclease is not simultaneous and that at least occasionally hydrolysis occurs only on the 3' side or on the 5' side of the damage site. The possible mechanisms of UVRABC nuclease incision for AF-DNA are discussed

High-resolution inversion of OMI formaldehyde columns to quantify isoprene emission on ecosystem-relevant scales: application to the southeast US

Science.gov (United States)

Kaiser, Jennifer; Jacob, Daniel J.; Zhu, Lei; Travis, Katherine R.; Fisher, Jenny A.; González Abad, Gonzalo; Zhang, Lin; Zhang, Xuesong; Fried, Alan; Crounse, John D.; St. Clair, Jason M.; Wisthaler, Armin

2018-04-01

Isoprene emissions from vegetation have a large effect on atmospheric chemistry and air quality. Bottom-up isoprene emission inventories used in atmospheric models are based on limited vegetation information and uncertain land cover data, leading to potentially large errors. Satellite observations of atmospheric formaldehyde (HCHO), a high-yield isoprene oxidation product, provide top-down information to evaluate isoprene emission inventories through inverse analyses. Past inverse analyses have however been hampered by uncertainty in the HCHO satellite data, uncertainty in the time- and NOx-dependent yield of HCHO from isoprene oxidation, and coarse resolution of the atmospheric models used for the inversion. Here we demonstrate the ability to use HCHO satellite data from OMI in a high-resolution inversion to constrain isoprene emissions on ecosystem-relevant scales. The inversion uses the adjoint of the GEOS-Chem chemical transport model at 0.25° × 0.3125° horizontal resolution to interpret observations over the southeast US in August-September 2013. It takes advantage of concurrent NASA SEAC4RS aircraft observations of isoprene and its oxidation products including HCHO to validate the OMI HCHO data over the region, test the GEOS-Chem isoprene oxidation mechanism and NOx environment, and independently evaluate the inversion. This evaluation shows in particular that local model errors in NOx concentrations propagate to biases in inferring isoprene emissions from HCHO data. It is thus essential to correct model NOx biases, which was done here using SEAC4RS observations but can be done more generally using satellite NO2 data concurrently with HCHO. We find in our inversion that isoprene emissions from the widely used MEGAN v2.1 inventory are biased high over the southeast US by 40 % on average, although the broad-scale distributions are correct including maximum emissions in Arkansas/Louisiana and high base emission factors in the oak-covered Ozarks of southeast

STABILITY OF HEMOGLOBIN AND ALBUMIN ADDUCTS OF BENZENE OXIDE AND 1,4-BENZOQUINONE AFTER ADMINISTRATION OF BENZENE TO F344 RATS

Science.gov (United States)

The stability of cysteinyl adducts of benzene oxide (BO) and mono-S-substituted cysteinyl adducts of 1,4-benzoquinone (1,4-BQ) was investigated in both hemoglobin (Hb) and albumin (Alb) following administration of a single oral dose of 400 mg [U-14C/13C6]benzene/kg body weight ...

Future changes in biogenic isoprene emissions: how might they affect regional and global atmospheric chemistry?

Science.gov (United States)

Christine Wiedinmyer; Xuexi Tie; Alex Guenther; Ron Neilson; Claire. Granier

2006-01-01

Isoprene is emitted from vegetation to the atmosphere in significant quantities, and it plays an important role in the reactions that control tropospheric oxidant concentrations. As future climatic and land-cover changes occur, the spatial and temporal variations, as well as the magnitude of these biogenic isoprene emissions, are expected to change. This paper presents...

DNA adduct measurements in zebra mussels, Dreissena polymorpha, Pallas

International Nuclear Information System (INIS)

Le Goff, J.; Gallois, J.; Pelhuet, L.; Devier, M.H.; Budzinski, H.; Pottier, D.; Andre, V.; Cachot, J.

2006-01-01

The purpose of this study was to examine PAH accumulation and bulky DNA adduct formation in the digestive gland of zebra mussels exposed in their habitat or in controlled laboratory conditions to complex mixture of PAH. DNA adducts were measured using a 32 P-postlabelling protocol with nuclease P1 enrichment adapted from Reddy and Randerath [Reddy, M.V., Randerath, K., 1986. Nuclease P1-mediated enhancement of sensitivity of 32 P-postlabelling test for structurally diverse DNA adducts. Carcinogenesis 7, 1543-1551]. Specimens collected in the upper part of the Seine estuary were shown to accumulate higher levels of PAH (up to 1.6 μg g -1 dry weight) in comparison to individuals from the reference site (0.053 μg g -1 dry weight). The former exhibited elevated levels of DNA adducts (up to 4.0/10 8 nucleotides) and higher diversity of individual adducts with five distinct spots being specifically detected in individuals originating from the Seine estuary. Zebra mussels exposed for 5 days to 0.01% (v/v) of organic extract of sediment from the Seine estuary were shown to accumulate high amounts of PAH (up to 138 μg g -1 dry weight) but exhibited relatively low levels of DNA adducts. Exposure to benzo[a]pyrene led to a dose-dependent accumulation of B[a]P (up to 7063 μg g -1 dry weight) and a clear induction of DNA adduct formation in the digestive gland of mussels (up to 1.13/10 8 nucleotides). Comparisons with other bivalves exposed to the same model PAH, revealed similar levels of adducts and comparable adduct profiles with a main adduct spot and a second faint one. This study clearly demonstrated that zebra mussels are able to biotransform B[a]P and probably other PAH into reactive metabolites with DNA-binding activity. This work also demonstrated the applicability of the nuclease P1 enhanced 32 P-postlabelling method for bulky adduct detection in the digestive gland of zebra mussels. DNA adduct measurement in zebra mussels could be a suitable biomarker to monitor

DNA adduct measurements in zebra mussels, Dreissena polymorpha, Pallas

Energy Technology Data Exchange (ETDEWEB)

Le Goff, J. [GRECAN, UPRES EA-1772, University of Caen, Caen (France); Gallois, J. [Laboratory F. Duncombe, Conseil General du Calvados, Caen (France); Pelhuet, L. [LPTC, UMR-5472 CNRS, University Bordeaux I, Bordeaux (France); Devier, M.H. [LPTC, UMR-5472 CNRS, University Bordeaux I, Bordeaux (France); Budzinski, H. [LPTC, UMR-5472 CNRS, University Bordeaux I, Bordeaux (France); Pottier, D. [GRECAN, UPRES EA-1772, University of Caen, Caen (France); Andre, V. [GRECAN, UPRES EA-1772, University of Caen, Caen (France); Cachot, J. [LEMA, UPRES EA-3222, IFRMP 23, University of Le Havre, 25 rue Philippe Lebon, B.P. 540, 76058 Le Havre Cedex (France)]. E-mail: jerome.cachot@univ-lehavre.fr

2006-08-12

The purpose of this study was to examine PAH accumulation and bulky DNA adduct formation in the digestive gland of zebra mussels exposed in their habitat or in controlled laboratory conditions to complex mixture of PAH. DNA adducts were measured using a {sup 32}P-postlabelling protocol with nuclease P1 enrichment adapted from Reddy and Randerath [Reddy, M.V., Randerath, K., 1986. Nuclease P1-mediated enhancement of sensitivity of {sup 32}P-postlabelling test for structurally diverse DNA adducts. Carcinogenesis 7, 1543-1551]. Specimens collected in the upper part of the Seine estuary were shown to accumulate higher levels of PAH (up to 1.6 {mu}g g{sup -1} dry weight) in comparison to individuals from the reference site (0.053 {mu}g g{sup -1} dry weight). The former exhibited elevated levels of DNA adducts (up to 4.0/10{sup 8} nucleotides) and higher diversity of individual adducts with five distinct spots being specifically detected in individuals originating from the Seine estuary. Zebra mussels exposed for 5 days to 0.01% (v/v) of organic extract of sediment from the Seine estuary were shown to accumulate high amounts of PAH (up to 138 {mu}g g{sup -1} dry weight) but exhibited relatively low levels of DNA adducts. Exposure to benzo[a]pyrene led to a dose-dependent accumulation of B[a]P (up to 7063 {mu}g g{sup -1} dry weight) and a clear induction of DNA adduct formation in the digestive gland of mussels (up to 1.13/10{sup 8} nucleotides). Comparisons with other bivalves exposed to the same model PAH, revealed similar levels of adducts and comparable adduct profiles with a main adduct spot and a second faint one. This study clearly demonstrated that zebra mussels are able to biotransform B[a]P and probably other PAH into reactive metabolites with DNA-binding activity. This work also demonstrated the applicability of the nuclease P1 enhanced {sup 32}P-postlabelling method for bulky adduct detection in the digestive gland of zebra mussels. DNA adduct measurement in

Polycyclic aromatic hydrocarbons and PAH-related DNA adducts.

Science.gov (United States)

Ewa, Błaszczyk; Danuta, Mielżyńska-Švach

2017-08-01

Investigations on the impact of chemicals on the environment and human health have led to the development of an exposome concept. The exposome refers to the totality of exposures received by a person during life, including exposures to life-style factors, from the prenatal period to death. The exposure to genotoxic chemicals and their reactive metabolites can induce chemical modifications of DNA, such as, for example, DNA adducts, which have been extensively studied and which play a key role in chemically induced carcinogenesis. Development of different methods for the identification of DNA adducts has led to adopting DNA adductomic approaches. The ability to simultaneously detect multiple PAH-derived DNA adducts may allow for the improved assessment of exposure, and offer a mechanistic insight into the carcinogenic process following exposure to PAH mixtures. The major advantage of measuring chemical-specific DNA adducts is the assessment of a biologically effective dose. This review provides information about the occurrence of the polycyclic aromatic hydrocarbons (PAHs) and their influence on human exposure and biological effects, including PAH-derived DNA adduct formation and repair processes. Selected methods used for determination of DNA adducts have been presented.

Syntheses of DNA adducts of two heterocyclic amines, 2-amino-3-methyl-9H-pyrido[2,3-b]indole (MeA alpha C) and 2-amino-9H-pyrido[2,3-b]indole (A alpha C) and identification of DNA adducts in organs from rats dosed with MeA alpha C

DEFF Research Database (Denmark)

Frederiksen, Hanne; Frandsen, Henrik Lauritz; Pfau, W.

2004-01-01

2-Amino-3-methyl-9H-pyrido[2,3-b]indole (MeAalphaC) and 2-amino-3-methyl-9H-pyrido[2,3-b]indole (AalphaC) are mutagenic and carcinogenic heterocyclic amines formed during ordinary cooking. MeAalphaC and AalphaC are activated to mutagenic metabolites by cytochrome P450-mediated N-oxidation...... by reaction of the parent amines with acetylated guanine N3-oxide. N-2-OH-MeAalphaC and N-2-OH-AalphaC reacted with calf thymus DNA after addition of acetic anhydride. P-32-postlabelling analysis of modified DNA showed one major adduct co-migrating with N-2-(3',5'-diphospho-2'-deoxyguanosin-8-yl...

Adduction of acrylamide with biomacromolecules at environmental dose level measured by accelerator mass spectrometry (AMS)

International Nuclear Information System (INIS)

Xie, Q.Y.; Sun, H.F.; Liu, Y.F.; Ding, X.F.; Fu, D.P.; Liu, K.X.

2005-01-01

Acrylamide (AA) is a well-known neurotoxin, which also has developmental, reproductive as well as genetic toxicity. AA has been classified as a probable human carcinogen by IARC in 1994 since its carcinogenic effects in animals were reported after repetitive high level dosing. Over the last 10 years, there have been a large number of studies investigating the effects of AA on rodent reproductive performance. In 2002, the Swedish Food Administration reported the presence of AA in the heat-treated food products. which again elicited great concern on the toxicity of AA. However most of these studies were investigated at a dose level of mg/kg b.w and above, which is much higher than the actual human relevant dose. In this study we investigate the adduction of environmental level AA with biomacromolecules by the ultra-sensitive AMS technique. This may provide some information on the reproductive toxicity of AA under extremely low level exposure. A series doses of [2, 3- 14 C] AA (0, 0.1, 1, 10, 100, 250, 1000 μg/kg bw) were administrated with a single intraperitoneal injection (i.p.) to ICR adult male mice. The blood and spermatozoon were collected 24 h post dosing. Hemoglobin (Hb), serum albumin (SA), protamine, spermatozoon DNA, spermatozoon head and tail were isolated respectively, and then transformed into graphite following our previous procedure, The adduct levels were determined by a 0.6 MV compact AMS facility at the Institute of Heavy Ion Physics of Peking University. The results indicate that: (1) AA adduct number increases with the doses within 0.1-1000 μg/kg b.w. range in a log/log linear mode, except for DNA within 10-1000 μg/kg b.w. range. (2) Comparing protamine, Hb, and SA adducts with that of spermatozoon DNA (see Fig. 1), AA mainly adducts to proteins. For instance, at 1000 μg/kg b.w. dose level, spermatozoon DNA adducts only account for about 0.71%, 1.36% and 0.82% of protamine, Hb and SA adducts, respectively. (3) AA-protamine adducts, AA

Characterization of the Major Purine and Pyrimidine Adducts Formed after Incubations of 1-Chloro-3-buten-2-one with Single-/Double-Stranded DNA and Human Cells.

Science.gov (United States)

Liu, Ling-Yan; Zheng, Jin; Kong, Cong; An, Jing; Yu, Ying-Xin; Zhang, Xin-Yu; Elfarra, Adnan A

2017-02-20

We have previously shown that 1-chloro-3-buten-2-one (CBO), a potential reactive metabolite of 1,3-butadiene (BD), exhibits potent cytotoxicity and genotoxicity that have been attributed in part to its reactivity toward DNA. In an effort to identify the DNA adducts of CBO, we characterized the CBO reactions with 2'-deoxyguanosine (dG), 2'-deoxycytidine (dC), and 2'-deoxyadenosine (dA) under in vitro physiological conditions (pH 7.4, 37 °C). In the present study, we investigated the CBO reaction with 2'-deoxythymidine (dT) and compared the rate constants of the reactions of CBO with dA, dC, dG, and dT at both individual- and mixed-nucleosides levels. We also investigated the reactions of CBO with single- and double-stranded DNA using HPLC with UV detection after adducts were released by either acid or enzymatic hydrolysis of DNA. Consistent with the results from the nucleoside reactions and the rate constant experiments, 1,N 6 -(1-hydroxy-1-chloromethylpropan-1,3-diyl)adenine (A-2D) was identified as the major DNA adduct detected after acid hydrolysis, followed by N7-(4-chloro-3-oxobutyl)guanine (CG-2H) and a small amount of 1,N 6 -(1-hydroxy-1-hydroxymethylpropan-1,3-diyl)adenine (A-1D). After enzymatic hydrolysis, 1,N 6 -(1-hydroxy-1-hydroxymethylpropan-1,3-diyl)-2'-dexoyadenosine (dA-1), 3,N 4 -(1-hydroxy-1-hydroxymethylpropan-1,3-diyl)-2'-deoxycytidine (dC-1/2), and 1,N 2 -(3-hydroxy-3-hydroxymethylpropan-1,3-diyl)-2'-dexoyguanosine (CG-1) were detected, with dA-1 being the major product, followed by dC-1/2. When a nontoxic concentration of CBO (1 μM) was incubated with HepG2 cells, no adducts could be detected by LC-MS. However, pretreatment of cells with l-buthionine sulfoximine to deplete GSH levels allowed A-2D to be consistently detected in cellular DNA. These results may contribute to a better understanding of the role of the DNA adducts in CBO genotoxicity and mutagenicity. It also suggests that A-2D could be developed as a biomarker of CBO formation

Hip adduction and abduction strength profiles in elite soccer players

DEFF Research Database (Denmark)

Thorborg, Kristian; Serner, Andreas; Petersen, Jesper

2011-01-01

An ipsilateral hip adduction/abduction strength ratio of more than 90%, and hip adduction strength equal to that of the contralateral side have been suggested to clinically represent adequate strength recovery of hip adduction strength in athletes after groin injury. However, to what extent side-......-to-side symmetry in isometric hip adduction and abduction strength can be assumed in soccer players remains uncertain....

Oxidation of aromatic amines and diamines by OH radicals. Formation and ionization constants of amine cation radicals in water

International Nuclear Information System (INIS)

Hayon, E.; Rao, P.S.

1975-01-01

The one-electron oxidation by hydroxyl radicals of aromatic amines and diamines in water was studied using the fast-reaction technique of pulse radiolysis and kinetic absorption spectrophotometry. The following compounds were examined: N,N,N 1 ,N 1 - tetramethyl-p-phenylenediamine (TMPD), p-phenylenediamine (PD), N,N-dimethyl-p-phenylenediamene (DMPD), N,N,N 1 ,N 1 -tetramethylbenzidine (TMB), and diphenylamine (DPA). The main initial reaction of the OH radicals is suggested to be an addition to these compounds to give absorption spectra which absorb strongly in the visible and uv regions. These OH radical adducts decay by first-order kinetics and have lifetimes of approximately 5-50 μsec, dependent on the pH, buffer concentration, and the nature of the aromatic amines and diamines. They decay to give species with somewhat similar absorption spectra and extinction coefficients, which are very long lived in the absence of oxygen. The latter species are assigned to the cation radicals TMPD. + , PD. + , DMPD. + , TMB. + , and DPA. + . The OH radical adducts and the cation radicals have acid-base properties. The pK/sub a/ values of the cation radicals TMPDH. 2+ , PDH. 2+ , DMPDH. 2+ , TMBH. 2+ , and DPAH. 2+ were found to be 5.3, 5.9, 6.1, 5.1, and 4.2, respectively. The results indicate that these aromatic amines and diamines can be oxidized by free radicals to yield the corresponding cation radicals. (U.S.)

NITRO MUSK ADDUCTS OF RAINBOW TROUT ...

Science.gov (United States)

Rainbow trout and other fish species can serve as 'sentinel' species for the assessment of ecological status and the presence of certain environmental contaminants. As such they act as bioindicators of exposure. Here we present seminal data regarding dose-response and toxicokinetics of trout hemoglobin adduct formation from exposure to nitro musks that are frequently used as fragrance ingredients in formulations of personal care products. Hemoglobin adducts serve as biomarkers of exposure of the sentinel species as we have shown in previous studies of hemoglobin adducts formed in trout and environmental carp exposed to musk xylene (MX) and musk ketone (MK). Gas chromatography-electron capture negative ion chemical ionization-mass spectrometry (GC-NICI-MS) employing selected ion monitoring is used to measure 4-amino-MX (4-AMX), 2-amino-MX (2-AMX), and 2-amino-MK (2-AMK) released by alkaline hydrolysis from the sulfinamide adducts of hemoglobin. Dose-response and toxicokinetics were investigated using this sensitive method for analysis of these metabolites. In the dose-response investigation, the concentrations of 4-AMX and 2-2AMX are observed to pass through a maximum at 0.10 mg/g. In the case of 2-AMK, the adduct concentration is almost the same at dosages in the range of 0.030 to 0.10 mg/g. For toxicokinetics, the concentration of the metabolites in the Hb reaches a maximum in the 3-day sample after administration of MX or MK. Further elimination of the metabo

Including the Copenhagen Adduction Exercise in the FIFA 11+ Provides Missing Eccentric Hip Adduction Strength Effect in Male Soccer Players: A Randomized Controlled Trial.

Science.gov (United States)

Harøy, Joar; Thorborg, Kristian; Serner, Andreas; Bjørkheim, André; Rolstad, Linn E; Hölmich, Per; Bahr, Roald; Andersen, Thor Einar

2017-11-01

The FIFA 11+ was developed as a complete warm-up program to prevent injuries in soccer players. Although reduced hip adduction strength is associated with groin injuries, none of the exercises included in the FIFA 11+ seem to specifically target hip adduction strength. To investigate the effect on eccentric hip adduction strength of the FIFA 11+ warm-up program with or without the Copenhagen adduction exercise. Randomized controlled trial; Level of evidence, 1. We recruited 45 eligible players from 2 U19 elite male soccer teams. Players were randomized into 2 groups; 1 group carried out the standard FIFA 11+ program, while the other carried out the FIFA 11+ but replaced the Nordic hamstring exercise with the Copenhagen adduction exercise. Both groups performed the intervention 3 times weekly for 8 weeks. Players completed eccentric strength and sprint testing before and after the intervention. Per-protocol analyses were performed, and 12 players were excluded due to low compliance (<67% of sessions completed). The main outcome was eccentric hip adduction strength (N·m/kg). Between-group analyses revealed a significantly greater increase in eccentric hip adduction strength of 0.29 Nm/kg (8.9%; P = .01) in favor of the group performing the Copenhagen adduction exercise, whereas no within-group change was noted in the group that used the standard FIFA 11+ program (-0.02 N·m/kg [-0.7%]; P = .69). Including the Copenhagen adduction exercise in the FIFA 11+ program increases eccentric hip adduction strength, while the standard FIFA 11+ program does not. Registration: Registration: ISRCTN13731446 (International Standard Randomised Controlled Trial Number registry).

Discrepancies between modeled and observed nocturnal isoprene in an urban environment and the possible causes: A case study in Houston

Science.gov (United States)

Diao, Lijun; Choi, Yunsoo; Czader, Beata; Li, Xiangshang; Pan, Shuai; Roy, Anirban; Souri, Amir Hossein; Estes, Mark; Jeon, Wonbae

2016-11-01

Air quality simulations were conducted using the Community Multiscale Air Quality (CMAQ) model for nocturnal isoprene in September 2013 using the United States Environmental Protection Agency's (EPA's) National Emissions Inventory of 2011 (NEI, 2011). The results were evaluated against measurements collected at eight Texas Commission on Environmental Quality (TCEQ) Automated Gas Chromatographs (AutoGCs) monitoring stations. The comparisons demonstrated two distinctive behaviors: overestimation before midnight (20:00-23:00 p.m. local time) versus underestimation after midnight (00:00-06:00 a.m.). Analyses identify the uncertainties in nitrate radical (NO3) concentration and vertical mixing as the possible minor factors contributing to the underestimation, and the underestimated wind speed as the major factor contributing to the overestimation. Further analysis links isoprene underestimation to the uncertainties in the nocturnal isoprene anthropogenic emissions in the NEI (2011) over industrial areas in Houston. This can be substantiated by the fact that the observed nighttime isoprene concentrations increased when the wind direction veered back from southeast to northeast, placing the stations downwind of industrial facilities. A sensitivity run with adjusted anthropogenic isoprene emissions in the later part of the night (i.e., the emissions were multiplied by the hourly underestimation factors ranging from 3.81 to 14.82) yielded closer isoprene predictions after midnight with slightly improved model mean (0.15 to 0.20 ppb), mean error (- 0.10 to - 0.04 ppb), mean absolute error (0.18 to 0.15 ppb), root mean squared error (RMSE, 0.27 to 0.25 ppb), and index of agreement (IOA, 0.66 to 0.68). The insignificant improvement was likely due to the uncertainties in the location of the high-peaked anthropogenic emissions. The impacts of the nighttime-adjusted isoprene emissions on the isoprene oxidation products, organic nitrate and ozone, were found to be minimal. This

Determination of adducts of polycyclic aromatic hydrocarbons to DNA

International Nuclear Information System (INIS)

Bean, R.M.; Chess, E.K.; Thomas, B.L.; Mann, D.B.; Dankovic, D.A.; Franz, J.A.; Springer, D.L.

1987-01-01

Adducts to deoxyribonucleic acid (DNA), formed from metabolites of polynuclear aromatic compounds, are relatively persistent and correlate with bioresponse (carcinogenicity). Therefore, qualitative and quantitative analysis of adducts in the DNA of individuals may provide valuable information as to recent exposure to carcinogenic hydrocarbons. Further, the ability to detect adducts in a large segment of a population may have significant epidemiological significance. The current thrust of the analytical development at PNL is to isolate the DNA, liberate the adducted hydrocarbon residue from the DNA with acid hydrolysis, and prepare derivatives of the hydrolyzed species that will enhance its detection, quantitation, and characterization using gas chromatography/mass spectrometry (GC/MS). They have initiated the development of the necessary techniques using benzo[a]pyrene (B[a]P). Samples of DNA adducts of radiolabeled B[a]P have been prepared for study by reacting DNA isolated from calf thymus with benzo[a]pyrene-7,8-diol-9,10-epoxide (the ultimate carcinogenic form of B[a]P). Other DNA/B[a]P samples have been prepared by painting the skin of mice with radiolabeled B[a]P. The ability to prepare research quantities of adducts using the hepatocyte preparation method reported by Dankovic et al is a significant development to their DNA adduct analysis program

Simulating atmospheric composition over a South-East Asian tropical rainforest: performance of a chemistry box model

Directory of Open Access Journals (Sweden)

T. A. M. Pugh

2010-01-01

Full Text Available Atmospheric composition and chemistry above tropical rainforests is currently not well established, particularly for south-east Asia. In order to examine our understanding of chemical processes in this region, the performance of a box model of atmospheric boundary layer chemistry is tested against measurements made at the top of the rainforest canopy near Danum Valley, Malaysian Borneo. Multi-variate optimisation against ambient concentration measurements was used to estimate average canopy-scale emissions for isoprene, total monoterpenes and nitric oxide. The excellent agreement between estimated values and measured fluxes of isoprene and total monoterpenes provides confidence in the overall modelling strategy, and suggests that this method may be applied where measured fluxes are not available, assuming that the local chemistry and mixing are adequately understood. The largest contributors to the optimisation cost function at the point of best-fit are OH (29%, NO (22% and total peroxy radicals (27%. Several factors affect the modelled VOC chemistry. In particular concentrations of methacrolein (MACR and methyl-vinyl ketone (MVK are substantially overestimated, and the hydroxyl radical (OH concentration is substantially underestimated; as has been seen before in tropical rainforest studies. It is shown that inclusion of dry deposition of MACR and MVK and wet deposition of species with high Henry's Law values substantially improves the fit of these oxidised species, whilst also substantially decreasing the OH sink. Increasing OH production arbitrarily, through a simple OH recycling mechanism , adversely affects the model fit for volatile organic compounds (VOCs. Given the constraints on isoprene flux provided by measurements, a substantial decrease in the rate of reaction of VOCs with OH is the only remaining option to explain the measurement/model discrepancy for OH. A reduction in the isoprene+OH rate constant of 50%, in conjunction with

Repair of furocoumarin adducts in mammalian cells

International Nuclear Information System (INIS)

Zolan, M.E.; Smith, C.A.; Hanawalt, P.C.

1984-01-01

DNA repair was studied in cultured mammalian cells treated with the furocoumarins 8-methoxypsoralen (8-MOP), aminomethyl trioxsalen, or angelicin and irradiated with near UV light. The amount of DNA cross-linked by 8-MOP in normal human cells decreased by about one-half in 24 hours after treatment; no decrease was observed in xeroderma pigmentosum cells, group A. At present, it is not known to what extent this decrease represents complete repair events at the sites of cross-links. Furocoumarin adducts elicited excision repair in normal human and monkey cells but not in xeroderma pigmentosum group A cells. This excision repair resembled in several aspects that elicited by pyrimidine dimers, formed in DNA by irradiation with 254-nm UV light; however, it appeared that for at least 8-MOP and aminomethyl trioxsalen, removal of adducts was not as efficient as was the removal of pyrimidine dimers. A comparison was also made of repair in the 172-base-pair repetitive alpha-DNA component of monkey cells to repair in the bulk of the genome. Although repair elicited by pyrimidine dimers in alpha-DNA was the same as in the bulk DNA, that following treatment of cells with either aminomethyl trioxsalen or angelicin and near UV was markedly deficient in alpha-DNA. This deficiency reflected the removal of fewer adducts from alpha-DNA after the same initial adduct frequencies. These results could mean that each furocoumarin may produce several structurally distinct adducts to DNA in cells and that the capacity of cellular repair systems to remove these various adducts may vary greatly

Formation and persistence of DNA adducts from the carcinogen N-hydroxy-2-acetylaminofluorene in rat mammary gland in vivo

International Nuclear Information System (INIS)

Allaben, W.T.; Weis, C.C.; Fullerton, N.F.; Beland, F.A.

1983-01-01

The rat mammary carcinogen, N-hydroxy-2-acetylaminofluorene (N-hydroxy-2-AAF), has been proposed to be metabolically activated by mammary cytosolic N,O-acetyltransferase to a DNA binding species. To test this hypothesis, adult female Sprague-Dawley derived CD rats were treated, i.p., with 4.0 mg/kg [ring- 3 H]N-hydroxy-2-AAF. After 4 h, 1, 3, 14, and 28 days, the animals were killed, the mammary epithelium DNA was isolated and the carcinogen-deoxyribonucleoside adducts present were analyzed by high pressure liquid chromatography. At each time, only one adduct was detected and it was chromatographically identical to N-(deoxyguanosin-8-yl)-2-aminofluorene. The level of the adduct was maximal at 4 h (1.5 adducts/10(6) nucleotides) and then decreased, following first order kinetics with a t1/2 of 14.2 days. The detection of a single non-acetylated aminofluorene adduct is consistent with N,O-acyltransferase being involved in the metabolic activation of N-hydroxy-2-AAF in the rat mammary gland

Linking the generation of DNA adducts to lung cancer.

Science.gov (United States)

Ceppi, Marcello; Munnia, Armelle; Cellai, Filippo; Bruzzone, Marco; Peluso, Marco E M

2017-09-01

Worldwide, lung cancer is the leading cause of cancer death. DNA adducts are considered a reliable biomarker that reflects carcinogen exposure to tobacco smoke, but the central question is what is the relationship of DNA adducts and cancer? Therefore, we investigated this relationship by a meta-analysis of twenty-two studies with bronchial adducts for a total of 1091 subjects, 887 lung cancer cases and 204 apparently healthy individuals with no evidence of lung cancer. Our study shows that these adducts are significantly associated to increase lung cancer risk. The value of Mean Ratio lung-cancer (MR) of bronchial adducts resulting from the random effects model was 2.64, 95% C.I. 2.00-3.50, in overall lung cancer cases as compared to controls. The significant difference, with lung cancer patients having significant higher levels of bronchial adducts than controls, persisted after stratification for smoking habits. The MR lung-cancer value between lung cancer patients and controls for smokers was 2.03, 95% C.I. 1.42-2.91, for ex-smokers 3.27, 95% C.I. 1.49-7.18, and for non-smokers was 3.81, 95% C.I. 1.85-7.85. Next, we found that the generation of bronchial adducts is significantly related to inhalation exposure to tobacco smoke carcinogens confirming its association with volatile carcinogens. The MR smoking estimate of bronchial adducts resulting from meta-regression was 2.28, 95% Confidence Interval (C.I.) 1.10-4.73, in overall smokers in respect to non-smokers. The present work provides strengthening of the hypothesis that bronchial adducts are not simply relate to exposure, but are a cause of chemical-induced lung cancer. Copyright © 2017 Elsevier B.V. All rights reserved.

Modeling the response of forest isoprene emissions to future increases in atmospheric CO2 concentration and changes in climate (Invited)

Science.gov (United States)

Monson, R. K.; Heald, C. L.; Guenther, A. B.; Wilkinson, M.

2009-12-01

Isoprene emissions from plants to the atmosphere are sensitive to changes in temperature, light and atmospheric CO2 concentration in both the short- (seconds-to-minutes) and long-term (hours-to-months). We now understand that the different time constants for these responses are due to controls by different sets of biochemical and physiological processes n leaves. Progress has been made in the past few years toward converting this process-level understanding into quantitative models. In this talk, we consider this progress with special emphasis on the short- and long-term responses to atmospheric CO2 concentration and temperature. A new biochemically-based model is presented for describing the CO2 responses, and the model is deployed in a global context to predict interactions between the influences of temperature and CO2 on the global isoprene emission rate. The model is based on the theory of enzyme-substrate kinetics, particularly with regard to those reactions that produce puruvate or glyceraldehyde 3-phosphate, the two chloroplastic substrates for isoprene biosynthesis. In the global model, when we accounted for CO2 inhibition of isoprene emission in the long-term response, we observed little impact on present-day global isoprene emission (increase from 508 to 523 Tg C yr-1). However, the large increases in future isoprene emissions predicted from past models which are due to a projected warmer climate, were entirely offset by including the CO2 effects. The isoprene emission response to CO2 was dominated by the long-term growth environment effect, with modulations of 10% or less from the short-term effect. We use this analysis as a framework for grounding future global models of isoprene emission in biochemical and physiological observations.

Isoprene emission potentials from European oak forests derived from canopy flux measurements: an assessment of uncertainties and inter-algorithm variability

Science.gov (United States)

Langford, Ben; Cash, James; Acton, W. Joe F.; Valach, Amy C.; Hewitt, C. Nicholas; Fares, Silvano; Goded, Ignacio; Gruening, Carsten; House, Emily; Kalogridis, Athina-Cerise; Gros, Valérie; Schafers, Richard; Thomas, Rick; Broadmeadow, Mark; Nemitz, Eiko

2017-12-01

Biogenic emission algorithms predict that oak forests account for ˜ 70 % of the total European isoprene budget. Yet the isoprene emission potentials (IEPs) that underpin these model estimates are calculated from a very limited number of leaf-level observations and hence are highly uncertain. Increasingly, micrometeorological techniques such as eddy covariance are used to measure whole-canopy fluxes directly, from which isoprene emission potentials can be calculated. Here, we review five observational datasets of isoprene fluxes from a range of oak forests in the UK, Italy and France. We outline procedures to correct the measured net fluxes for losses from deposition and chemical flux divergence, which were found to be on the order of 5-8 and 4-5 %, respectively. The corrected observational data were used to derive isoprene emission potentials at each site in a two-step process. Firstly, six commonly used emission algorithms were inverted to back out time series of isoprene emission potential, and then an average isoprene emission potential was calculated for each site with an associated uncertainty. We used these data to assess how the derived emission potentials change depending upon the specific emission algorithm used and, importantly, on the particular approach adopted to derive an average site-specific emission potential. Our results show that isoprene emission potentials can vary by up to a factor of 4 depending on the specific algorithm used and whether or not it is used in a big-leaf or canopy environment (CE) model format. When using the same algorithm, the calculated average isoprene emission potential was found to vary by as much as 34 % depending on how the average was derived. Using a consistent approach with version 2.1 of the Model for Emissions of Gases and Aerosols from Nature (MEGAN), we derive new ecosystem-scale isoprene emission potentials for the five measurement sites: Alice Holt, UK (10 500 ± 2500 µg m-2 h-1); Bosco Fontana, Italy (1610 �

Top-down Estimates of Isoprene Emissions in Australia Inferred from OMI Satellite Data.

Science.gov (United States)

Greenslade, J.; Fisher, J. A.; Surl, L.; Palmer, P. I.

2017-12-01

Australia is a global hotspot for biogenic isoprene emission factors predicted by process-based models such as the Model of Emissions of Gases and Aerosols from Nature (MEGAN). It is also prone to increasingly frequent temperature extremes that can drive episodically high emissions. Estimates of biogenic isoprene emissions from Australia are poorly constrained, with the frequently used MEGAN model overestimating emissions by a factor of 4-6 in some areas. Evaluating MEGAN and other models in Australia is difficult due to sparse measurements of emissions and their ensuing chemical products. In this talk, we will describe efforts to better quantify Australian isoprene emissions using top-down estimates based on formaldehyde (HCHO) observations from the OMI satellite instrument, combined with modelled isoprene to HCHO yields obtained from the GEOS-Chem chemical transport model. The OMI-based estimates are evaluated using in situ observations from field campaigns conducted in southeast Australia. We also investigate the impact on the inferred emission of horizontal resolution used for the yield calculations, particularly in regions on the boundary between low- and high-NOx chemistry. The prevalence of fire smoke plumes roughly halves the available satellite dataset over Australia for much of the year; however, seasonal averages remain robust. Preliminary results show that the top-down isoprene emissions are lower than MEGAN estimates by up to 90% in summer. The overestimates are greatest along the eastern coast, including areas surrounding Australia's major population centres in Sydney, Melbourne, and Brisbane. The coarse horizontal resolution of the model significantly affects the emissions estimates, as many biogenic emitting regions lie along narrow coastal stretches. Our results confirm previous findings that the MEGAN biogenic emission model is poorly calibrated for the Australian environment and suggests that chemical transport models driven by MEGAN are likely

Hydrothermal synthesis of ultralong and single-crystalline Cd(OH)2 nanowires using alkali salts as mineralizers.

Science.gov (United States)

Tang, Bo; Zhuo, Linhai; Ge, Jiechao; Niu, Jinye; Shi, Zhiqiang

2005-04-18

Ultralong and single-crystalline Cd(OH)(2) nanowires were fabricated by a hydrothermal method using alkali salts as mineralizers. The morphology and size of the final products strongly depend on the effects of the alkali salts (e.g., KCl, KNO(3), and K(2)SO(4) or NaCl, NaNO(3), and Na(2)SO(4)). When the salt is absent, only nanoparticles are observed in TEM images of the products. The 1D nanostructure growth method presented herein offers an excellent tool for the design of other advanced materials with anisotropic properties. In addition, the Cd(OH)(2) nanowires might act as a template or precursor that is potentially converted into 1D cadmium oxide through dehydration or into 1D nanostructures of other functional materials (e.g., CdS, CdSe).

Elevated atmospheric CO2 concentration leads to increased whole-plant isoprene emission in hybrid aspen (Populus tremula × Populus tremuloides).

Science.gov (United States)

Sun, Zhihong; Niinemets, Ülo; Hüve, Katja; Rasulov, Bahtijor; Noe, Steffen M

2013-05-01

Effects of elevated atmospheric [CO2] on plant isoprene emissions are controversial. Relying on leaf-scale measurements, most models simulating isoprene emissions in future higher [CO2] atmospheres suggest reduced emission fluxes. However, combined effects of elevated [CO2] on leaf area growth, net assimilation and isoprene emission rates have rarely been studied on the canopy scale, but stimulation of leaf area growth may largely compensate for possible [CO2] inhibition reported at the leaf scale. This study tests the hypothesis that stimulated leaf area growth leads to increased canopy isoprene emission rates. We studied the dynamics of canopy growth, and net assimilation and isoprene emission rates in hybrid aspen (Populus tremula × Populus tremuloides) grown under 380 and 780 μmol mol(-1) [CO2]. A theoretical framework based on the Chapman-Richards function to model canopy growth and numerically compare the growth dynamics among ambient and elevated atmospheric [CO2]-grown plants was developed. Plants grown under elevated [CO2] had higher C : N ratio, and greater total leaf area, and canopy net assimilation and isoprene emission rates. During ontogeny, these key canopy characteristics developed faster and stabilized earlier under elevated [CO2]. However, on a leaf area basis, foliage physiological traits remained in a transient state over the whole experiment. These results demonstrate that canopy-scale dynamics importantly complements the leaf-scale processes, and that isoprene emissions may actually increase under higher [CO2] as a result of enhanced leaf area production. © 2013 The Authors. New Phytologist © 2013 New Phytologist Trust.

DNA adducts-chemical addons

Directory of Open Access Journals (Sweden)

T R Rajalakshmi

2015-01-01

Full Text Available DNA adduct is a piece of DNA covalently bond to a chemical (safrole, benzopyrenediol epoxide, acetaldehyde. This process could be the start of a cancerous cell. When a chemical binds to DNA, it gets damaged resulting in abnormal replication. This could be the start of a mutation and without proper DNA repair, this can lead to cancer. It is this chemical that binds with the DNA is our prime area of concern. Instead of performing the whole body analysis for diagnosing cancer, this test could be carried out for early detection of cancer. When scanning tunneling microscope is used, the DNA results can be obtained earlier. DNA adducts in scientific experiments are used as biomarkers.

Formation of DNA adducts in mouse tissues after 1-nitropyrene administration

International Nuclear Information System (INIS)

Mitchell, C.E.

1986-01-01

DNA adducts were isolated and characterized in mouse lung, liver and kidney after intratracheal instillation of [ 3 H]-1-nitropyrene (1-NP). HPLC analysis of the enzymatically digested DNA indicated the presence of multiple DNA adducts in mouse lung, liver and kidney. These results indicate that DNA adducts of 1-NP are formed in mouse lung, liver and kidney after intratracheal instillation of 1-NP; the HPLC profiles of the multiple adducts suggests that adducts may be formed via metabolic pathways that involve both nitroreduction and ring-oxidation. 6 references, 1 figure

Inhalation developmental toxicology studies: Teratology study of isoprene in mice and rats: Final report

Energy Technology Data Exchange (ETDEWEB)

Mast, T.J.; Evanoff, J.J.; Stoney, K.H.; Westerberg, R.B.; Rommereim, R.L.; Weigel, R.J.

1989-01-01

Isoprene, a reactive, branched diene, is used in large quantities in the manufacture of polyisoprene and as a copolymer in the synthesis of butyl rubber. The potential for isoprene to cause developmental toxicity was assessed in rodents, by exposing four groups each of Sprague-Dawley rats and Swiss (CD-1) mice to 0, 280, 1400, or 7000 ppM isoprene vapors, 6 h/day, 7 day/wk. Each treatment group consisted of 10 virgin females (for comparison), and approx.30 positively mated rats or mice. Positively mated mice were exposed on days 6-17 of gestation (dg), and rats on 6-19 dg. The day of plug or sperm detection was designated as 0 dg. Body weights were obtained throughout the study period, and uterine and fetal body weights were obtained at sacrifice (rats, 20 dg; mice, 18 dg). Implants were enumerated and their status recorded. Live fetuses were sexed and examined for gross, visceral, skeletal, and soft-tissue craniofacial defects. 31 refs., 6 figs., 19 tabs.

Measuring urinary N-acetyl-S-(4-hydroxy-2-methyl-2-buten-1-yl)-L-cysteine (IPMA3) as a potential biomarker of isoprene exposure.

Science.gov (United States)

Alwis, K Udeni; Bailey, T Liz; Patel, Dhrusti; Wang, Liqun; Blount, Benjamin C

2016-10-19

Isoprene, the 2-methyl analog of 1,3-butadiene, is identified as a possible human carcinogen by the International Agency for Research on Cancer (IARC). Isoprene is ubiquitous in the environment with numerous natural and anthropogenic sources. Tobacco smoke is the main exogenous source of isoprene exposure in indoor environments. Among smoke constituents, isoprene is thought to contribute significantly to cancer risk; however, no selective urinary biomarkers of isoprene exposure have been identified for humans. In this manuscript, we measured the minor isoprene metabolite IPMA1 (mixture of N-acetyl-S-(1-[hydroxymethyl]-2-methyl-2-propen-1-yl)-L-cysteine and N-acetyl-S-(2-hydroxy-3-methyl-3-buten-1-yl)-L-cysteine), and we identified IPMA3 (N-acetyl-S-(4-hydroxy-2-methyl-2-buten-1-yl)-L-cysteine) as a major isoprene metabolite and novel isoprene exposure biomarker for humans. Urinary isoprene metabolites were measured using ultra high performance liquid chromatography coupled with electrospray ionization triple quad tandem mass spectrometry (UPLC/ESI-MSMS). The detection rates of IPMA1 and IPMA3 are <20% and 82%, respectively. The selectivity and abundance of IPMA3 make it a useful urinary biomarker of isoprene exposure. The limit of detection of IPMA3 in urine was 0.5 ng mL -1 . IPMA3 was stable under different storage temperatures and following ten freeze-thaw cycles. The average recovery of urine spiked with IPMA3 at three different levels was 99%. IPMA3 was measured in urine samples received from 75 anonymous subjects; the median (25th percentile, 75th percentile) IPMA3 level in smokers was 36.2 (18.2, 56.8) ng mL -1 and non-smokers 2.31 (2.31, 4.38) ng mL -1 . Application of this method to large population studies will help to characterize isoprene exposure and assess potential health impact. Published by Elsevier B.V.

Real-Time Analysis of Isoprene in Breath by Using Ultraviolet-Absorption Spectroscopy with a Hollow Optical Fiber Gas Cell.

Science.gov (United States)

Iwata, Takuro; Katagiri, Takashi; Matsuura, Yuji

2016-12-05

A breath analysis system based on ultraviolet-absorption spectroscopy was developed by using a hollow optical fiber as a gas cell for real-time monitoring of isoprene in breath. The hollow optical fiber functions as an ultra-small-volume gas cell with a long path. The measurement sensitivity of the system was evaluated by using nitric-oxide gas as a gas sample. The evaluation result showed that the developed system, using a laser-driven, high-intensity light source and a 3-m-long, aluminum-coated hollow optical fiber, could successfully measure nitric-oxide gas with a 50 ppb concentration. An absorption spectrum of a breath sample in the wavelength region of around 200-300 nm was measured, and the measured spectrum revealed the main absorbing components in breath as water vapor, isoprene, and ozone converted from oxygen by radiation of ultraviolet light. The concentration of isoprene in breath was estimated by multiple linear regression. The regression analysis results showed that the proposed analysis system enables real-time monitoring of isoprene during the exhaling of breath. Accordingly, it is suitable for measuring the circadian variation of isoprene.

Real-Time Analysis of Isoprene in Breath by Using Ultraviolet-Absorption Spectroscopy with a Hollow Optical Fiber Gas Cell

Directory of Open Access Journals (Sweden)

Takuro Iwata

2016-12-01

Full Text Available A breath analysis system based on ultraviolet-absorption spectroscopy was developed by using a hollow optical fiber as a gas cell for real-time monitoring of isoprene in breath. The hollow optical fiber functions as an ultra-small-volume gas cell with a long path. The measurement sensitivity of the system was evaluated by using nitric-oxide gas as a gas sample. The evaluation result showed that the developed system, using a laser-driven, high-intensity light source and a 3-m-long, aluminum-coated hollow optical fiber, could successfully measure nitric-oxide gas with a 50 ppb concentration. An absorption spectrum of a breath sample in the wavelength region of around 200–300 nm was measured, and the measured spectrum revealed the main absorbing components in breath as water vapor, isoprene, and ozone converted from oxygen by radiation of ultraviolet light. The concentration of isoprene in breath was estimated by multiple linear regression. The regression analysis results showed that the proposed analysis system enables real-time monitoring of isoprene during the exhaling of breath. Accordingly, it is suitable for measuring the circadian variation of isoprene.

Infrared spectra of volatile adduct of uranyl pivaloyltrifluoroacetonate with hexamethylphosphorotriamide

International Nuclear Information System (INIS)

Bukhmarina, V.N.; Dushin, R.B.; Sidorenko, G.V.; Suglobov, D.N.

1983-01-01

Adduct of uranyl pivaloyltrifluoroacetonate with hexamethylphosphortriamide (1), sublimated without decomposition and characterized by a high thermal stability, has been synthesized, as well as adducts of uranyl dipivaloylmethanate with hexamethylphosphortriamide (2) and dimethyl sulfoxide (3), sublimated with partial dissociation. IR spectra of crystalline adducts 1-3, their solutions in benzene; gaseous and matrix-isolated adduct 1 have been measured. It is shown that in gaseous phase 1 exists practically completely in non-dissociated form. It is detected that uranyl group in crystalline 1 and 2 and in matrix-isolated 1 in contrast to crystalline 3 and previously studied adducts of uranyl β-diketonates has an asymmetric structure. Strength constants of uranyl group in crystalline 1-3 and matrix-isolated 1 are determined

Potential repair of free radical adducts of dGMP and dG by a series of reductants. A pulse radiolytic study

International Nuclear Information System (INIS)

O'Neill, P.; Chapman, P.W.

1985-01-01

Using the technique of pulse radiolysis, it has been demonstrated that the interaction of hydroxyl-radical adducts of dG and dGMP with a series of reductants with different oxidation potentials at pH 7.0-7.4 proceeds via an electron transfer process (k approx. 1.4-34 x 10 8 dm 3 mol -1 s -1 ). The one-electron oxidation of dGMP (dG) by Br2-anion radicals was shown to result in the formation of a species, the properties of which are similar to those of the OH-radical adduct of dGMP with oxidizing properties based upon both spectral and kinetic information. The nature of the dGMP species produced on interaction with Br2-anion radicals to produce specific base damage. The implications of these findings are presented in terms of potential free radical repair of hydroxyl radical damage and of synergistic effects whereby one reductant may be regenerated at the expense of another reductant. (author)

Isoprene emissions over Asia 1979-2012: impact of climate and land use changes

Science.gov (United States)

Stavrakou, T.; Müller, J.-F.; Bauwens, M.; De Smedt, I.; Van Roozendael, M.; Guenther, A.; Wild, M.; Xia, X.

2013-11-01

Due to the scarcity of observational constraints and the rapidly changing environment in East and Southeast Asia, isoprene emissions predicted by models are expected to bear substantial uncertainties. The aim of this study is to improve upon the existing bottom-up estimates, and investigate the temporal evolution of the fluxes in Asia over 1979-2012. To this purpose, we calculate the hourly emissions at 0.5° × 0.5° resolution using the MEGAN-MOHYCAN model driven by ECMWF ERA-Interim climatology. This study incorporates (i) changes in land use, including the rapid expansion of oil palms, (ii) meteorological variability according to ERA-Interim, (iii) long-term changes in solar radiation (dimming/brightening) constrained by surface network radiation measurements, and (iv) recent experimental evidence that South Asian tropical forests are much weaker isoprene emitters than previously assumed, and on the other hand, that oil palms hold a strong isoprene emission capacity. These effects lead to a significant lowering (factor of two) in the total isoprene fluxes over the studied domain, and to emission reductions reaching a~factor of 3.5 in Southeast Asia. The bottom-up annual isoprene emissions for 2005 are estimated at 7.0, 4.8, 8.3, 2.9 Tg in China, India, Indonesia and Malaysia, respectively. Changes in temperature and solar radiation are the major drivers of the interannual variability and trend in the emissions. An annual positive flux trend of 0.2% and 0.52% is found in Asia and China, respectively, through the entire period, related to positive trend in temperature and solar radiation. The impact of oil palm expansion in Indonesia and Malaysia is to enhance the trends over that region, e.g. from 1.17% to 1.5% in 1979-2005 in Malaysia. A negative emission trend is derived in India (-0.4%), owing to the negative trend in solar radiation data associated to the strong dimming effect likely due to increasing aerosol loadings. The bottom-up emissions are evaluated

Environmental air pollution and DNA adducts in Copenhagen bus drivers - effect of GSTM1 and NAT2 genotypes on adduct level

DEFF Research Database (Denmark)

Nielsen, Per Sabro; de Pater, Nettie; Okkels, Henrik

1996-01-01

The lymphocyte bulky PAH-DNA adduct levels have been studied in persons occupationally exposed to ambient air pollution. The exposure group consisted of 90 healthy, nonsmoking bus drivers from the Copenhagen area, divided into three exposure groups according to driving area, and 60 rural controls...... (smokers and non-smokers). PAH-DNA adducts were determined by 32P-postlabelling with the butanol enrichment procedure. The bus drivers answered a comprehensive questionnaire on passive smoking, residential area, diet and other potential confounding variables. A significantly higher adduct level...... was observed in bus drivers working in central Copenhagen (1.214 fmol/microg DNA, n = 49) compared with both those driving in the dormitory (median: 0.507 fmol/microg DNA, P = 0.046, n = 16) and suburban (median: 0.585 fmol/microg DNA, P = 0.041, n = 25) areas. All three groups had higher adduct levels than...

Isoprene emission potentials from European oak forests derived from canopy flux measurements: an assessment of uncertainties and inter-algorithm variability

Directory of Open Access Journals (Sweden)

B. Langford

2017-12-01

Full Text Available Biogenic emission algorithms predict that oak forests account for ∼ 70 % of the total European isoprene budget. Yet the isoprene emission potentials (IEPs that underpin these model estimates are calculated from a very limited number of leaf-level observations and hence are highly uncertain. Increasingly, micrometeorological techniques such as eddy covariance are used to measure whole-canopy fluxes directly, from which isoprene emission potentials can be calculated. Here, we review five observational datasets of isoprene fluxes from a range of oak forests in the UK, Italy and France. We outline procedures to correct the measured net fluxes for losses from deposition and chemical flux divergence, which were found to be on the order of 5–8 and 4–5 %, respectively. The corrected observational data were used to derive isoprene emission potentials at each site in a two-step process. Firstly, six commonly used emission algorithms were inverted to back out time series of isoprene emission potential, and then an average isoprene emission potential was calculated for each site with an associated uncertainty. We used these data to assess how the derived emission potentials change depending upon the specific emission algorithm used and, importantly, on the particular approach adopted to derive an average site-specific emission potential. Our results show that isoprene emission potentials can vary by up to a factor of 4 depending on the specific algorithm used and whether or not it is used in a big-leaf or canopy environment (CE model format. When using the same algorithm, the calculated average isoprene emission potential was found to vary by as much as 34 % depending on how the average was derived. Using a consistent approach with version 2.1 of the Model for Emissions of Gases and Aerosols from Nature (MEGAN, we derive new ecosystem-scale isoprene emission potentials for the five measurement sites: Alice Holt, UK (10 500 ± 2500�

Measurements of a potential interference with laser-induced fluorescence measurements of ambient OH from the ozonolysis of biogenic alkenes

Science.gov (United States)

Rickly, Pamela; Stevens, Philip S.

2018-01-01

Reactions of the hydroxyl radical (OH) play a central role in the chemistry of the atmosphere, and measurements of its concentration can provide a rigorous test of our understanding of atmospheric oxidation. Several recent studies have shown large discrepancies between measured and modeled OH concentrations in forested areas impacted by emissions of biogenic volatile organic compounds (BVOCs), where modeled concentrations were significantly lower than measurements. A potential reason for some of these discrepancies involves interferences associated with the measurement of OH using the laser-induced fluorescence-fluorescence assay by gas expansion (LIF-FAGE) technique in these environments. In this study, a turbulent flow reactor operating at atmospheric pressure was coupled to a LIF-FAGE cell and the OH signal produced from the ozonolysis of α-pinene, β-pinene, ocimene, isoprene, and 2-methyl-3-buten-2-ol (MBO) was measured. To distinguish between OH produced from the ozonolysis reactions and any OH artifact produced inside the LIF-FAGE cell, an external chemical scrubbing technique was used, allowing for the direct measurement of any interference. An interference under high ozone (between 2 × 1013 and 10 × 1013 cm-3) and BVOC concentrations (between approximately 0.1 × 1012 and 40 × 1012 cm-3) was observed that was not laser generated and was independent of the ozonolysis reaction time. For the ozonolysis of α- and β-pinene, the observed interference accounted for approximately 40 % of the total OH signal, while for the ozonolysis of ocimene the observed interference accounted for approximately 70 % of the total OH signal. Addition of acetic acid to the reactor eliminated the interference, suggesting that the source of the interference in these experiments involved the decomposition of stabilized Criegee intermediates (SCIs) inside the FAGE detection cell. Extrapolation of these measurements to ambient concentrations suggests that these interferences

Why are estimates of global terrestrial isoprene emissions so similar (and why is this not so for monoterpenes?

Directory of Open Access Journals (Sweden)

A. Arneth

2008-08-01

Full Text Available Emissions of biogenic volatile organic compounds (BVOC are a chief uncertainty in calculating the burdens of important atmospheric compounds like tropospheric ozone or secondary organic aerosol, reflecting either imperfect chemical oxidation mechanisms or unreliable emission estimates, or both. To provide a starting point for a more systematic discussion we review here global isoprene and monoterpene emission estimates to-date. We note a surprisingly small variation in the predictions of global isoprene emission rate that is in stark contrast with our lack of process understanding and the small number of observations for model parameterisation and evaluation. Most of the models are based on similar emission algorithms, using fixed values for the emission capacity of various plant functional types. In some cases, these values are very similar but differ substantially in other models. The similarities with regard to the global isoprene emission rate would suggest that the dominant parameters driving the ultimate global estimate, and thus the dominant determinant of model sensitivity, are the specific emission algorithm and isoprene emission capacity. But the models also differ broadly with regard to their representation of net primary productivity, method of biome coverage determination and climate data. Contrary to isoprene, monoterpene estimates show significantly larger model-to-model variation although variation in terms of leaf algorithm, emission capacities, the way of model upscaling, vegetation cover or climatology used in terpene models are comparable to those used for isoprene. From our summary of published studies there appears to be no evidence that the terrestrial modelling community has been any more successful in "resolving unknowns" in the mechanisms that control global isoprene emissions, compared to global monoterpene emissions. Rather, the proliferation of common parameterization schemes within a large variety of model platforms

Remote sensing estimation of isoprene and monoterpene emissions generated by natural vegetation in Monterrey, Mexico.

Science.gov (United States)

Gastelum, Sandra L; Mejía-Velázquez, G M; Lozano-García, D Fabián

2016-06-01

In addition to oxygen, hydrocarbons are the most reactive chemical compounds produced by plants into the atmosphere. These compounds are part of the family of volatile organic compounds (VOCs) and are discharged in a great variety of forms. Among the VOCs produced by natural sources such as vegetation, the most studied until today are the isoprene and monoterpene. These substances can play an important role in the chemical balance of the atmosphere of a region. In this project, we develop a methodology to estimate the natural (vegetation) emission of isoprene and monoterpenes and applied it to the Monterrey Metropolitan Area, Mexico and its surrounding areas. Landsat-TM data was used to identify the dominant vegetation communities and field work to determine the foliage biomass density of key species. The studied communities were submontane scrub, oak, and pine forests and a combination of both. We carried out the estimation of emissions for isoprene and monoterpenes compounds in the different plant communities, with two different criteria: (1) taking into account the average foliage biomass density obtained from the various sample point in each vegetation community, and (2) using the foliage biomass density obtained for each transect, associated to an individual spectral class within a particular vegetation type. With this information, we obtained emission maps for each case. The results show that the main producers of isoprene are the communities that include species of the genus Quercus, located mainly on the Sierra Madre Oriental and Sierra de Picachos, with average isoprene emissions of 314.6 ton/day and 207.3 ton/day for the two methods utilized. The higher estimates of monoterpenes were found in the submontane scrub areas distributed along the valley of the metropolitan zone, with an estimated average emissions of 47.1 ton/day and 181.4 tons for the two methods respectively.

Effect of acetylator genotype on the levels of carcinogen-DNA adducts in inbred hamsters treated with 2-aminofluorene

International Nuclear Information System (INIS)

Flammang, T.J.; Yerokun, T.; Hein, D.W.; Talaska, G.; Kirlin, W.G.; Ogolla, F.; Ferguson, R.J.

1990-01-01

A genetic polymorphism in N-acetyltransferase has been described previously in humans and in animal models that is known to affect an individual's susceptibility to certain drug toxicities and diseases including bladder cancer. In hamsters, the polymorphism is known to regulate the conversion of carcinogenic 2-aminofluorene to its amide and of N-hydroxy-2-aminofluorene to a reactive electrophile that forms a covalently-bound adduct with DNA; an event thought to initiate the tumorigenic process. A single dose of 2-aminofluorene (60 mg/kg body wt., i.p) was administered to homozygous rapid- (rr) and homozygous slow-acetylator (ss) hamsters, and the levels of aminofluorene-DNA adducts in bladder and liver were evaluated by a 32 P-postlabeling assay. Only a non-acetylated aminofluorene-DNA adduct was detected in the DNA samples. In this study, no differences were detected between the levels of hepatic 2-aminofluorene-DNA adducts in males or females or between the rr or ss hamsters. In contrast, the levels of 2-amino-fluorene-adducts in bladder DNA were 5-fold higher in the male rr than in the ss hamsters, and were 2-fold higher in the male rr than in the female rr animals

Quantification of volatile organic compounds in exhaled human breath. Acetonitrile as biomarker for passive smoking. Model for isoprene in human breath; Quantifizierung organischer Spurenkomponenten in der menschlichen Atemluft. Acetonitril als Biomarker fuer Passivrauchen. Modell fuer Isopren im Atem, Zusammenhang Isoprenkonzentration, Cholesterinsynthese, lebensmittelchemische Untersuchungen an Knoblauch und Zwiebel

Energy Technology Data Exchange (ETDEWEB)

Prazeller, P

2000-03-01

The topic of this thesis is the quantification of volatile organic compounds in human breath under various circumstances. The composition of exhaled breath reflects metabolic processes in the human body. Breath analysis is a non invasive technique which makes it most interesting especially for medical or toxicological applications. Measurements were done with Proton-Transfer-Reaction Mass-Spectrometry (PTR-MS). This technique combines the advantage of small fragmentation of chemical ionization with highly time resolved mass spectrometry. A big part of this work is about investigations of exposition due to tobacco smoke. After smoking cigarettes the initial increase and time dependence of some compounds in the human breath are monitored . The calculated decrease resulting only from breathing out the compounds is presented and compared to the measured decline in the breath. This allows the distinction whether breathing is the dominant loss of a compound or a different metabolic process remover it more efficiently. Acetonitrile measured in human breath is presented as a biomarker for exposition to tobacco smoke. Especially its use for quantification of passive smoking, the exposition to environmental tobacco smoke (ETS) is shown. The reached accuracy and the fast way of measuring of acetonitrile in human breath using PTR-MS offer a good alternative to common used biomarkers. Numerous publications have described measurements of breath isoprene in humans, and there has been a hope that breath isoprene analyses could be a non-invasive diagnostic tool to assess serum cholesterol levels or cholesterol synthesis rate. However, significant analytical problems in breath isoprene analysis and variability in isoprene levels with age, exercise, diet, etc. have limited the usefulness of these measurements. Here, we have applied proton-transfer-reaction mass spectrometry (PTR-MS) to this problem, allowing on-line detection of breath isoprene. We show that breath isoprene

Inhibition of nitrobenzene-induced DNA and hemoglobin adductions by dietary constituents

Energy Technology Data Exchange (ETDEWEB)

Li Hongli; Cheng Yan; Wang Haifang; Sun Hongfang; Liu Yuanfang E-mail: yliu@pku.edu.cn; Liu Kexin; Peng Shixiang

2003-03-01

Nitrobenzene (NB), a widely used industrial chemical, is a likely human carcinogen. Many dietary constituents can suppress the DNA-adduction, acting as the inhibitors of cancer. In this study, we investigated the inhibitory effects of vitamin C (VC), vitamin E (VE), tea polyphenols (TP), garlic squeeze, curcumin, and grapestone extract on NB-DNA and NB-hemoglobin (Hb) adductions in mice using an ultrasensitive method of accelerator mass spectrometry (AMS) with {sup 14}C-labelled nitrobenzene. All of these dietary constituents showed their inhibitory effects on DNA or Hb adduction. VC, VE, TP and grapestone extract could efficaciously inhibit the adductions by 33-50%, and all of these six agents could inhibit Hb adduction by 30-64%. We also investigated resveratrol, curcumin, VC and VE as inhibitors of NB-DNA adduction in vitro using liquid scintillation counting technique. These agents in the presence of NADPH and S9 components also pronouncedly blocked DNA adduction in a dose-dependent profile. Our study suggests that these seven constituents may interrupt the process of NB-induced chemical carcinogenesis.

CYP1A2 and NAT2 phenotyping and 3-aminobiphenyl and 4-aminobiphenyl hemoglobin adduct levels in smokers and non-smokers

International Nuclear Information System (INIS)

Sarkar, Mohamadi; Stabbert, Regina; Kinser, Robin D.; Oey, Jan; Rustemeier, Klaus; Holt, Klaus von; Schepers, Georg; Walk, Roger A.; Roethig, Hans J.

2006-01-01

Some aromatic amines are considered to be putative bladder carcinogens. Hemoglobin (Hb) adducts of 3-aminobiphenyl (3-ABP) and 4-aminobiphenyl (4-ABP) have been used as biomarkers of exposure to aromatic amines from cigarette smoke. One of the goals of this study was to determine intra- and inter-individual variability in 3-ABP and 4-ABP Hb adducts and to explore the predictability of ABP Hb adduct levels based on caffeine phenotyping. The study was conducted in adult smokers (S, n = 65) and non-smokers (NS, n 65). The subjects were phenotyped for CYP1A2 and NAT2 using urinary caffeine metabolites. Blood samples were collected twice within 6 weeks and adducts measured by GC/MS. The levels of 4-ABP Hb adducts were significantly (p < 0.0001) greater in S (34.5 ± 21.06 pg/g Hb) compared to NS (6.3 ± 3.02 pg/g Hb). The levels of 3-ABP Hb adducts were below the limit of quantification (BLOQ) in most (82%) of the NS and about 10-fold lower in S (3.6 ± 3.29 pg/g Hb) compared to 4-ABP Hb adducts. No differences were observed in the adduct levels between weeks 1 and 6 in the smokers, suggesting that a single sample would be adequate to monitor cigarette smoke exposure. The regression model developed with CYP1A2, NAT2 phenotype and number of cigarettes smoked (NCIG) accounted for 47% of the variability in 3-ABP adducts, whereas 32% variability in 4-ABP adducts was accounted by CYP1A2 and NCIG. The ratio of 4-ABP Hb adducts in adult S:NS was ∼ 5:1, whereas 3-ABP Hb adducts levels were BLOQ in some S, exhibited large interindividual variability (∼ 91% compared to 57% for 4-ABP Hb) and poor dose response relationship. Therefore, 4-ABP Hb adduct levels may be a more useful biomarker of aminobiphenyl exposure from cigarette smoke

Isoprene emissions over Asia 1979-2012: impact of climate and land-use changes

Science.gov (United States)

Stavrakou, T.; Müller, J.-F.; Bauwens, M.; De Smedt, I.; Van Roozendael, M.; Guenther, A.; Wild, M.; Xia, X.

2014-05-01

Due to the scarcity of observational constraints and the rapidly changing environment in East and Southeast Asia, isoprene emissions predicted by models are expected to bear substantial uncertainties. The aim of this study is to improve upon the existing bottom-up estimates, and to investigate the temporal evolution of the fluxes in Asia over 1979-2012. To this purpose, we calculate the hourly emissions at 0.5°×0.5° resolution using the MEGAN-MOHYCAN model driven by ECMWF ERA-Interim climatology. In order to remedy for known biases identified in previous studies, and to improve the simulation of interannual variability and trends in emissions, this study incorporates (i) changes in land use, including the rapid expansion of oil palms, (ii) meteorological variability according to ERA-Interim, (iii) long-term changes in solar radiation (dimming/brightening) constrained by surface network radiation measurements, and (iv) recent experimental evidence that South Asian tropical forests are much weaker isoprene emitters than previously assumed, and on the other hand, that oil palms have a strong isoprene emission capacity. These effects lead to a significant lowering (factor of 2) in the total isoprene fluxes over the studied domain, and to emission reductions reaching a factor of 3.5 in Southeast Asia. The bottom-up annual isoprene emissions for 2005 are estimated at 7.0, 4.8, 8.3, and 2.9 Tg in China, India, Indonesia and Malaysia, respectively. The isoprene flux anomaly over the whole domain and studied period is found to be strongly correlated with the Oceanic Niño Index (r = 0.73), with positive (negative) anomalies related to El Niño (La Niña) years. Changes in temperature and solar radiation are the major drivers of the interannual variability and trends in the emissions, except over semi-arid areas such as northwestern China, Pakistan and Kazakhstan, where soil moisture is by far the main cause of interannual emission changes. In our base simulation, annual

Differential repair of etheno-DNA adducts by bacterial and human AlkB proteins.

Science.gov (United States)

Zdżalik, Daria; Domańska, Anna; Prorok, Paulina; Kosicki, Konrad; van den Born, Erwin; Falnes, Pål Ø; Rizzo, Carmelo J; Guengerich, F Peter; Tudek, Barbara

2015-06-01

AlkB proteins are evolutionary conserved Fe(II)/2-oxoglutarate-dependent dioxygenases, which remove alkyl and highly promutagenic etheno(ɛ)-DNA adducts, but their substrate specificity has not been fully determined. We developed a novel assay for the repair of ɛ-adducts by AlkB enzymes using oligodeoxynucleotides with a single lesion and specific DNA glycosylases and AP-endonuclease for identification of the repair products. We compared the repair of three ɛ-adducts, 1,N(6)-ethenoadenine (ɛA), 3,N(4)-ethenocytosine (ɛC) and 1,N(2)-ethenoguanine (1,N(2)-ɛG) by nine bacterial and two human AlkBs, representing four different structural groups defined on the basis of conserved amino acids in the nucleotide recognition lid, engaged in the enzyme binding to the substrate. Two bacterial AlkB proteins, MT-2B (from Mycobacterium tuberculosis) and SC-2B (Streptomyces coelicolor) did not repair these lesions in either double-stranded (ds) or single-stranded (ss) DNA. Three proteins, RE-2A (Rhizobium etli), SA-2B (Streptomyces avermitilis), and XC-2B (Xanthomonas campestris) efficiently removed all three lesions from the DNA substrates. Interestingly, XC-2B and RE-2A are the first AlkB proteins shown to be specialized for ɛ-adducts, since they do not repair methylated bases. Three other proteins, EcAlkB (Escherichia coli), SA-1A, and XC-1B removed ɛA and ɛC from ds and ssDNA but were inactive toward 1,N(2)-ɛG. SC-1A repaired only ɛA with the preference for dsDNA. The human enzyme ALKBH2 repaired all three ɛ-adducts in dsDNA, while only ɛA and ɛC in ssDNA and repair was less efficient in ssDNA. ALKBH3 repaired only ɛC in ssDNA. Altogether, we have shown for the first time that some AlkB proteins, namely ALKBH2, RE-2A, SA-2B and XC-2B can repair 1,N(2)-ɛG and that ALKBH3 removes only ɛC from ssDNA. Our results also suggest that the nucleotide recognition lid is not the sole determinant of the substrate specificity of AlkB proteins. Copyright © 2015 Elsevier B

Quantification of volatile organic compounds in exhaled human breath. Acetonitrile as biomarker for passive smoking. Model for isoprene in human breath

International Nuclear Information System (INIS)

Prazeller, P.

2000-03-01

The topic of this thesis is the quantification of volatile organic compounds in human breath under various circumstances. The composition of exhaled breath reflects metabolic processes in the human body. Breath analysis is a non invasive technique which makes it most interesting especially for medical or toxicological applications. Measurements were done with Proton-Transfer-Reaction Mass-Spectrometry (PTR-MS). This technique combines the advantage of small fragmentation of chemical ionization with highly time resolved mass spectrometry. A big part of this work is about investigations of exposition due to tobacco smoke. After smoking cigarettes the initial increase and time dependence of some compounds in the human breath are monitored . The calculated decrease resulting only from breathing out the compounds is presented and compared to the measured decline in the breath. This allows the distinction whether breathing is the dominant loss of a compound or a different metabolic process remover it more efficiently. Acetonitrile measured in human breath is presented as a biomarker for exposition to tobacco smoke. Especially its use for quantification of passive smoking, the exposition to environmental tobacco smoke (ETS) is shown. The reached accuracy and the fast way of measuring of acetonitrile in human breath using PTR-MS offer a good alternative to common used biomarkers. Numerous publications have described measurements of breath isoprene in humans, and there has been a hope that breath isoprene analyses could be a non-invasive diagnostic tool to assess serum cholesterol levels or cholesterol synthesis rate. However, significant analytical problems in breath isoprene analysis and variability in isoprene levels with age, exercise, diet, etc. have limited the usefulness of these measurements. Here, we have applied proton-transfer-reaction mass spectrometry (PTR-MS) to this problem, allowing on-line detection of breath isoprene. We show that breath isoprene

Elevated [CO2] magnifies isoprene emissions under heat and improves thermal resistance in hybrid aspen

OpenAIRE

Sun, Zhihong; H?ve, Katja; Vislap, Vivian; Niinemets, ?lo

2013-01-01

Isoprene emissions importantly protect plants from heat stress, but the emissions become inhibited by instantaneous increase of [CO2], and it is currently unclear how isoprene-emitting plants cope with future more frequent and severe heat episodes under high [CO2]. Hybrid aspen (Populus tremula x Populus tremuloides) saplings grown under ambient [CO2] of 380 ?mol mol?1 and elevated [CO2] of 780 ?mol mol?1 were used to test the hypothesis that acclimation to elevated [CO2] reduces the inhibito...

Efficient syntheses of climate relevant isoprene nitrates and (1R,5S)-(-)-myrtenol nitrate.

Science.gov (United States)

Bew, Sean P; Hiatt-Gipson, Glyn D; Mills, Graham P; Reeves, Claire E

2016-01-01

Here we report the chemoselective synthesis of several important, climate relevant isoprene nitrates using silver nitrate to mediate a 'halide for nitrate' substitution. Employing readily available starting materials, reagents and Horner-Wadsworth-Emmons chemistry the synthesis of easily separable, synthetically versatile 'key building blocks' (E)- and (Z)-3-methyl-4-chlorobut-2-en-1-ol as well as (E)- and (Z)-1-((2-methyl-4-bromobut-2-enyloxy)methyl)-4-methoxybenzene has been achieved using cheap, 'off the shelf' materials. Exploiting their reactivity we have studied their ability to undergo an 'allylic halide for allylic nitrate' substitution reaction which we demonstrate generates (E)- and (Z)-3-methyl-4-hydroxybut-2-enyl nitrate, and (E)- and (Z)-2-methyl-4-hydroxybut-2-enyl nitrates ('isoprene nitrates') in 66-80% overall yields. Using NOESY experiments the elucidation of the carbon-carbon double bond configuration within the purified isoprene nitrates has been established. Further exemplifying our 'halide for nitrate' substitution chemistry we outline the straightforward transformation of (1R,2S)-(-)-myrtenol bromide into the previously unknown monoterpene nitrate (1R,2S)-(-)-myrtenol nitrate.

The influence of auxins on the biosynthesis of isoprene derivatives in callus cultures of Vaccinium corymbosum var. bluecrop.

Science.gov (United States)

Migas, Piotr; Luczkiewicz, Maria; Cisowski, Wojciech

2006-01-01

Callus cultures of Vaccinium corymbosum var. bluecrop were optimized for their isoprene derivatives production by supplementing Schenk-Hildebrandt (SH) medium with constant concentration of kinetin (2.32 microM) and two different amounts of selected auxins. Every auxin, except for IBA, used in 10-time higher concentration (2,4D, NAA, IAA, NOA) stimulated biosynthesis of beta-sitosterol and inhibited triterpene synthesis. Quantitative analysis of isoprene derivatives in callus biomass collected on the 25th day of the experiment proved that the analyzed callus of Vaccinium corymbosum var. bluecrop synthesized the highest amount of isoprene derivatives after subculturing on SH medium modified with 22.6 microM of 2,4D and 2.32 microM of kinetin.

DNA adducts: Mass spectrometry methods and future prospects

International Nuclear Information System (INIS)

Farmer, P.B.; Brown, K.; Tompkins, E.; Emms, V.L.; Jones, D.J.L.; Singh, R.; Phillips, D.H.

2005-01-01

Detection of DNA adducts is widely used for the monitoring of exposure to genotoxic carcinogens. Knowledge of the nature and amounts of DNA adducts formed in vivo also gives valuable information regarding the mutational effects that may result from particular exposures. The power of mass spectrometry (MS) to achieve qualitative and quantitative analyses of human DNA adducts has increased greatly in recent years with the development of improved chromatographic interfaces and ionisation sources. Adducts have been detected on nucleic acid bases, 2'-deoxynucleosides or 2'-deoxynucleotides, with LC-MS/MS being the favoured technique for many of these analyses. Our current applications of this technique include the determination of N7-(2-carbamoyl-2-hydroxyethyl)-guanine, which was postulated to be found as a DNA repair product in urine following exposure to acrylamide, and of 8-oxo-7,8-dihydro-2'-deoxyguanosine and 8-oxo-7,8-dihydro-2'-deoxyadenosine, as markers of oxidative damage in human lymphocyte DNA. Higher sensitivity (with a detection limit of 1-10 adducts/10 12 nucleotides) may be achieved by the use of accelerator mass spectrometry (AMS), although this requires the presence of certain isotopes, such as [ 14 C], in the material being analysed. In order to make this technique more amenable for studies of human exposure to environmental carcinogens, new postlabelling techniques, incorporating [ 14 C] into specific DNA adducts after formation, are being developed. It is expected that combining the use of advanced MS techniques with existing 32 P-postlabelling and immunochemical methodologies will contribute greatly to the understanding of the burden of human exposure to environmental carcinogens

Chamber simulation of photooxidation of dimethyl sulfide and isoprene in the presence of NOx

Directory of Open Access Journals (Sweden)

M. Jang

2012-11-01

Full Text Available To improve the model prediction for the formation of H2SO4 and methanesulfonic acid (MSA, aerosol-phase reactions of gaseous dimethyl sulfide (DMS oxidation products [e.g., dimethyl sulfoxide (DMSO] in aerosol have been included in the DMS kinetic model with the recently reported gas-phase reactions and their rate constants. To determine the rate constants of aerosol-phase reactions of both DMSO and its major gaseous products [e.g., dimethyl sulfone (DMSO2 and methanesulfinic acid (MSIA], DMSO was photooxidized in the presence of NOx using a 2 m3 Teflon film chamber. The rate constants tested in the DMSO kinetic mechanisms were then incorporated into the DMS photooxidation mechanism. The model simulation using the newly constructed DMS oxidation mechanims was compared to chamber data obtained from the phototoxiation of DMS in the presence of NOx. Within 120-min simulation, the predicted concentrations of MSA increase by 200–400% and those of H2SO4, by 50–200% due to aerosol-phase chemistry. This was well substantiated with experimental data. To study the effect of coexisting volatile organic compounds, the photooxidation of DMS in the presence of isoprene and NOx has been simulated using the newly constructed DMS kinetic model integrated with the Master Chemical Mechanism (MCM for isoprene oxidation, and compared to chamber data. With the high concentrations of DMS (250 ppb and isoprene (560–2248 ppb, both the model simulation and experimental data showed an increase in the yields of MSA and H2SO4 as the isoprene concentration increased.

Synergy between methylerythritol phosphate pathway and mevalonate pathway for isoprene production in Escherichia coli.

Science.gov (United States)

Yang, Chen; Gao, Xiang; Jiang, Yu; Sun, Bingbing; Gao, Fang; Yang, Sheng

2016-09-01

Isoprene, a key building block of synthetic rubber, is currently produced entirely from petrochemical sources. In this work, we engineered both the methylerythritol phosphate (MEP) pathway and the mevalonate (MVA) pathway for isoprene production in E. coli. The synergy between the MEP pathway and the MVA pathway was demonstrated by the production experiment, in which overexpression of both pathways improved the isoprene yield about 20-fold and 3-fold, respectively, compared to overexpression of the MEP pathway or the MVA pathway alone. The (13)C metabolic flux analysis revealed that simultaneous utilization of the two pathways resulted in a 4.8-fold increase in the MEP pathway flux and a 1.5-fold increase in the MVA pathway flux. The synergy of the dual pathway was further verified by quantifying intracellular flux responses of the MEP pathway and the MVA pathway to fosmidomycin treatment and mevalonate supplementation. Our results strongly suggest that coupling of the complementary reducing equivalent demand and ATP requirement plays an important role in the synergy of the dual pathway. Fed-batch cultivation of the engineered strain overexpressing the dual pathway resulted in production of 24.0g/L isoprene with a yield of 0.267g/g of glucose. The synergy of the MEP pathway and the MVA pathway also successfully increased the lycopene productivity in E. coli, which demonstrates that it can be used to improve the production of a broad range of terpenoids in microorganisms. Copyright © 2016 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.

Isomerization of Second-Generation Isoprene Peroxy Radicals

DEFF Research Database (Denmark)

D'Ambro, Emma L.; Møller, Kristian Holten; Lopez-Hilfiker, Felipe D.

2017-01-01

kinetics box model, we find that to explain the behavior of low-volatility products and SOA mass yields relative to input H2O2 concentrations, the second-generation dihydroxy hydroperoxy peroxy radical (C5H11O6·) must undergo an intramolecular H-shift with a net forward rate constant of order 0.1 s-1...... products under atmospheric conditions and, thus, on the importance of nonreactive gas-particle partitioning of isoprene oxidation products as an SOA source....

Single measurement of serum 25(OH)D: is classification into month-specific cutpoints useful in accounting for seasonal variation?

Science.gov (United States)

Saliba, W; Barnett-Griness, O; Rennert, G

2012-09-01

Classification into month-specific cutpoints is used to minimize misclassification associated with single measurement of serum 25(OH)D. This study aims to evaluate this strategy, and to compare it with the widely used classification into overall cutpoints. For this purpose, we studied 69,553 subjects in whom serum 25(OH)D was tested on two different occasions. The level of agreement between the quartiles of the first and second tests was 43.8% between the month-specific quartiles and 43.1% between the overall quartiles. The level of agreement between the quartiles of the two approaches was 80.0% and 94.3% in the first and second test, respectively. The extent of seasonal variation (summer-autumn as compared with winter-spring) of serum 25(OH)D was higher in males and in Jews, inversely associated with baseline levels, body mass index and age, and directly associated with socioeconomic class. The month-specific cutpoint strategy does not seem to offer advantage over the overall cutpoints strategy.

Lamellar-crossing-structured Ni(OH){sub 2}/CNTs/Ni(OH){sub 2} nanocomposite for electrochemical supercapacitor materials

Energy Technology Data Exchange (ETDEWEB)

Wu, Qingnan [Department of Chemistry, State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, Shanghai 200092 (China); Wen, Ming, E-mail: m_wen@tongji.edu.cn [Department of Chemistry, State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, Shanghai 200092 (China); Shanghai Key Lab of Chemical Assessment and Sustainability, Tongji University, Shanghai 200092 (China); Chen, Shipei [Department of Chemistry, State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, Shanghai 200092 (China); Wu, Qingsheng [Department of Chemistry, State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, Shanghai 200092 (China); Shanghai Key Lab of Chemical Assessment and Sustainability, Tongji University, Shanghai 200092 (China)

2015-10-15

Ni(OH){sub 2}/CNTs/Ni(OH){sub 2} lamellar-crossing-nanostructure with a single lamellar spacing of ∼5 nm was effectively constructed through two-phase-interface reaction process followed by the CNTs crossed among the lamellar-nanostructured Ni(OH){sub 2}. The resultant nanocomposite can offer large active surface areas and short diffusion paths for electrons and ions, and is investigated as a potential pseudocapacitor electrode material for electrochemical energy storage applications. Electrochemical data demonstrate that the as-prepared nanocomposite exhibits a high specific capacitance of ∼1600 F g{sup −1} at the scan rate of 1 mV s{sup −1} in 6 M KOH solution at normal pressure and temperature, which is great higher than Ni(OH){sub 2} (∼1200 F g{sup −1}). Furthermore, Ni(OH){sub 2}/CNTs/Ni(OH){sub 2} nanocomposite shows a higher energy density (∼125 Wh kg{sup −1}, 2 A g{sup −1}) and has a slightly decrease of 5% in specific capacitance after 1000 continuous charge/discharge cycles. - Graphical abstract: As-constructed Ni(OH){sub 2}/CNTs/Ni(OH){sub 2} lamellar-crossing-nanostructure exhibits remarkable enhancement in electrochemical stability and high specific capacity of ∼1600 F g{sup −1} at a scan rate of 1 mV s{sup −1}, suggesting promising potential for supercapacitor applications. - Highlights: • New designed lamellar-crossing-structured Ni(OH){sub 2}/CNTs/Ni(OH){sub 2} nanocomposites have been firstly reported in this work. • Ni(OH){sub 2}/CNTs/Ni(OH){sub 2} lamellar-crossing-nanostructures show firm nanostructure and excellent electrochemical stability. • Ni(OH){sub 2}/CNTs/Ni(OH){sub 2} nanocomposites exhibit excellent specific capacitance. • Ni(OH){sub 2}/CNTs/Ni(OH){sub 2} nanocomposites have the potential application in electrochemical energy storage applications.

Quantitation of DNA adducts by stable isotope dilution mass spectrometry

Science.gov (United States)

Tretyakova, Natalia; Goggin, Melissa; Janis, Gregory

2012-01-01

Exposure to endogenous and exogenous chemicals can lead to the formation of structurally modified DNA bases (DNA adducts). If not repaired, these nucleobase lesions can cause polymerase errors during DNA replication, leading to heritable mutations potentially contributing to the development of cancer. Due to their critical role in cancer initiation, DNA adducts represent mechanism-based biomarkers of carcinogen exposure, and their quantitation is particularly useful for cancer risk assessment. DNA adducts are also valuable in mechanistic studies linking tumorigenic effects of environmental and industrial carcinogens to specific electrophilic species generated from their metabolism. While multiple experimental methodologies have been developed for DNA adduct analysis in biological samples – including immunoassay, HPLC, and 32P-postlabeling – isotope dilution high performance liquid chromatography-electrospray ionization-tandem mass spectrometry (HPLC-ESI-MS/MS) generally has superior selectivity, sensitivity, accuracy, and reproducibility. As typical DNA adducts concentrations in biological samples are between 0.01 – 10 adducts per 108 normal nucleotides, ultrasensitive HPLC-ESI-MS/MS methodologies are required for their analysis. Recent developments in analytical separations and biological mass spectrometry – especially nanoflow HPLC, nanospray ionization MS, chip-MS, and high resolution MS – have pushed the limits of analytical HPLC-ESI-MS/MS methodologies for DNA adducts, allowing researchers to accurately measure their concentrations in biological samples from patients treated with DNA alkylating drugs and in populations exposed to carcinogens from urban air, drinking water, cooked food, alcohol, and cigarette smoke. PMID:22827593

Xeroderma Pigmentosum Group A Suppresses Mutagenesis Caused by Clustered Oxidative DNA Adducts in the Human Genome

Science.gov (United States)

Sassa, Akira; Kamoshita, Nagisa; Kanemaru, Yuki; Honma, Masamitsu; Yasui, Manabu

2015-01-01

Clustered DNA damage is defined as multiple sites of DNA damage within one or two helical turns of the duplex DNA. This complex damage is often formed by exposure of the genome to ionizing radiation and is difficult to repair. The mutagenic potential and repair mechanisms of clustered DNA damage in human cells remain to be elucidated. In this study, we investigated the involvement of nucleotide excision repair (NER) in clustered oxidative DNA adducts. To identify the in vivo protective roles of NER, we established a human cell line lacking the NER gene xeroderma pigmentosum group A (XPA). XPA knockout (KO) cells were generated from TSCER122 cells derived from the human lymphoblastoid TK6 cell line. To analyze the mutagenic events in DNA adducts in vivo, we previously employed a system of tracing DNA adducts in the targeted mutagenesis (TATAM), in which DNA adducts were site-specifically introduced into intron 4 of thymidine kinase genes. Using the TATAM system, one or two tandem 7,8-dihydro-8-oxoguanine (8-oxoG) adducts were introduced into the genomes of TSCER122 or XPA KO cells. In XPA KO cells, the proportion of mutants induced by a single 8-oxoG (7.6%) was comparable with that in TSCER122 cells (8.1%). In contrast, the lack of XPA significantly enhanced the mutant proportion of tandem 8-oxoG in the transcribed strand (12%) compared with that in TSCER122 cells (7.4%) but not in the non-transcribed strand (12% and 11% in XPA KO and TSCER122 cells, respectively). By sequencing the tandem 8-oxoG-integrated loci in the transcribed strand, we found that the proportion of tandem mutations was markedly increased in XPA KO cells. These results indicate that NER is involved in repairing clustered DNA adducts in the transcribed strand in vivo. PMID:26559182

Xeroderma Pigmentosum Group A Suppresses Mutagenesis Caused by Clustered Oxidative DNA Adducts in the Human Genome.

Science.gov (United States)

Sassa, Akira; Kamoshita, Nagisa; Kanemaru, Yuki; Honma, Masamitsu; Yasui, Manabu

2015-01-01

Clustered DNA damage is defined as multiple sites of DNA damage within one or two helical turns of the duplex DNA. This complex damage is often formed by exposure of the genome to ionizing radiation and is difficult to repair. The mutagenic potential and repair mechanisms of clustered DNA damage in human cells remain to be elucidated. In this study, we investigated the involvement of nucleotide excision repair (NER) in clustered oxidative DNA adducts. To identify the in vivo protective roles of NER, we established a human cell line lacking the NER gene xeroderma pigmentosum group A (XPA). XPA knockout (KO) cells were generated from TSCER122 cells derived from the human lymphoblastoid TK6 cell line. To analyze the mutagenic events in DNA adducts in vivo, we previously employed a system of tracing DNA adducts in the targeted mutagenesis (TATAM), in which DNA adducts were site-specifically introduced into intron 4 of thymidine kinase genes. Using the TATAM system, one or two tandem 7,8-dihydro-8-oxoguanine (8-oxoG) adducts were introduced into the genomes of TSCER122 or XPA KO cells. In XPA KO cells, the proportion of mutants induced by a single 8-oxoG (7.6%) was comparable with that in TSCER122 cells (8.1%). In contrast, the lack of XPA significantly enhanced the mutant proportion of tandem 8-oxoG in the transcribed strand (12%) compared with that in TSCER122 cells (7.4%) but not in the non-transcribed strand (12% and 11% in XPA KO and TSCER122 cells, respectively). By sequencing the tandem 8-oxoG-integrated loci in the transcribed strand, we found that the proportion of tandem mutations was markedly increased in XPA KO cells. These results indicate that NER is involved in repairing clustered DNA adducts in the transcribed strand in vivo.

Sensitivity of isoprene emissions estimated using MEGAN to the time resolution of input climate data

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K. Ashworth

2010-02-01

Full Text Available We evaluate the effect of varying the temporal resolution of the input climate data on isoprene emission estimates generated by the community emissions model MEGAN (Model of Emissions of Gases and Aerosols from Nature. The estimated total global annual emissions of isoprene is reduced from 766 Tg y⁻¹ when using hourly input data to 746 Tg y⁻¹ (a reduction of 3% for daily average input data and 711 Tg y⁻¹ (down 7% for monthly average input data. The impact on a local scale can be more significant with reductions of up to 55% at some locations when using monthly average data compared with using hourly data. If the daily and monthly average temperature data are used without the imposition of a diurnal cycle the global emissions estimates fall by 27–32%, and local annual emissions by up to 77%. A similar pattern emerges if hourly isoprene fluxes are considered. In order to better simulate and predict isoprene emission rates using MEGAN, we show it is necessary to use temperature and radiation data resolved to one hour. Given the importance of land-atmosphere interactions in the Earth system and the low computational cost of the MEGAN algorithms, we recommend that chemistry-climate models and the new generation of Earth system models input biogenic emissions at the highest temporal resolution possible.

SCIAMACHY formaldehyde observations: constraint for isoprene emission estimates over Europe?

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G. Dufour

2009-03-01

Full Text Available Formaldehyde (HCHO is an important intermediate compound in the degradation of volatile organic compounds (VOCs in the troposphere. Sources of HCHO are largely dominated by its secondary production from VOC oxidation, methane and isoprene being the main precursors in unpolluted areas. As a result of the moderate lifetime of HCHO, its spatial distribution is determined by reactive hydrocarbon emissions. We focus here on Europe and investigate the influence of the different emissions on HCHO tropospheric columns with the CHIMERE chemical transport model in order to interpret the comparisons between SCIAMACHY and simulated HCHO columns. Europe was never specifically studied before for these purposes using satellite observations. The bias between measurements and model is less than 20% on average. The differences are discussed according to the errors on the model and the observations and remaining discrepancies are attributed to a misrepresentation of biogenic emissions. This study requires the characterisation of: (1 the model errors and performances concerning formaldehyde. The errors on the HCHO columns, mainly related to chemistry and mixed emission types, are evaluated to 2×10¹⁵ molecule/cm² and the model performances evaluated using surface measurements are satisfactory (~13%; (2 the observation errors that define the needs in spatial and temporal averaging for meaningful comparisons. Using SCIAMACHY observations as constraint for biogenic isoprene emissions in an inverse modelling scheme reduces their uncertainties by about a factor of two in region of intense emissions. The retrieved correction factors for the isoprene emissions range from a factor of 0.15 (North Africa to a factor of 2 (Poland, the United Kingdom depending on the regions.

Synthesis, spectral and thermal studies of pyridyl adducts of Zn(II) and Cd(II) dithiocarbamates, and their use as single source precursors for ZnS and CdS nanoparticles

OpenAIRE

Onwudiwe, Damian C.; Strydom, Christien A.; Jordaan, Anine; Oluwafemi, Oluwatobi S.; Hosten, Eric

2014-01-01

The synthesis, spectroscopic characterisation, and thermal studies of pyridyl adducts of Zn(II) and Cd(II) complexes of N-ethyl-N-phenyl dithiocarbamate, represented as [ZnL2py] and [CdL2py2], are reported. Single-crystal X-ray structural analysis of the Zn compound showed that it is five-coordinate with four sulphurs from dithiocarbamate and one nitrogen from pyridine in a distorted square pyramidal geometry. The thermogravimetric studies indicate that the zinc and cadmium compou...

Analysis of trends in isoprene and monoterpenes in a remote forest and an anthropogenic influenced forest

Science.gov (United States)

Usenko, S.; Sheesley, R. J.; Winfield, Z.; Yoon, S.; Erickson, M.; Flynn, J. H., III; Alvarez, S. L.; Wallace, H. W., IV; Griffin, R. J.

2017-12-01

The University of Houston Mobile Air Quality Laboratory (MAQL) was deployed to the University of Michigan Biological Station (UMBS) in July 2016 as part of the PROPHET-AMOS study and then was deployed to Jones Forest located north of Houston, TX from August 12 through September 23, 2016. Both sites are heavily forested, but UMBS is remote with no anthropogenic influence while Jones Forest sees frequent pollution transport from Houston. UMBS experienced periods of high isoprene:monoterpenes and periods of equivalent isoprene:monoterpenes, while Jones Forest had a consistently high isoprene:monoterpenes. This provided for a test bed to look at the interactions within two forested environments as well as the influence of anthropogenic sources. The MAQL was outfitted to measure O3 (2B Technology), NOy and SO2 (Thermo Scientific), NO/NOx (Air Quality Design), CO (Los Gatos), and select biogenic volatile organic carbon (BVOC) with their oxidation products (Ionicon PTR-MS). The instruments sampled from MAQL's 6 m tower at both sites. The UMBS site was below canopy and the Jones Forest site was in an open field surrounded by forest. The trends in isoprene and monoterpenes were explored in relation to time-of-day, temperature, and precipitation for both locations. In addition, the production of methyl vinyl ketone and methacrolein under these different conditions of meteorology, trace gas composition and BVOC composition was explored.

Detection of carcinogen-DNA adducts by radioimmunoassay

International Nuclear Information System (INIS)

Poirier, M.C.; Yuspa, S.H.; Weinstein, I.B.; Blobstein, S.

1977-01-01

Covalent binding of carcinogen to nucleic acids is believed to be an essential component of the carcinogenic process, so it is desirable to have highly sensitive and specific methods for detecting such adducts in cells and tissues exposed to known and suspected carcinogens. A radioimmunoassay is here described capable of detecting nanogram amounts of DNA adducts resulting from the covalent binding of the carcinogen N-2-acetylaminofluorene and its activated N-acetoxy derivative. (author)

Investigation of the oxidation of methyl vinyl ketone (MVK) by OH radicals in the atmospheric simulation chamber SAPHIR

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Fuchs, Hendrik; Albrecht, Sascha; Acir, Ismail-Hakki; Bohn, Birger; Breitenlechner, Martin; Dorn, Hans-Peter; Gkatzelis, Georgios I.; Hofzumahaus, Andreas; Holland, Frank; Kaminski, Martin; Keutsch, Frank N.; Novelli, Anna; Reimer, David; Rohrer, Franz; Tillmann, Ralf; Vereecken, Luc; Wegener, Robert; Zaytsev, Alexander; Kiendler-Scharr, Astrid; Wahner, Andreas

2018-06-01

The photooxidation of methyl vinyl ketone (MVK) was investigated in the atmospheric simulation chamber SAPHIR for conditions at which organic peroxy radicals (RO2) mainly reacted with NO (high NO case) and for conditions at which other reaction channels could compete (low NO case). Measurements of trace gas concentrations were compared to calculated concentration time series applying the Master Chemical Mechanism (MCM version 3.3.1). Product yields of methylglyoxal and glycolaldehyde were determined from measurements. For the high NO case, the methylglyoxal yield was (19 ± 3) % and the glycolaldehyde yield was (65 ± 14) %, consistent with recent literature studies. For the low NO case, the methylglyoxal yield reduced to (5 ± 2) % because other RO2 reaction channels that do not form methylglyoxal became important. Consistent with literature data, the glycolaldehyde yield of (37 ± 9) % determined in the experiment was not reduced as much as implemented in the MCM, suggesting additional reaction channels producing glycolaldehyde. At the same time, direct quantification of OH radicals in the experiments shows the need for an enhanced OH radical production at low NO conditions similar to previous studies investigating the oxidation of the parent VOC isoprene and methacrolein, the second major oxidation product of isoprene. For MVK the model-measurement discrepancy was up to a factor of 2. Product yields and OH observations were consistent with assumptions of additional RO2 plus HO2 reaction channels as proposed in literature for the major RO2 species formed from the reaction of MVK with OH. However, this study shows that also HO2 radical concentrations are underestimated by the model, suggesting that additional OH is not directly produced from RO2 radical reactions, but indirectly via increased HO2. Quantum chemical calculations show that HO2 could be produced from a fast 1,4-H shift of the second most important MVK derived RO2 species (reaction rate constant 0

Synthesis and physicochemical investigation of adducts of rare earth thenoyltrifluoroacetonates

International Nuclear Information System (INIS)

Anufrieva, S.I.; Snezhko, N.I.; Martynenko, L.I.; Pechurova, N.I.

1982-01-01

Adducts of rare earth thenoyltrifluoroacetonates (3) have been synthesized with tributylphosphate (TBP), trioctylphosphenoxide (TOPO), triphenylphosphenoxide (TPO) of 1:1 and 1:2 composition as well as with α, α'-dipyridine (Dipy), o-phenanthroline (Phen) of 1:1 composition. The separated adducts have been studied by methods of element analysis, X-ray phase and derivatographic analyses and IR spectroscopy. It is shown that the adducts are more thermostable compared to the corresponding rare earth thenoyltrifluoroacetonate hydrates

Chemical aging of single and multicomponent biomass burning aerosol surrogate particles by OH: implications for cloud condensation nucleus activity

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J. H. Slade

2015-09-01

Full Text Available Multiphase OH and O3 oxidation reactions with atmospheric organic aerosol (OA can influence particle physicochemical properties including composition, morphology, and lifetime. Chemical aging of initially insoluble or low-soluble single-component OA by OH and O3 can increase their water solubility and hygroscopicity, making them more active as cloud condensation nuclei (CCN and susceptible to wet deposition. However, an outstanding problem is whether the effects of chemical aging on their CCN activity are preserved when mixed with other organic or inorganic compounds exhibiting greater water solubility. In this work, the CCN activity of laboratory-generated biomass burning aerosol (BBA surrogate particles exposed to OH and O3 is evaluated by determining the hygroscopicity parameter, κ, as a function of particle type, mixing state, and OH and O3 exposure applying a CCN counter (CCNc coupled to an aerosol flow reactor (AFR. Levoglucosan (LEV, 4-methyl-5-nitrocatechol (MNC, and potassium sulfate (KS serve as representative BBA compounds that exhibit different hygroscopicity, water solubility, chemical functionalities, and reactivity with OH radicals, and thus exemplify the complexity of mixed inorganic/organic aerosol in the atmosphere. The CCN activities of all of the particles were unaffected by O3 exposure. Following exposure to OH, κ of MNC was enhanced by an order of magnitude, from 0.009 to ~ 0.1, indicating that chemically aged MNC particles are better CCN and more prone to wet deposition than pure MNC particles. No significant enhancement in κ was observed for pure LEV particles following OH exposure. κ of the internally mixed particles was not affected by OH oxidation. Furthermore, the CCN activity of OH-exposed MNC-coated KS particles is similar to the OH unexposed atomized 1 : 1 by mass MNC : KS binary-component particles. Our results strongly suggest that when OA is dominated by water-soluble organic carbon (WSOC or inorganic ions

Detection and quantification of 4-ABP adducts in DNA from bladder cancer patients.

Science.gov (United States)

Zayas, Beatriz; Stillwell, Sara W; Wishnok, John S; Trudel, Laura J; Skipper, Paul; Yu, Mimi C; Tannenbaum, Steven R; Wogan, Gerald N

2007-02-01

We analyzed bladder DNA from 27 cancer patients for dG-C8-4-aminobiphenyl (dG-C8-ABP) adducts using the liquid chromatography tandem mass spectrometry method with a 700 attomol (1 adduct in 10(9) bases) detection limit. Hemoglobin (Hb) 4-aminobiphenyl (4-ABP) adduct levels were measured by gas chromatography-mass spectrometry. After isolation of dG-C8-ABP by immunoaffinity chromatography and further purification, deuterated (d9) dG-C8-ABP (MW=443 Da) was added to each sample. Structural evidence and adduct quantification were determined by selected reaction monitoring, based on the expected adduct ion [M+H+]+1, at m/z 435 with fragmentation to the product ion at m/z 319, and monitoring of the transition for the internal standard, m/z 444-->328. The method was validated by analysis of DNA (100 microg each) from calf thymus; livers from ABP-treated and untreated rats; human placentas; and TK6 lymphoblastoid cells. Adduct was detected at femtomol levels in DNA from livers of ABP-treated rats and calf thymus, but not in other controls. The method was applied to 41 DNA samples (200 microg each) from 27 human bladders; 28 from tumor and 14 from surrounding non-tumor tissue. Of 27 tissues analyzed, 44% (12) contained 5-80 dG-C8-ABP adducts per 10(9) bases; only 1 out of 27 (4%) contained adduct in both tumor and surrounding tissues. The Hb adduct was detected in samples from all patients, at levels of 12-1960 pg per gram Hb. There was no correlation between levels of DNA and Hb adducts. The presence of DNA adducts in 44% of the subjects and high levels of Hb adducts in these non-smokers indicate environmental sources of exposure to 4-ABP.

Mass-spectrometric study of volatile uranyl β-diketonates and their adducts

International Nuclear Information System (INIS)

Adamov, V.M.; Belyaev, B.N.; Berezinskij, S.O.; Sidorenko, G.V.; Suglobov, D.N.

1985-01-01

The mass spectra of a number of uranyl β-diketonates containing methyl, trifluoromethyl and tert-butyl substituents in β-diketonate anion, and their adducts are measured. The form of the unsolvated β-diketonates and their adducts in gas phase is studied. The ways of fragmentation of uranyl β-diketonates and their adducts are investigated. The data concerning the thermal and chemical side reactions proceeding with uranyl β-diketonates and their addicts in an ion source are obtained. The mass spectra of the samples of neptunyl and plutonyl β-diketonate adducts synthesized for the first time are measured

Synthesis and physicochemical investigation of adducts of rare earth thenoyltrifluoroacetonates

Energy Technology Data Exchange (ETDEWEB)

Anufrieva, S.I.; Snezhko, N.I.; Martynenko, L.I.; Pechurova, N.I. (Moskovskij Gosudarstvennyj Univ. (USSR))

1982-11-01

Adducts of rare earth thenoyltrifluoroacetonates (3) have been synthesized with tributylphosphate (TBP), trioctylphosphenoxide (TOPO), triphenylphosphenoxide (TPO) of 1:1 and 1:2 composition as well as with ..cap alpha.., ..cap alpha..'-dipyridine (Dipy), o-phenanthroline (Phen) of 1:1 composition. The separated adducts have been studied by methods of element analysis, X-ray phase and derivatographic analyses and IR spectroscopy. It is shown that the adducts are more thermostable compared to the corresponding rare earth thenoyltrifluoroacetonate hydrates.

Detection of Adriamycin-DNA adducts by accelerator mass spectrometry at clinically relevant Adriamycin concentrations.

Science.gov (United States)

Coldwell, Kate E; Cutts, Suzanne M; Ognibene, Ted J; Henderson, Paul T; Phillips, Don R

2008-09-01

Limited sensitivity of existing assays has prevented investigation of whether Adriamycin-DNA adducts are involved in the anti-tumour potential of Adriamycin. Previous detection has achieved a sensitivity of a few Adriamycin-DNA adducts/10(4) bp DNA, but has required the use of supra-clinical drug concentrations. This work sought to measure Adriamycin-DNA adducts at sub-micromolar doses using accelerator mass spectrometry (AMS), a technique with origins in geochemistry for radiocarbon dating. We have used conditions previously validated (by less sensitive decay counting) to extract [(14)C]Adriamycin-DNA adducts from cells and adapted the methodology to AMS detection. Here we show the first direct evidence of Adriamycin-DNA adducts at clinically-relevant Adriamycin concentrations. [(14)C]Adriamycin treatment (25 nM) resulted in 4.4 +/- 1.0 adducts/10(7) bp ( approximately 1300 adducts/cell) in MCF-7 breast cancer cells, representing the best sensitivity and precision reported to date for the covalent binding of Adriamycin to DNA. The exceedingly sensitive nature of AMS has enabled over three orders of magnitude increased sensitivity of Adriamycin-DNA adduct detection and revealed adduct formation within an hour of drug treatment. This method has been shown to be highly reproducible for the measurement of Adriamycin-DNA adducts in tumour cells in culture and can now be applied to the detection of these adducts in human tissues.

Characterization of hemoglobin-benzo[a]pyrene adducts

International Nuclear Information System (INIS)

Haugen, D.A.; Myers, S.R.

1987-01-01

Cultures of Syrian hamster embryo (SHE) cells were supplemented with human Hb (0.2 mM heme) and [ 3 H]BP (1 μM). After a 24-h incubation, the medium was removed and subjected to cation-exchange liquid chromatography (CM-Sepharose) to resolve hemoglobins from serum proteins in the medium. The BP-treated Hb was subjected to analysis in each of three column chromatographic systems established for isolation and characterization of human hemoglobin and its genetic and post-translationally modified variants. Results demonstrate that hemoglobin-carcinogen adducts can be resolved from native hemoglobin by established conventional and high-performance liquid chromatographic procedures, suggesting the basis for development of general approaches for isolating and characterizing hemoglobin-carcinogen adducts. The results also suggest the basis for a model system in which adducts between carcinogens and human hemoglobin are formed in cultures of mammalian cells or tissues

Redetermination of eveite, Mn2AsO4(OH, based on single-crystal X-ray diffraction data

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Yongbo W. Yang

2011-12-01

Full Text Available The crystal structure of eveite, ideally Mn2(AsO4(OH [dimanganese(II arsenate(V hydroxide], was refined from a single crystal selected from a co-type sample from Långban, Filipstad, Varmland, Sweden. Eveite, dimorphic with sarkinite, is structurally analogous with the important rock-forming mineral andalusite, Al2OSiO4, and belongs to the libethenite group. Its structure consists of chains of edge-sharing distorted [MnO4(OH2] octahedra (..2 symmetry extending parallel to [001]. These chains are cross-linked by isolated AsO4 tetrahedra (..m symmetry through corner-sharing, forming channels in which dimers of edge-sharing [MnO4(OH] trigonal bipyramids (..m symmetry are located. In contrast to the previous refinement from Weissenberg photographic data [Moore & Smyth (1968. Am. Mineral. 53, 1841–1845], all non-H atoms were refined with anisotropic displacement parameters and the H atom was located. The distance of the donor and acceptor O atoms involved in hydrogen bonding is in agreement with Raman spectroscopic data. Examination of the Raman spectra for arsenate minerals in the libethenite group reveals that the position of the peak originating from the O—H stretching vibration shifts to lower wavenumbers from eveite, to adamite, zincolivenite, and olivenite.

Environmental, Dietary, Maternal, and Fetal Predictors of Bulky DNA Adducts in Cord Blood

DEFF Research Database (Denmark)

Pedersen, Marie; Mendez, Michelle A; Schoket, Bernadette

2015-01-01

and drinking-water disinfection by-products, mainly trihalomethanes (THMs), were available for a large proportion of the study population. RESULTS: Greek and Spanish neonates had higher adduct levels than the northern European neonates [median, 12.1 (n = 179) vs. 6.8 (n = 332) adducts per 108 nucleotides, p...... with higher adduct levels in adjusted models. Exposure to fine particulate matter and nitrogen dioxide was associated with significantly higher adducts in the Danish subsample only. Overall, the pooled results for THMs in water show no evidence of association with adduct levels; however, there are country...

The use of isoprene as a novel dopant in negative ion atmospheric pressure photoionization mass spectrometry coupled to high-performance liquid chromatography.

Science.gov (United States)

Dousty, Faezeh; O'Brien, Rob

2015-06-15

As in the case with positive ion atmospheric pressure photoionization (PI-APPI), the addition of dopants significantly improves the sensitivity of negative ion APPI (NI-APPI). However, the research on dopant-assisted-NI-APPI has been quite limited compared to the studies on dopant-assisted PI-APPI. This work presents the potential of isoprene as a novel dopant for NI-APPI. Thirteen compounds, possessing suitable gas-phase ion energetic properties in order to make stable negative ions, were selected. Dopants were continuously introduced into a tee junction prior to the ion source through a fused-silica capillary, while analytes were directly injected into the same tee. Then both were mixed with the continuous solvent from high-performance liquid chromatography (HPLC), nebulized, and entered the source. The nebulized stream was analyzed by APPI tandem quadrupole mass spectrometry in the negative ion mode. The results obtained using isoprene were compared with those obtained by using toluene as a dopant and dopant-free NI-APPI. Isoprene enhanced the ionization intensities of the studied compounds, which were found to be comparable and, in some cases, more effective than toluene. The mechanisms leading to the observed set of negative analyte ions were also discussed. Because in NI-APPI, thermal electrons, which are produced during the photoionization of a dopant, are considered the main reagent ions, both isoprene and toluene promoted the ionization of analytes through the same mechanisms, as expected. Isoprene was shown to perform well as a novel dopant for NI-APPI. Isoprene has a high photoabsorption cross section in the VUV region; therefore, its photoionization leads to a highly effective production of thermal electrons, which further promotes the ionization of analytes. In addition, isoprene is environmentally benign and less toxic compared to currently used dopants. Copyright © 2015 John Wiley & Sons, Ltd.

Mathematical modeling of blood-gas kinetics for the volatile organic compounds isoprene and acetone

International Nuclear Information System (INIS)

King, J.

2010-01-01

Breath gas analysis is based on the compelling concept that the exhaled breath levels of endogenously produced volatile organic compounds (VOCs) can provide a direct, non-invasive window to the blood and hence, by inference, to the body. In this sense, breath VOCs are regarded as a comprehensive repository of valuable physiological and clinical information, that might be exploited in such diverse areas as diagnostics, therapeutic monitoring or general dynamic assessments of metabolic function, pharmacodynamics (e.g., in drug testing) and environmental exposure (e.g., in occupational health). Despite this enormous potential, the lack of standardized breath sampling regimes as well as the poor mechanistic understanding of VOC exhalation kinetics could cast a cloud over the widespread use of breath gas analysis in the biomedical sciences. In this context, a primary goal of the present thesis is to provide a better quantitative insight into the breath behavior of two prototypic VOCs, isoprene and acetone. A compartmental modeling framework is developed and validated by virtue of real-time breath measurements of these trace gases during distinct physiological states. In particular, the influence of various hemodynamic and ventilatory parameters on VOC concentrations in exhaled breath is investigated. This approach also complements previous steady state investigations in toxicology. From a phenomenological point of view, both acetone and isoprene concentrations in end-tidal breath are demonstrated to exhibit a reproducible non-steady state behavior during moderate workload challenges on a stationary bicycle. However, these dynamics depart drastically from what is expected on the basis of classical pulmonary inert gas elimination theory. More specifically, the start of exercise is accompanied by an abrupt increase in breath isoprene levels, usually by a factor of 3 to 4 compared with the steady state value during rest. This phase is followed by a gradual decline and the

Scavenging of Toxic Acrolein by Resveratrol and Hesperetin and Identification of Adducts.

Science.gov (United States)

Wang, Weixin; Qi, Yajing; Rocca, James R; Sarnoski, Paul J; Jia, Aiqun; Gu, Liwei

2015-11-04

The objective of this study was to investigate the ability of resveratrol and hesperetin to scavenge acrolein at pH 7.4 and 37 °C. About 6.4 or 5.2% of acrolein remained after reaction with resveratrol or hesperetin for 12 h at equimolar concentrations. An acrolein-resveratrol adduct and two acrolein-hesperetin adducts were isolated. Their structures were elucidated using mass and NMR spectroscopy. Acrolein reacted with resveratrol at the C-2 and C-3 positions through nucleophilic addition and formed an additional heterocyclic ring. Two similar monoacrolein-conjugated adducts were identified for hesperetin. Spectroscopic data suggested each acrolein-hesperetin adduct was a mixture of four stereoisomers due to the existence of two chiral carbon atoms. Yield of adducts was low at pH 5.4 but increased at pH 7.4 and 8.4. Higher pH also promoted the formation of diacrolein adducts. Results suggest that resveratrol and hesperetin exert health benefits in part through neutralizing toxic acrolein in vivo.

Impact of isoprene and nitrogen oxides on O3 chemistry at the local and the regional scale : the ESCOMPTE experiment

Science.gov (United States)

Cortinovis, J.; Solmon, F.; Personne, E.; Serça, D.; Rosset, R.

2003-04-01

Concentrations of nitrogen oxides (NOx = NO+NO2) and volatile organic compounds (VOCs) play a crucial role in the atmospheric chemistry through the production-destruction of tropospheric O3. In rural areas, NOx concentrations are much lower than in urban areas, whereas VOCs emissions can be relatively high. This is due to a relative longer residence time of VOCs, and to the substantial contribution of Biogenic VOCs (BVOCs) representing more than 85% of all the VOCs emitted at the Earth surface (half of it being isoprene). For these reasons, O3 production in rural areas is most of the time NOx-limited. Taking into account biogenic emissions of isoprene in global scale atmospheric chemistry modeling adds from 10 to 40% to the ozone produced when compared to the same simulation without isoprene. This suggests that BVOCs and NOx emissions must be accounted for in models of atmospheric pollution forecasting at local and regional scales. In this study, we present a sensitivity analysis on the impact of the isoprene and nitrogen oxides emissions at the local and the regional scale. This study is done from data collected during the ESCOMPTE campaign which took place in June and July 2001 in the Marseille region (Southwest France) characterized by both strong natural and anthropogenic sources of trace gases. Isoprene emission experimental data from a Quercus Pubescens Mediterranean forest are used to constrain the 1Dz Soil-Vegetation-Atmospheric-Transfer ISBA model. This SVAT is used in the 3D MESO-NH-Chemistry model to simulate scenarios of pollution at the regional scale including the measured biogenic source for isoprene, and GENEMIS anthropogenic sources for other trace gases. To focus on the chemistry aspect of these simulations, the atmospheric dynamics are set to an "ideal" configuration. We have investigated the impact of the relative position and distance between the biogenic and anthropogenic sources on the O3 budget. According to this, and to the intensity of the

Conformations of stereoisomeric base adducts to 4-hydroxyequilenin.

Science.gov (United States)

Ding, Shuang; Shapiro, Robert; Geacintov, Nicholas E; Broyde, Suse

2003-06-01

Exposure to estrogen through estrogen replacement therapy increases the risk of women developing cancer in hormone sensitive tissues. Premarin (Wyeth), which has been the most frequent choice for estrogen replacement therapy in the United States, contains the equine estrogens equilin and equilenin as major components. 4-Hydroxyequilenin (4-OHEN) is a phase I metabolite of both of these substances. This catechol estrogen autoxidizes to potent cytotoxic quinoids that can react with dG, dA, and dC to form unusual stereoisomeric cyclic adducts (Bolton, J. L., et al. (1998) Chem. Res. Toxicol. 11, 1113-1127). Like other bulky DNA adducts, these lesions may exhibit different susceptibilities to DNA repair and mutagenic potential, if not repaired in a structure-dependent manner. To ultimately gain insights into structure-function relationships, we computed conformations of stereoisomeric guanine, adenine, and cytosine base adducts using density functional theory. We find near mirror image conformations in stereoisomer adduct pairs for each modified base, suggesting opposite orientations with respect to the 5' --> 3' direction of the modified strand when the stereoisomer pairs are incorporated into duplex DNA. Such opposite orientations could cause stereoisomer pairs of lesions to respond differently to DNA replication and repair enzymes.

Assessment of high to low frequency variations of isoprene emission rates using a neural network approach

Science.gov (United States)

Boissard, C.; Chervier, F.; Dutot, A. L.

2007-08-01

Using a statistical approach based on artificial neural networks, an emission algorithm (ISO_LF) accounting for high (instantaneous) to low (seasonal) frequency variations was developed for isoprene. ISO_LF was optimised using an isoprene emission data base (ISO-DB) specifically designed for this work. ISO-DB consists of 1321 emission rates collected in the literature, together with 34 environmental variables, measured or assessed using NCDC (National Climatic Data Center) or NCEP (National Centers for Environmental Predictions) meteorological databases. ISO-DB covers a large variety of emitters (25 species) and environmental conditions (10° S to 60° N). When only instantaneous environmental regressors (air temperature and photosynthetic active radiation, PAR) were used, a maximum of 60% of the overall isoprene variability was assessed and the highest emissions were underestimated. Considering a total of 9 high (instantaneous) to low (up to 3 weeks) frequency regressors, ISO_LF accounts for up to 91% of the isoprene emission variability, whatever the emission range, species or climate. Diurnal and seasonal variations are correctly reproduced for textit{Ulex europaeus} with a maximum factor of discrepancy of 4. ISO-LF was found to be mainly sensitive to air temperature cumulated over 3 weeks T21 and to instantaneous light L0 and air temperature T0 variations. T21, T0 and L0 only accounts for 76% of the overall variability. The use of ISO-LF for non stored monoterpene emissions was shown to give poor results.

Effects of benzo[a]pyrene-DNA adducts on a reconstituted replication system

International Nuclear Information System (INIS)

Brown, W.C.; Romano, L.J.

1991-01-01

The authors have used a partially reconstituted replication system consisting of T7 DNA polymerase and T7 gene 4 protein to examine the effect of benzo[a]pyrene (B[a]P) adducts on DNA synthesis and gene 4 protein activities. The gene 4 protein is required for T7 DNA replication because of its ability to act as both a primase and helicase. They show here that total synthesis decreases as the level of adducts per molecule of DNA increases, suggesting that the B[a]P adducts are blocking an aspect of the replication process. By challenging synthesis on oligonucleotide-primed B[a]P-modified DNA with unmodified DNA, they present evidence that the T7 DNA polymerase freely dissociates after encountering an adduct. Prior studies have shown that the gene 4 protein alone does not dissociate from the template during translocation upon encountering an adduct. However, when gene 4 protein primed DNA synthesis is challenged, they observe an increase in synthesis but to a lesser extent than observed on oligonucleotide-primed synthesis. Finally, they have examined DNA synthesis on duplex templates and show the B[a]P adducts inhibit synthesis by the T7 DNA polymerase and gene 4 protein to the same extent regardless of whether the adducts are positioned in the leading or lagging strand, while synthesis by the polymerase alone is inhibited only when the adducts are in the template strand

Isoprene emissions over Asia 1979–2012: impact of climate and land-use changes

Energy Technology Data Exchange (ETDEWEB)

Stavrakou, T.; Müller, J. -F.; Bauwens, M.; De Smedt, I.; Van Roozendael, M.; Guenther, A.; Wild, M.; Xia, X.

2014-01-01

Due to the scarcity of observational constraints and the rapidly changing environment in East and Southeast Asia, isoprene emissions predicted by models are expected to bear substantial uncertainties. The aim of this study is to improve upon the existing bottom-up estimates, and to investigate the temporal evolution of the fluxes in Asia over 1979–2012. To this purpose, we calculate the hourly emissions at 0.5°×0.5° resolution using the MEGAN–MOHYCAN model driven by ECMWF ERA-Interim climatology. In order to remedy for known biases identified in previous studies, and to improve the simulation of interannual variability and trends in emissions, this study incorporates (i) changes in land use, including the rapid expansion of oil palms, (ii) meteorological variability according to ERA-Interim, (iii) long-term changes in solar radiation (dimming/brightening) constrained by surface network radiation measurements, and (iv) recent experimental evidence that South Asian tropical forests are much weaker isoprene emitters than previously assumed, and on the other hand, that oil palms have a strong isoprene emission capacity. These effects lead to a significant lowering (factor of 2) in the total isoprene fluxes over the studied domain, and to emission reductions reaching a factor of 3.5 in Southeast Asia. The bottom-up annual isoprene emissions for 2005 are estimated at 7.0, 4.8, 8.3, and 2.9 Tg in China, India, Indonesia and Malaysia, respectively. The isoprene flux anomaly over the whole domain and studied period is found to be strongly correlated with the Oceanic Niño Index (r = 0.73), with positive (negative) anomalies related to El Niño (La Niña) years. Changes in temperature and solar radiation are the major drivers of the interannual variability and trends in the emissions, except over semi-arid areas such as northwestern China, Pakistan and Kazakhstan, where soil moisture is by far the main cause of interannual emission changes. In our base simulation

Small-angle neutron scattering investigation of the chain conformation of lamellar polystyrene/isoprene phase in solid state

International Nuclear Information System (INIS)

Constantinescu, L.M.

1994-01-01

Small-angle neutron scattering has been used in the study of chain conformation of lamellar styrene/isoprene block copolymers oriented in large single crystals. The radius of gyration of deuterated polystyrene chains around the normal to the interface has been measured. By comparing this direct evolution of the lateral dimension of the chains with the average chain separation given by the molecular area (the surface available at the interface for each covalent bond linking the blocks together) we characterized the transverse interpenetration degree of the chains. The polystyrene chains are displayed in simple strata own micro-domains, without an important interpenetration. (Author) 9 Figs., 2 Tabs., 25 Refs

Engineering isoprene synthesis in cyanobacteria.

Science.gov (United States)

Chaves, Julie E; Melis, Anastasios

2018-04-24

The renewable production of isoprene (Isp) hydrocarbons, to serve as fuel and synthetic chemistry feedstock, has attracted interest in the field recently. Isp (C 5 H 8 ) is naturally produced from sunlight, CO 2 and H 2 O photosynthetically in terrestrial plant chloroplasts via the terpenoid biosynthetic pathway and emitted in the atmosphere as a response to heat stress. Efforts to institute a high capacity continuous and renewable process have included heterologous expression of the Isp synthesis pathway in photosynthetic microorganisms. This review examines the premise and promise emanating from this relatively new research effort. Also examined are the metabolic engineering approaches applied in the quest of renewable Isp hydrocarbons production, the progress achieved so far, and barriers encountered along the way. © 2018 Federation of European Biochemical Societies.

Adducts of uranium tetrachloride with neutral Schiff bases

Energy Technology Data Exchange (ETDEWEB)

Doretti, L; Madalosso, F; Sitran, S; Faleschini, S; Vigato, P A [Consiglio Nazionale delle Ricerche, Padua (Italy). Lab. di Chimica e Tecnologia dei Radioelementi

1977-01-01

Studies are reported of adducts of UCl/sub 4/ with various Schiff base ligands: N-(phenyl)benzalaldimine, N-(propyl) salicylaldimine, N-(phenyl) salicylaldimine, N-(2-hydroxyphenyl)benzalaldimine, N-(4-chlorophenyl)salcylaldimine, N-(4-nitrophenyl)salicylaldimine, N,N'-o-phenylenebis(salycylideneimine). The synthesis and characterization of these ligands is reported, and the preparation and characterization of the relative adducts of UCl/sub 4/: their IR spectra are reported and discussed.

Adducts of uranium tetrachloride with neutral Schiff bases

International Nuclear Information System (INIS)

Doretti, L.; Madalosso, F.; Sitran, S.; Faleschini, S.; Vigato, P.A.

1977-01-01

Studies are reported of adducts of UCl 4 with various Schiff base ligands: N-(phenyl)benzalaldimine, N-(propyl) salicylaldimine, N-(phenyl) salicylaldimine, N-(2-hydroxyphenyl)benzalaldimine, N-(4-chlorophenyl)salcylaldimine, N-(4-nitrophenyl)salicylaldimine, N,N'-o-phenylenebis (salycylideneimine). The synthesis and characterization of these ligands is reported, and the preparation and characterization of the relative adducts of UCl 4 : their IR spectra are reported and discussed. (author)

Molecular dosimetry of DNA adducts in rainbow trout (Oncorhynchus mykiss) exposed to benzo(a)pyrene by different routes

International Nuclear Information System (INIS)

Potter, D.; Clarius, T.M.; Wright, A.S.; Watson, W.P.

1994-01-01

Farm raised rainbow trout (Oncorhynchus mykiss) were exposed by various routes to benzo(a)pyrene (BP) as a representative carcinogenic polycyclic aromatic hydrocarbon (PAH). Following exposure of fish to the chemical by intraperitoneal (i.p.) injection, 32 P-postlabelling studies indicated that non-feral trout were relatively resistant to the formation of BP-DNA adducts in liver. No adducts were detected in fish exposed to single doses (20 mg/kg) of BP. Multiple exposures (e.g. 2 x 25 mg/kg) were necessary in order for adducts to be detected, indicating that induction of the metabolising enzymes required for the bioactivation of BP is necessary. These studies provided reference information on DNA adducts for comparison with data from subsequent experiments at environmentally realistic low level exposures. Two types of low level aquatic exposure were carried out. The first procedure exposed fish for 30 days to a nominally constant low level (1.2 and 0.4 μg/l) of a homogeneous dispersion of BP in water, to simulate low level aquatic environmental exposures. Following 32 P-postlabelling analysis of the liver DNA of exposed fish, BP-DNA adducts were not detected. In the second procedure, fish were exposed to a constant low level of BP (ca. 0.5 μg/l) for 15 days then to a pulse (60 μg/l) which was allowed to naturally decline (to ca. 2 μg/l) during a further 15 days. Following this exposure, significant levels of BP-DNA adducts were detected in livers of trout. The effect of dietary exposures was investigated by feeding trout a diet containing either 58 μg or 288 μg BP per day for 6 days, equivalent to total doses of 43 mg/kg and 216 mg/kg. In both cases BP-DNA adducts were detected in livers of exposed fish. The results provide useful information on the types of exposures to PAHs which may pose a genotoxic risk to fish in the environment. (orig.)

Potential sensitivity of photosynthesis and isoprene emission to direct radiative effects of atmospheric aerosol pollution

Science.gov (United States)

Strada, Susanna; Unger, Nadine

2016-04-01

A global Earth system model is applied to quantify the impacts of direct anthropogenic aerosol effective radiative forcing on gross primary productivity (GPP) and isoprene emission. The impacts of different pollution aerosol sources (anthropogenic, biomass burning, and non-biomass burning) are investigated by performing sensitivity experiments. The model framework includes all known light and meteorological responses of photosynthesis, but uses fixed canopy structures and phenology. On a global scale, our results show that global land carbon fluxes (GPP and isoprene emission) are not sensitive to pollution aerosols, even under a global decline in surface solar radiation (direct + diffuse) by ˜ 9 %. At a regional scale, GPP and isoprene emission show a robust but opposite sensitivity to pollution aerosols in regions where forested canopies dominate. In eastern North America and Eurasia, anthropogenic pollution aerosols (mainly from non-biomass burning sources) enhance GPP by +5-8 % on an annual average. In the northwestern Amazon Basin and central Africa, biomass burning aerosols increase GPP by +2-5 % on an annual average, with a peak in the northwestern Amazon Basin during the dry-fire season (+5-8 %). The prevailing mechanism varies across regions: light scattering dominates in eastern North America, while a reduction in direct radiation dominates in Europe and China. Aerosol-induced GPP productivity increases in the Amazon and central Africa include an additional positive feedback from reduced canopy temperatures in response to increases in canopy conductance. In Eurasia and northeastern China, anthropogenic pollution aerosols drive a decrease in isoprene emission of -2 to -12 % on an annual average. Future research needs to incorporate the indirect effects of aerosols and possible feedbacks from dynamic carbon allocation and phenology.

Inert Reassessment Document for Poly(oxyethylene) adducts of mixed phytosterols

Science.gov (United States)

Poly(oxyethy1ene) adducts of mixed phytosterols is uncategorized as to list classification status. Based upon the reasonable certainty of no harm safety finding, the List 4B classification for poly(oxyethy1ene) adducts of mixed phytosterols is affirmed.

Ferrous ion oxidations by ·H, ·OH and H2O2 in aerated FBX dosimetry system

International Nuclear Information System (INIS)

Gupta, B.L.; Nilekani, S.R.

1998-01-01

In the ferrous ion, benzoic acid and xylenol orange (FBX) dosimetric system, benzoic acid (BA) increases the G(Fe 3+ ) value. Xylenol orange (XO) controls the BA sensitized chain reaction as well as forms a complex with Fe 3+ . In the aerated FBX system each ·H, ·OH and H 2 O 2 oxidizes 8.5, 6.6 and 7.6 Fe 2+ ions, respectively; and these values respectively increase to 11.3, 7.6 and 8.6 in oxygenated solution. About 8% ·OH reacts with XO and the remaining with BA. The above fractional values are due to this competition. This ·OH reaction with XO oxidizes 1.8% and 2.1% ferrous ions only in aerated and oxygenated solutions, respectively. There is a competition between ·H reactions with O 2 and with BA, but both lead to the production of H 2 O 2 . The oxidation of Fe 2+ by ·OH reactions at different concentrations of H 2 O 2 is linear with absorbed dose while the ·H reactions make the oxidation of Fe 2+ non-linear with dose. This is due to competition reaction of H-adduct of BA between O 2 and Fe 3+

Tyrosine-lipid peroxide adducts from radical termination: para coupling and intramolecular Diels-Alder cyclization.

Science.gov (United States)

Shchepin, Roman; Möller, Matias N; Kim, Hye-young H; Hatch, Duane M; Bartesaghi, Silvina; Kalyanaraman, Balaraman; Radi, Rafael; Porter, Ned A

2010-12-15

Free radical co-oxidation of polyunsaturated lipids with tyrosine or phenolic analogues of tyrosine gave rise to lipid peroxide-tyrosine (phenol) adducts in both aqueous micellar and organic solutions. The novel adducts were isolated and characterized by 1D and 2D NMR spectroscopy as well as by mass spectrometry (MS). The spectral data suggest that the polyunsaturated lipid peroxyl radicals give stable peroxide coupling products exclusively at the para position of the tyrosyl (phenoxy) radicals. These adducts have characteristic (13)C chemical shifts at 185 ppm due to the cross-conjugated carbonyl of the phenol-derived cyclohexadienone. The primary peroxide adducts subsequently undergo intramolecular Diels-Alder (IMDA) cyclization, affording a number of diastereomeric tricyclic adducts that have characteristic carbonyl (13)C chemical shifts at ~198 ppm. All of the NMR HMBC and HSQC correlations support the structure assignments of the primary and Diels-Alder adducts, as does MS collision-induced dissociation data. Kinetic rate constants and activation parameters for the IMDA reaction were determined, and the primary adducts were reduced with cuprous ion to give a phenol-derived 4-hydroxycyclohexa-2,5-dienone. No products from adduction of peroxyls at the phenolic ortho position were found in either the primary or cuprous reduction product mixtures. These studies provide a framework for understanding the nature of lipid-protein adducts formed by peroxyl-tyrosyl radical-radical termination processes. Coupling of lipid peroxyl radicals with tyrosyl radicals leads to cyclohexenone and cyclohexadienone adducts, which are of interest in and of themselves since, as electrophiles, they are likely targets for protein nucleophiles. One consequence of lipid peroxyl reactions with tyrosyls may therefore be protein-protein cross-links via interprotein Michael adducts.

Overview of VOC emissions and chemistry from PTR-TOF-MS measurements during the SusKat-ABC campaign: high acetaldehyde, isoprene and isocyanic acid in wintertime air of the Kathmandu Valley

Science.gov (United States)

Sarkar, Chinmoy; Sinha, Vinayak; Kumar, Vinod; Rupakheti, Maheswar; Panday, Arnico; Mahata, Khadak S.; Rupakheti, Dipesh; Kathayat, Bhogendra; Lawrence, Mark G.

2016-03-01

= 60.051), which can photochemically produce isocyanic acid in the atmosphere, are reported in this study along with nitromethane (a tracer for diesel exhaust), which has only recently been detected in ambient studies. Two distinct periods were selected during the campaign for detailed analysis: the first was associated with high wintertime emissions of biogenic isoprene and the second with elevated levels of ambient acetonitrile, benzene and isocyanic acid from biomass burning activities. Emissions from biomass burning and biomass co-fired brick kilns were found to be the dominant sources for compounds such as propyne, propene, benzene and propanenitrile, which correlated strongly with acetonitrile (r2 > 0.7), a chemical tracer for biomass burning. The calculated total VOC OH reactivity was dominated by acetaldehyde (24.0 %), isoprene (20.2 %) and propene (18.7 %), while oxygenated VOCs and isoprene collectively contributed to more than 68 % of the total ozone production potential. Based on known secondary organic aerosol (SOA) yields and measured ambient concentrations in the Kathmandu Valley, the relative SOA production potential of VOCs were benzene > naphthalene > toluene > xylenes > monoterpenes > trimethylbenzenes > styrene > isoprene. The first ambient measurements from any site in South Asia of compounds with significant health effects such as isocyanic acid, formamide, acetamide, naphthalene and nitromethane have been reported in this study. Our results suggest that mitigation of intense wintertime biomass burning activities, in particular point sources such biomass co-fired brick kilns, would be important to reduce the emission and formation of toxic VOCs (such as benzene and isocyanic acid) in the Kathmandu Valley.

DNA-nicotine adduction of lung and liver of mice exposed to passive smoking studied by AMS

International Nuclear Information System (INIS)

Hou Qin; Sun Hongfang; Shi Jingyuan; Liu Yuanfang; Wang Jianjun; Lu Xiangyang; Li Kun; Zhao Qiang

1997-01-01

The author presents the measurement of adduction of mice lung or liver DNA with nicotine by accelerator mass spectrometry (AMS). Mice were exposed in a toxicity infecting chamber filled up with cigarette smoke for a period of time of simulate the exposure of mice to passive smoking. The dose of nicotine inhaled by mice was determined. The results of AMS showed, when the dose of inhaled nicotine ranged from 33 μg/kg to 330 μg/kg, the adducts number of lung DNA was 10 3 -10 4 adducts/10 12 nucleotides, and the adducts increased linearly with increasing dose of nicotine; the adducts number of liver DNA reached to 10 4 -10 5 adducts/10 12 nucleotides, when the dose of nicotine ranged from 99 μg/kg to 330 μg/kg, and the adducts increased vigorously as dose of nicotine increased. Comparing the DNA adducts levels of the same nicotine dose, liver DNA adducts were more than lung DNA adducts. This study also suggested that the other components of cigarette smoke have synergic effect on the formation of nicotine derived DNA adducts

The nature of OH/IR stars

International Nuclear Information System (INIS)

Herman, J.

1983-01-01

In this work masers in evolved stars are studied, in particular the emission from the OH radical. The time variability of the OH masers was measured over a period of five years with the Dwingeloo Radio Telescope. These single-dish observations proved that most of the underlying stars are very long period variables, apparently a kind of extension of the well-known long period Mira variables. The mean OH fluxes and epochs were obtained as well as a confirmation of the radiative coupling between the maser and the star (by comparison with infrared data provided by other observers), the degree of saturation, and, most important of all, a determination of the linear dimensions of the circumstellar shells. Multi-element interferometer observations were made in order to study the spatial structure of OH masers. By combining the phase lag measurements and the spatial extent distances to individual stars could be determined with a high, unprecedented accuracy. Infrared broad-band photometry was done in the wavelength region from 3 μm to 20 μm, where most of the energy of these objects is radiated. The space density and galactic distribution of OH/IR stars are discussed and compared with the appearance of OH masers in the solar neighbourhood. (Auth.)

Chemistry and Chemical Equilibrium Dynamics of BMAA and Its Carbamate Adducts.

Science.gov (United States)

Diaz-Parga, Pedro; Goto, Joy J; Krishnan, V V

2018-01-01

Beta-N-methylamino-L-alanine (BMAA) has been demonstrated to contribute to the onset of the ALS/Parkinsonism-dementia complex (ALS/PDC) and is implicated in the progression of other neurodegenerative diseases. While the role of BMAA in these diseases is still debated, one of the suggested mechanisms involves the activation of excitatory glutamate receptors. In particular, the excitatory effects of BMAA are shown to be dependent on the presence of bicarbonate ions, which in turn forms carbamate adducts in physiological conditions. The formation of carbamate adducts from BMAA and bicarbonate is similar to the formation of carbamate adducts from non-proteinogenic amino acids. Structural, chemical, and biological information related to non-proteinogenic amino acids provide insight into the formation of and possible neurological action of BMAA. This article reviews the carbamate formation of BMAA in the presence of bicarbonate ions, with a particular focus on how the chemical equilibrium of BMAA carbamate adducts may affect the molecular mechanism of its function. Highlights of nuclear magnetic resonance (NMR)-based studies on the equilibrium process between free BMAA and its adducts are presented. The role of divalent metals on the equilibrium process is also explored. The formation and the equilibrium process of carbamate adducts of BMAA may answer questions on their neuroactive potency and provide strong motivation for further investigations into other toxic mechanisms.

Diagnosis and dosimetry of exposure to sulfur mustard: Development of a standard operating procedure for hemoglobin adducts: Exploratory research on albumin and keratin adducts

NARCIS (Netherlands)

Noort, D.; Fidder, A.; Jong, L.P.A. de; Schans, G.P. van der; Benschop, H.P.

2000-01-01

A standard operating procedure (SOP) for determination of the sulfur mustard adduct to the N-terminal valine in hemoglobin was developed. By using this SOP, it was found that the Nterminal valine adduct in globin of hairless guinea pigs and marmosets which had been exposed to sulfur mustard (0.5

Reaction mechanisms of phosphate with Al(OH)3 and a sandy soil

NARCIS (Netherlands)

Riemsdijk, van W.H.

1979-01-01

Al(OH) ₃ is a very effective sorbent for orthophosphate especially at low pH. At low phosphate concentration c _p , phosphate is adsorbed by an exchange mechanism with singly coordinated OH(H) groups residing on the surface of the Al(OH)

Formation of cyclic 1,N2-propanodeoxyguanosine and thymidine adducts in the reaction of the mutagen 2-bromoacrolein with calf thymus DNA

International Nuclear Information System (INIS)

Meerman, J.H.; Smith, T.R.; Pearson, P.G.; Meier, G.P.; Nelson, S.D.

1989-01-01

The interaction of the mutagen 2-bromoacrolein (2BA) with DNA and thymidine was studied in vitro by reaction of [3-3H]2BA with thymidine, RNA, single-stranded DNA, and double-stranded DNA in phosphate buffer (pH 7.4). After purification of the nucleic acids, they were incubated at alkaline pH to convert any (hydroxybromo)propano(deoxy)-guanosine adducts to their dihydroxy analogues. After acid or enzymatic hydrolysis, the hydrolysates were analyzed by reversed-phase high-performance liquid chromatography. At a concentration of 1.6 mM, the fraction of 2BA that became covalently bound to DNA was 2.3% of the amount added. Only 3% of the radioactivity bound to DNA after extensive purification could be accounted for as cyclic 1,N2-(6,7-dihydroxy)-propanoguanine adducts. More 2BA became covalently bound to single-stranded DNA and RNA as compared with double-stranded DNA. However, high-performance liquid chromatographic analyses showed that formation of cyclic 1,N2-(6,7-dihydroxy)propanoguanine adducts was also a minor reaction with these macromolecules. Because these data showed that other type(s) of reaction(s) are more important in the reaction of 2BA with nucleic acids, we have investigated the reaction of 2BA with other nucleosides. It was found that 2BA reacted well with thymidine in vitro, and the major product was identified by 500 MHz 1H and 75.43 MHz 13C nuclear magnetic resonance and thermospray mass spectrometry as 3-(2-bromo-3-oxopropyl)thymidine. This adduct was unstable and decomposed upon storage. After enzymatic hydrolysis of [3H]2BA-modified double-stranded DNA and subsequent analysis of the hydrolysate by high-performance liquid chromatography, 22% of the covalently bound radioactivity to DNA coeluted with decomposition products of the 3-(bromooxypropyl)thymidine adduct

Potential sensitivity of photosynthesis and isoprene emission to direct radiative effects of atmospheric aerosol pollution

Directory of Open Access Journals (Sweden)

S. Strada

2016-04-01

Full Text Available A global Earth system model is applied to quantify the impacts of direct anthropogenic aerosol effective radiative forcing on gross primary productivity (GPP and isoprene emission. The impacts of different pollution aerosol sources (anthropogenic, biomass burning, and non-biomass burning are investigated by performing sensitivity experiments. The model framework includes all known light and meteorological responses of photosynthesis, but uses fixed canopy structures and phenology. On a global scale, our results show that global land carbon fluxes (GPP and isoprene emission are not sensitive to pollution aerosols, even under a global decline in surface solar radiation (direct + diffuse by  ∼ 9 %. At a regional scale, GPP and isoprene emission show a robust but opposite sensitivity to pollution aerosols in regions where forested canopies dominate. In eastern North America and Eurasia, anthropogenic pollution aerosols (mainly from non-biomass burning sources enhance GPP by +5–8 % on an annual average. In the northwestern Amazon Basin and central Africa, biomass burning aerosols increase GPP by +2–5 % on an annual average, with a peak in the northwestern Amazon Basin during the dry-fire season (+5–8 %. The prevailing mechanism varies across regions: light scattering dominates in eastern North America, while a reduction in direct radiation dominates in Europe and China. Aerosol-induced GPP productivity increases in the Amazon and central Africa include an additional positive feedback from reduced canopy temperatures in response to increases in canopy conductance. In Eurasia and northeastern China, anthropogenic pollution aerosols drive a decrease in isoprene emission of −2 to −12 % on an annual average. Future research needs to incorporate the indirect effects of aerosols and possible feedbacks from dynamic carbon allocation and phenology.

Structure of 7,12-dimethylbenz(a)anthracene-guanosine adducts.

Science.gov (United States)

Jeffrey, A M; Blobstein, S H; Weinstein, I B; Beland, F A; Harvey, R G; Kasai, H; Nakanishi, K

1976-01-01

Arene oxides have been proposed as the reactive intermediates in the process of carcinogenesis induced by polycyclic aromatic hydrocarbons. The present study defines the structures of four guanosine adducts formed by the reaction of 7,12-dimethylbenz[a]anthracene-5,6-oxide with polyguanylic acid. The modified polymer was hydrolyzed to nucleotides and the hydrophobic guanosine adducts separated from unmodified guanosine by LH-20 column chromatograhy. The adducts were further resolved into four components (I-IV) by reverse phase high pressure liquid chromatography. Analysis of the ultraviolet, circular dichroism, mass, and proton magnetic resonance spectra of these compounds, or their acetate and free base derivatives, indicates that in all four compounds the aromatic hydrocarbon is present on the 2 amino group of guanine. Compounds I and IV, and II and III constitute diastereoisomeric pairs, respectively. In the I and IV pair, the adducts result from addition at the 6 position of the original dimethylbenz[a]anthracene oxide, whereas in the II and III pair, the addition occurs at the 5 position. Indirect evidence suggests that trans opening of the oxide occurred in all cases but this remains to be established. PMID:821053

Structure of 7,12-dimethylbenz(a)anthracene-guanosine adducts.

Science.gov (United States)

Jeffrey, A M; Blobstein, S H; Weinstein, I B; Beland, F A; Harvey, R G; Kasai, H; Nakanishi, K

1976-07-01

Arene oxides have been proposed as the reactive intermediates in the process of carcinogenesis induced by polycyclic aromatic hydrocarbons. The present study defines the structures of four guanosine adducts formed by the reaction of 7,12-dimethylbenz[a]anthracene-5,6-oxide with polyguanylic acid. The modified polymer was hydrolyzed to nucleotides and the hydrophobic guanosine adducts separated from unmodified guanosine by LH-20 column chromatograhy. The adducts were further resolved into four components (I-IV) by reverse phase high pressure liquid chromatography. Analysis of the ultraviolet, circular dichroism, mass, and proton magnetic resonance spectra of these compounds, or their acetate and free base derivatives, indicates that in all four compounds the aromatic hydrocarbon is present on the 2 amino group of guanine. Compounds I and IV, and II and III constitute diastereoisomeric pairs, respectively. In the I and IV pair, the adducts result from addition at the 6 position of the original dimethylbenz[a]anthracene oxide, whereas in the II and III pair, the addition occurs at the 5 position. Indirect evidence suggests that trans opening of the oxide occurred in all cases but this remains to be established.

A biomarker model of sublethal genotoxicity (DNA single-strand breaks and adducts) using the sentinel organism Aporrectodea longa in spiked soil

International Nuclear Information System (INIS)

Martin, Francis L.; Piearce, Trevor G.; Hewer, Alan; Phillips, David H.; Semple, Kirk T.

2005-01-01

There is a need to develop risk biomarkers during the remediation of contaminated land. We employed the earthworm, Aporrectodea longa (Ude), to determine whether genotoxicity measures could be applied to this organism's intestinal tissues. Earthworms were added, for 24 h or 7 days, to soil samples spiked with benzo[a]pyrene (B[a]P) and/or lindane. After exposure, intestinal tissues (crop/gizzard or intestine) were removed prior to the measurement in disaggregated cells of DNA single-strand breaks (SSBs) by the alkaline comet assay. Damage was quantified by comet tail length (CTL, μm). B[a]P 24-h exposure induced dose-related increases (P 32 P-postlabelling, showed a two-adduct-spot pattern. This preliminary investigation suggests that earthworm tissues may be incorporated into genotoxicity assays to facilitate hazard identification within terrestrial ecosystems. - Sublethal genotoxicity in the sentinel organism A. longa can be used to monitor the effects of contaminants in soil

Microdose-Induced Drug-DNA Adducts as Biomarkers of Chemotherapy Resistance in Humans and Mice.

Science.gov (United States)

Zimmermann, Maike; Wang, Si-Si; Zhang, Hongyong; Lin, Tzu-Yin; Malfatti, Michael; Haack, Kurt; Ognibene, Ted; Yang, Hongyuan; Airhart, Susan; Turteltaub, Kenneth W; Cimino, George D; Tepper, Clifford G; Drakaki, Alexandra; Chamie, Karim; de Vere White, Ralph; Pan, Chong-Xian; Henderson, Paul T

2017-02-01

We report progress on predicting tumor response to platinum-based chemotherapy with a novel mass spectrometry approach. Fourteen bladder cancer patients were administered one diagnostic microdose each of [ 14 C]carboplatin (1% of the therapeutic dose). Carboplatin-DNA adducts were quantified by accelerator mass spectrometry in blood and tumor samples collected within 24 hours, and compared with subsequent chemotherapy response. Patients with the highest adduct levels were responders, but not all responders had high adduct levels. Four patient-derived bladder cancer xenograft mouse models were used to test the possibility that another drug in the regimen could cause a response. The mice were dosed with [ 14 C]carboplatin or [ 14 C]gemcitabine and the resulting drug-DNA adduct levels were compared with tumor response to chemotherapy. At least one of the drugs had to induce high drug-DNA adduct levels or create a synergistic increase in overall adducts to prompt a corresponding therapeutic response, demonstrating proof-of-principle for drug-DNA adducts as predictive biomarkers. Mol Cancer Ther; 16(2); 376-87. ©2016 AACR. ©2016 American Association for Cancer Research.

40 CFR 721.3680 - Ethylene oxide adduct of fatty acid ester with pentaerythritol.

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Ethylene oxide adduct of fatty acid... New Uses for Specific Chemical Substances § 721.3680 Ethylene oxide adduct of fatty acid ester with... identified generically as ethylene oxide adduct of fatty acid ester with pentaerythritol (PMN P-91-442) is...

Aqueous-phase mechanism for secondary organic aerosol formation from isoprene: application to the southeast United States and co-benefit of SO2 emission controls

Science.gov (United States)

Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA), but the mechanism and yields are uncertain. Aerosol is prevailingly aqueous under the humid conditions typical of isoprene-emitting regions. Here we develop an aqueous-phase mechanism for...

/sup 32/P-postlabelling analysis of aromatic DNA adducts in human oral mucosal cells

Energy Technology Data Exchange (ETDEWEB)

Dunn, B.P.; Stich, H.F.

1986-07-01

Exfoliated mucosal cells were collected from the oral cavity of three groups at high risk for oral cancer: Indian betel nut chewers, Filipino inverted smokers (burning end of cigar in mouth) and Indian Khaini tobacco chewers. DNA was extracted from these samples, as well as from samples of exfoliated cells of Canadian non-smoking controls. DNA was analyzed for the presence of aromatic DNA adducts using /sup 32/P-postlabelling analysis. Five chromatographically distinct adducts were found in samples from both the high risk groups and the nonsmoking controls. Individual adducts were detectable in approximately 30-95% of samples, depending on the adduct and population group. Estimated levels of specific adducts ranged from non-detectable (prevalence relative to normal nucleotides less than 1 X 10(-9)) to occasionally greater than 1 X 10(-7). No adducts were found in high risk groups which did not also appear in control subjects.

A fluorescent-based HPLC assay for quantification of cysteine and cysteamine adducts in Escherichia coli-derived proteins.

Science.gov (United States)

Soriano, Brian D; Tam, Lei-Ting T; Lu, Hsieng S; Valladares, Violeta G

2012-01-01

Recombinant proteins expressed in Escherichia coli are often produced as unfolded, inactive forms accumulated in inclusion bodies. Redox-coupled thiols are typically employed in the refolding process in order to catalyze the formation of correct disulfide bonds at maximal folding efficiency. These thiols and the recombinant proteins can form mixed disulfide bonds to generate thiol-protein adducts. In this work, we apply a fluorescent-based assay for the quantification of cysteine and cysteamine adducts as observed in E. coli-derived proteins. The thiols are released by reduction of the adducted protein, collected and labeled with a fluorescent reagent, 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate. The derivatized thiols are separated by reversed-phase HPLC and can be accurately quantified after method optimization. The estimated thiol content represents total amount of adducted forms present in the analyzed samples. The limit of quantification (LOQ) was established; specifically, the lowest amount of quantifiable cysteine adduction is 30 picograms and the lowest amount of quantifiable cysteamine adduction is 60 picograms. The assay is useful for quantification of adducts in final purified products as well as in-process samples from various purification steps. The assay indicates that the purification process accomplishes a decrease in cysteine adduction from 0.19 nmol adduct/nmol protein to 0.03 nmol adduct/nmol protein as well as a decrease in cysteamine adduction from 0.24 nmol adduct/nmol protein to 0.14 nmol adduct/nmol protein. Copyright © 2011. Published by Elsevier B.V.

Adduct formation in Ce(IV) thenolytrifluoroacetonate

International Nuclear Information System (INIS)

Anufrieva, S.I.; Polyakova, G.V.; Snezhko, N.I.; Pechurova, N.I.; Martynenko, L.I.; Spitsyn, V.I.

1982-01-01

The literature contains no information on adduct formation in Ce(IV) β-diketonates with additional ligands. Since tetrakis-β-diketonates of Ce(IV) have four six-membered chelate rings, we can suppose that the introduction of an additional monodentate or bidentate ligand into the coordination sphere of Ce(IV) β-diketonates would lead to an increase in the coordination number (CN) of the Ce(IV) to nine or ten. The possibility of realization of such a high CN for Ce(IV) has not been proved; a study of adduct formation by Ce(IV) tetrakis-β-diketonates is thus of theoretical interest. Such an investigation might also be of practical interest, because the introduction of an additional ligand into the coordination sphere of a rare-earth β-diketonate usually increases the solubility of the β-diketonate in nonpolar solvents and increases the volatility of the compound; such a modification of the properties is important for various practical purposes. The aim of our work was to study the possibility of separating solid adducts of Ce(IV) tetrakis-thenoyltrifluoroacetonate with certain oxygen-containing and nitrogen-containing donor monodentate and bidentate ligands, and also to investigate their properties. As the β-diketone we used thenoyltrifluoroacetone (HTTFA), since in a parallel investigation it was found that Ce(TTFA) 4 has a high oxidation-reduction stability

Detection of Dichlorvos Adducts in a Hepatocyte Cell Line

Science.gov (United States)

2014-06-30

5453543 aldo -keto reductase family 1 member C1 aldo -keto reductase TRUE 3 156523970 alpha-2-HS-glycoprotein preproprotein 5 4503571 alpha-enolase...enolase, (YISPDQLADLYK), three variants were identified with adducts on the first, second, or both tyrosines (Figure 2), and for one peptide in aldo -keto...suggesting the possibility that DDVP adducts could alter biological activities. The modifications of aldo -keto reductase family 1 members at three

Zinc acetylacetonate hydrate adducted with nitrogen donor ligands: Synthesis, spectroscopic characterization, and thermal analysis

Science.gov (United States)

Brahma, Sanjaya; Shivashankar, S. A.

2015-12-01

We report synthesis, spectroscopic characterization, and thermal analysis of zinc acetylacetonate complex adducted by nitrogen donor ligands, such as pyridine, bipyridine, and phenanthroline. The pyridine adducted complex crystallizes to monoclinic crystal structure, whereas other two adducted complexes have orthorhombic structure. Addition of nitrogen donor ligands enhances the thermal property of these complexes as that with parent metal-organic complex. Zinc acetylacetonate adducted with pyridine shows much higher volatility (106 °C), decomposition temperature (202 °C) as that with zinc acetylacetonate (136 °C, 220 °C), and other adducted complexes. All the adducted complexes are thermally stable, highly volatile and are considered to be suitable precursors for metal organic chemical vapor deposition. The formation of these complexes is confirmed by powder X-ray diffraction, Fourier transform infrared spectroscopy, mass spectroscopy, and elemental analysis. The complexes are widely used as starting precursor materials for the synthesis of ZnO nanostructures by microwave irradiation assisted coating process.

Topotactic transition of α-Co(OH)2 to β-Co(OH)2 anchored on CoO nanoparticles during electrochemical water oxidation: synergistic electrocatalytic effects.

Science.gov (United States)

Kundu, Sumana; Malik, Bibhudatta; Prabhakaran, Amrutha; Pattanayak, Deepak K; Pillai, Vijayamohanan K

2017-08-29

Herein, we report a single step, anionic surfactant-assisted, low temperature-hydrothermal synthetic strategy of CoO nanoparticles anchored on β-Co(OH) 2 nanosheets which show a low overpotential (295 mV @ 10 mA cm -2 ) for the oxygen evolution reaction (OER). They also demonstrate much better kinetic parameters compared to the state-of-the-art RuO 2 . Interestingly, under the OER operational conditions (in alkaline medium), the topotactic transformation of α-Co(OH) 2 to a stable Brucite-like β-Co(OH) 2 phase leads to a synergistic interaction between the β-Co(OH) 2 sheets on the CoO nanoparticles for enhancing the OER electrocatalytic activity.

Inhibition of nicotine-DNA adduct formation by polyphenolic compounds in vitro

International Nuclear Information System (INIS)

Cheng Yan; Wang Haifang; Sun Hongfang; Li Hongli

2004-01-01

Nicotine[3-(1-methyl-2-pyrrolidinyl)-pyridine], a major alkaloid in tobacco products, has proven to be a potential genotoxic compound. Some polyphenolic compounds can suppress the DNA adduction, and hence act as the potential inhibitors of carcinogenesis. In this study, the inhibitory effects of three polyphenolic compounds, curcumin (diferuloylmethane), resveratrol (trans-3, 5, 4-trihydroxystilbene) and tea polyphenols, on the nicotine-DNA adduction have been investigated in vitro using radiolabelled nicotine and liquid scintillation counting (LSC) technique. Also, the inhibition mechanism of these chemopreventive agents in regard to the activity of the biotransformation enzymes, including cytochrome P450 (CYP450), cytochrome b 5 (CYb 5 ) and glutathione S-transferase (GST), has been studied. The results demonstrated that these three polyphenols induced marked dose-dependent decrease in nicotine-DNA adducts as compared with the controls. The elimination rate of adducts reached above 46% at the highest dose for all the three agents with 51.6% for resveratrol. Correspondingly, three polyphenols all suppressed CYP450 and CYb 5 , whereas curcumin and resveratrol induced GST. The authors may arrive at a point that the three polyphenols are beneficial to prevent the nicotine adduct formation, and thus may be used to block the potential carcinogenesis induced by nicotine. (authors)

Comparison of estimated dietary intake of acrylamide with hemoglobin adducts of acrylamide and glycidamide

DEFF Research Database (Denmark)

Bjellaas, Thomas; Olesen, Pelle Thonning; Frandsen, Henrik Lauritz

2007-01-01

, a significant positive correlation was found between the AA-Hb adduct concentration and the intake of chips/snacks and crisp bread. GA-Hb adduct did not correlate with consumption of any of the main food groups. Neither AA-Hb nor GA-Hb adduct concentration correlated with total dietary intake of AA...

Exposure of bus and taxi drivers to urban air pollutants as measured by DNA and protein adducts

DEFF Research Database (Denmark)

Hemminki, K.; Zhang, L.F.; Krüger, J.

1994-01-01

Urinary 1-hydroxypyrene, lymphocyte DNA adducts, serum protein-bound PAH and hemoglobin-bound alkene adducts were analysed from 4 groups of non-smoking men: urban and suburban bus drivers, taxi drivers and suburban controls. The only differences between the groups were in DNA adducts between...... suburban bus drivers and controls, and in DNA adduct and plasma protein PAH-adducts between taxi drivers and controls....

Knee adduction moment and medial contact force--facts about their correlation during gait.

Directory of Open Access Journals (Sweden)

Ines Kutzner

Full Text Available The external knee adduction moment is considered a surrogate measure for the medial tibiofemoral contact force and is commonly used to quantify the load reducing effect of orthopedic interventions. However, only limited and controversial data exist about the correlation between adduction moment and medial force. The objective of this study was to examine whether the adduction moment is indeed a strong predictor for the medial force by determining their correlation during gait. Instrumented knee implants with telemetric data transmission were used to measure tibiofemoral contact forces in nine subjects. Gait analyses were performed simultaneously to the joint load measurements. Skeletal kinematics, as well as the ground reaction forces and inertial parameters, were used as inputs in an inverse dynamics approach to calculate the external knee adduction moment. Linear regression analysis was used to analyze the correlation between adduction moment and medial force for the whole stance phase and separately for the early and late stance phase. Whereas only moderate correlations between adduction moment and medial force were observed throughout the whole stance phase (R(2 = 0.56 and during the late stance phase (R(2 = 0.51, a high correlation was observed at the early stance phase (R(2 = 0.76. Furthermore, the adduction moment was highly correlated to the medial force ratio throughout the whole stance phase (R(2 = 0.75. These results suggest that the adduction moment is a surrogate measure, well-suited to predicting the medial force ratio throughout the whole stance phase or medial force during the early stance phase. However, particularly during the late stance phase, moderate correlations and high inter-individual variations revealed that the predictive value of the adduction moment is limited. Further analyses are necessary to examine whether a combination of other kinematic, kinetic or neuromuscular factors may lead to a more

Temporal and spatial features of the formation of DNA adducts in sulfur mustard-exposed skin

Energy Technology Data Exchange (ETDEWEB)

Batal, Mohamed [Laboratoire «Lésions des Acides Nucléiques», Université Joseph Fourier – Grenoble 1, CEA/Institut Nanoscience et Cryogénie/SCIB, UMR-E3, Grenoble (France); Département de Toxicologie et Risques Chimiques, Unité de Brûlure Chimique, Institut de Recherche Biomédicale des Armées, Antenne de La Tronche (France); Boudry, Isabelle; Mouret, Stéphane; Wartelle, Julien; Emorine, Sandy; Bertoni, Marine [Département de Toxicologie et Risques Chimiques, Unité de Brûlure Chimique, Institut de Recherche Biomédicale des Armées, Antenne de La Tronche (France); Bérard, Izabel [Laboratoire «Lésions des Acides Nucléiques», Université Joseph Fourier – Grenoble 1, CEA/Institut Nanoscience et Cryogénie/SCIB, UMR-E3, Grenoble (France); Cléry-Barraud, Cécile [Département de Toxicologie et Risques Chimiques, Unité de Brûlure Chimique, Institut de Recherche Biomédicale des Armées, Antenne de La Tronche (France); and others

2013-12-15

Sulfur mustard (SM) is a chemical warfare agent that targets skin where it induces large blisters. DNA alkylation is a critical step to explain SM-induced cutaneous symptoms. We determined the kinetics of formation of main SM–DNA adducts and compare it with the development of the SM-induced pathogenesis in skin. SKH-1 mice were exposed to 2, 6 and 60 mg/kg of SM and treated skin was biopsied between 6 h and 21 days. Formation of SM DNA adducts was dose-dependent with a maximum immediately after exposure. However, adducts were persistent and still detectable 21 days post-exposure. The time-dependent formation of DNA adducts was also found to be correlated with the appearance of apoptotic cells. This temporal correlation suggests that these two early events are responsible for the severity of the damage to the skin. Besides, SM–DNA adducts were also detected in areas located next to contaminated zone, thus suggesting that SM diffuses in skin. Altogether, this work provides for the first time a clear picture of SM-induced genotoxicity using DNA adducts as a marker. - Highlights: • Sulfur mustard adducts are formed in DNA after skin exposure. • DNA damage formation is an early event in the pathological process of skin burn. • The amount of SM–DNA adducts is maximal at the earliest time point investigated. • Adducts are still detected 3 weeks after exposure. • Sulfur mustard diffuses in skin especially when large doses are applied.

MERLIN observations of the OH/IR stars OH 53.6-0.2, OH 138.0+7.2 and OH 141.7+3.5

International Nuclear Information System (INIS)

Chapman, J.; Cohen, R.J.; Norris, R.P.; Diamond, P.J.; Booth, R.S.

1984-01-01

OH maser emission from the three OH/IR stars OH 53.6-0.2, OH 138.0+7.2 and OH 141.7+3.5 has been mapped with an angular resolution of 0.28 arcsec and a velocity resolution of 0.7 km s -1 using the Jodrell Bank MERLIN array. Maps are presented of the 1612-MHz OH emission over individual velocity ranges. The maps are consistent with a uniform expanding shell model, and by fitting such models to the data the angular diameters of the shells have been estimated to an accuracy of approx. 25 per cent. (author)

Polycyclic Aromatic Hydrocarbon (PAH Exposure and DNA Adduct Semi-Quantitation in Archived Human Tissues

Directory of Open Access Journals (Sweden)

M. Margaret Pratt

2011-06-01

Full Text Available Polycyclic aromatic hydrocarbons (PAHs are combustion products of organic materials, mixtures of which contain multiple known and probable human carcinogens. PAHs occur in indoor and outdoor air, as well as in char-broiled meats and fish. Human exposure to PAHs occurs by inhalation, ingestion and topical absorption, and subsequently formed metabolites are either rendered hydrophilic and excreted, or bioactivated and bound to cellular macromolecules. The formation of PAH-DNA adducts (DNA binding products, considered a necessary step in PAH-initiated carcinogenesis, has been widely studied in experimental models and has been documented in human tissues. This review describes immunohistochemistry (IHC studies, which reveal localization of PAH-DNA adducts in human tissues, and semi-quantify PAH-DNA adduct levels using the Automated Cellular Imaging System (ACIS. These studies have shown that PAH-DNA adducts concentrate in: basal and supra-basal epithelium of the esophagus, cervix and vulva; glandular epithelium of the prostate; and cytotrophoblast cells and syncitiotrophoblast knots of the placenta. The IHC photomicrographs reveal the ubiquitous nature of PAH-DNA adduct formation in human tissues as well as PAH-DNA adduct accumulation in specific, vulnerable, cell types. This semi-quantative method for PAH-DNA adduct measurement could potentially see widespread use in molecular epidemiology studies.

Aminoazo dye-protein-adduct enhances inhibitory effect on digestibility and damages to Gastro-Duodenal-Hepatic axis.

Directory of Open Access Journals (Sweden)

Li-Yun Lin

Full Text Available 4-Dimethylaminoazobenzene (DAB, methyl yellow, or butter yellow, a human carcinogen, has been banned for use in foods since 1988. In 2014, DAB adulteration in Tofu occurred in Taiwan. We hypothesize that DAB can form [DAB•SBP]adduct adduct with soybean protein (SBP which could damage Gastro-Duodenal-Hepatic axis. Sprague-Dawley rats gavage fed [DAB•SBP]adduct adduct revealed severely reduced body weight and damaged duodenum, liver, hepatic mitochondria, and spleen. Hepatic levels of glutathione and ATP were severely reduced. Serum GOT and GPT were substantially elevated. Analysis by the adsorption isotherm clearly revealed DAB formed very stable [DAB•SBP]adduct adduct at 1:1 molar ration (Phase A. The equilibrium constant of this colloidal adduct [DAB•SBP]adduct was KeqA = ∝, behaving as the most stable and toxic species. At higher protein concentration (Phase C it formed conjugate [DAB×SBPgross]conjugate, with KeqC = 3.23×10-2 mg/mL, implicating a moderately strong adsorption. The in vitro pepsin digestibility test showed apparently reduced digestibility by 27% (by Ninhydrin assay or 8% (by Bradford assay. Conclusively, this is the first report indicating that [DAB•SBP]adduct potentially is capable to damage the Gastro-Duodenal-Hepatic axis.

Hemoglobin adducts in workers exposed to 1,6-hexamethylene diisocyanate.

Science.gov (United States)

Flack, Sheila L; Fent, Kenneth W; Gaines, Linda G T; Thomasen, Jennifer M; Whittaker, Stephen G; Ball, Louise M; Nylander-French, Leena A

2011-05-01

We investigated the utility of 1,6-hexamethylene diamine (HDA) hemoglobin adducts as biomarkers of exposure to 1,6-hexamethylene diisocyanate (HDI) monomer. Blood samples from 15 spray painters applying HDI-containing paint were analyzed for hemoglobin HDA (HDA-Hb) and N-acetyl-1,6-hexamethylene diamine (monoacetyl-HDA-Hb) by GC-MS. HDA-Hb was detected in the majority of workers (≤1.2-37 ng/g Hb), whereas monoacetyl-HDA-Hb was detected in one worker (0.06 ng/g Hb). The stronger, positive association between HDA-Hb and cumulative HDI exposure (r(2) = 0.3, p HDA-Hb adducts. This association demonstrates the suitability of HDA-Hb adducts for further validation as a biomarker of HDI exposure.

Isomerization of Second-Generation Isoprene Peroxy Radicals: Epoxide Formation and Implications for Secondary Organic Aerosol Yields

Energy Technology Data Exchange (ETDEWEB)

D’Ambro, Emma L.; Møller, Kristian H.; Lopez-Hilfiker, Felipe D.; Schobesberger, Siegfried; Liu, Jiumeng; Shilling, John E.; Lee, Ben Hwan; Kjaergaard, Henrik G.; Thornton, Joel A.

2017-04-11

We report chamber measurements of secondary organic aerosol (SOA) formation from isoprene photochemical oxidation, where radical concentrations were systematically varied and the molecular composition of semi to low volatility gases and SOA were measured online. Using a detailed chemical mechanism, we find that to explain the behavior of low volatility products and SOA mass yields relative to input H2O2 concentrations, the second generation dihydroxy hydroperoxy peroxy radical (C5H11O6•) must undergo an intra-molecular H-shift with a net forward rate constant of order 0.1 s-1 or higher, consistent with quantum chemical calculations which suggest a net forward rate constant of 0.3-0.9 s-1. Furthermore, these calculations suggest the dominant product of this isomerization is a dihydroxy hydroperoxy epoxide (C5H10O5) which is expected to have a saturation vapor pressure ~2 orders of magnitude higher than the dihydroxy dihydroperoxide, ISOP(OOH)2 (C5H12O6), a major product of the peroxy radical reacting with HO2. These results provide strong constraints on the likely volatility distribution of isoprene oxidation products under atmospheric conditions and thus on the importance of non-reactive gas-particle partitioning of isoprene oxidation products as an SOA source.

DNA adduct formation among workers in a Thai industrial estate and nearby residents.

Science.gov (United States)

Peluso, Marco; Srivatanakul, Petcharin; Munnia, Armelle; Jedpiyawongse, Adisorn; Meunier, Aurelie; Sangrajrang, Suleeporn; Piro, Sara; Ceppi, Marcello; Boffetta, Paolo

2008-01-25

The genotoxic effects of air pollutant exposures have been studied in people living and working in Map Ta Phut, Rayong province, Thailand, a site where is located the Map Ta Phut Industrial Estate (MIE) one of the largest steel, refinery and petrochemical complex in the South-Eastern Asia. This was done by the conduction of a transversal study aimed to compare the prevalence of bulky DNA adducts in groups of subjects experiencing various degree of air pollution. DNA adduct analysis was performed in the leukocytes of 201 volunteers by the (32)P-postlabelling assay: 79 were workers in the MIE complex, including 24 refinery workers, 40 steel workers and 15 tinplate workers, 72 were people residing downwind in the MIE area and 50 were residents in a control district of the same Rayong province but without industrial exposures. The groups of workers were analyzed separately to evaluate if DNA adduct formation differs by the type of industry. The levels of bulky DNA adducts were 1.17+/-0.17 (SE) adducts/10(8) nucleotides in refinery workers, 1.19+/-0.19 (SE) in steel workers, 0.87+/-0.17 (SE) in tinplate workers, 0.85+/-0.07 (SE) in MIE residents and 0.53+/-0.05 (SE) in district controls. No effects of smoking habits on DNA adducts was found. The multivariate regression analysis shows that the levels of DNA adducts were significantly increased among the individuals living near the MIE industrial complex in respect to those resident in a control district (pindustrial air pollution can experiment an excess of DNA adduct formation. The emissions from the MIE complex are the main source of air pollution in this area and can be the cause of such increment in the levels of DNA damage.

Smog chamber study on aging of combustion soot in isoprene/SO2/NOx system: Changes of mass, size, effective density, morphology and mixing state

Science.gov (United States)

Li, Kangwei; Chen, Linghong; Han, Ke; Lv, Biao; Bao, Kaiji; Wu, Xuecheng; Gao, Xiang; Cen, Kefa

2017-02-01

Atmospheric soot aging process is always accompanied by secondary particle formation, which is a comprehensive environmental issue that deserves great attention. On one hand, aging of primary soot could change its own physicochemical properties; on the other hand, complex air pollution caused by pollutant emission from various sources (e.g., vehicle exhausts, coal-fired flue gases and biogenic VOCs emission) may contribute to secondary particle formation onto primary particle surface. In this study, aging of combustion soot in isoprene/SO2/NOx system was investigated under controlled laboratory conditions in several smog chamber experiments. During the evolution of soot, several physical properties such as mass, size, effective density, morphology and mixing state were determined simultaneously by an integrated aerosol analytical system of Scanning Mobility Particle Sizer (SMPS), Differential Mobility Analyzer-Aerosol Particle Mass Analyzer-Condensation Particle Counter (DMA-APM-CPC) and Transmission Electron Microscopy coupled with Energy-dispersive X-ray Spectrometry (TEM/EDX) techniques. Here, based on the experimental results of soot aging under different gas-phase composition and relative humidity (RH), we firstly proposed possible aging pathways of soot in isoprene/SO2/NOx system. A synergetic effect was speculated to exist between SO2 and isoprene on soot aging process, which led to more secondary particle formation. At the same time, TEM/EDX analysis showed that a competitive mechanism between H2SO4(g) and isoprene oxidation vapor may exist: H2SO4(g) firstly condensed onto fresh soot, then an acceleration of isoprene oxidation products formed onto H2SO4 pre-coated soot. In isoprene/SO2/NOx system, high RH conditions could contribute to soot aging and new particle formation. The changes of effective density and dynamic shape factor of soot also indicated that high RH conditions could accelerate soot aging process, and led chain-like soot into more spherical

Differential cardiac effects in rats exposed to atmospheric smog generated from isoprene versus toluene

Science.gov (United States)

The results of this study demonstrate that atmospheric smog generated from both isoprene and toluene cause cardiac effects in rats. In addition, it appears that smog from toluene is more toxic in terms of cardiac arrhythmogenicity. Smog, which is a comple...

Low-dose DNA adduct dosimetry by accelerator mass spectrometry (AMS)

International Nuclear Information System (INIS)

Turteltaub, K.W.; Felton, J.S.; Vogel, J.S.; Gledhill, B.L.; Davis, J.C.; Snyderwine, E.G.; Thorgeirsson, S.S.; Adamson, R.H.

1991-01-01

DNA adduction was measured following exposure to low doses of [2- 14 C]-2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx) [2- 14 C]-2-amino-3-methylimidazo[4,5-f]quinoline (IQ) and [U- 14 C]-2,3,7,8-tetrachlorodibenzo-p-dioxin by AMS, a technique used in the earth sciences but not previously in toxicological research. The ability to measure low concentrations of rare isotopes suggested that biomedical research was a potentially powerful application for this technology. Sensitivity of the method was found to be one adduct per 10 11 nucleotides. No DNA adduct formation could be detected in TCDD treated rodents. DNA adducts in cynomolgus monkey lymphocytes following exposure to 500 μg/kg IQ peaked between 6 and 18 hrs following exposure. Sensitivity was limited mainly by the abundance of 14 C in contemporary carbon. Hosts depleted in radiocarbon are being developed, potentially increasing sensitivity another 3 orders of magnitude. These results demonstrate the high sensitivity of AMS for tracing molecules following administration of low levels of isotopically-labeled xenobiotics. In addition to 14 C measurement, AMS offers potential to conduct studies with other isotopes, particularly 3 H and 41 Ca

DNA-adducts in fish exposed to alkylating carcinogens

International Nuclear Information System (INIS)

Giam, C.S.; Holliday, T.L.; Williams, J.L.; Bahnson, A.; Weller, R.; Hinton, D.E.

1988-01-01

There are limited studies on DNA-adduct formation following exposure of fish or fish cells to carcinogens. It will be essential to determine if procarcinogens and carcinogens form the same DNA-adducts in different liver cells and how these compare to those reported in mammalian livers. They are also interested in the influence of different alkylating agents on the type and quantity of DNA-adduct formation and repair in fish. While eggs or small fish are ideal for routine screening, large fish such as trout (Salmo gairdneri) is needed initially for the development of analytical procedures for the isolation, quantitation and identification of various adducts. Trout (Salmo gairdneri) weighing approximately 250 grams were acclimatized at 13 degree C before being given i.p. injection of diethylnitrosoamine (DEN). The exposure period varied, though most animals were sacrificed after 24 hours. Their livers were excised and DNA was isolated mainly according the procedure of Croy et al. The neutral thermal hydrolysate and the acid hydrolysate were analyzed by HPLC-Fluorescent detector for 7-ethylguanine and O 6 -ethylguanine, respectively. O 6 -ethylguanine was detected, 7-ethylguanine was not detected. Attempts are being made to improve the detection of the latter compound. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) was used to establish nanogram quantities of the ethylated bases. Laser desorption FT-IC-MS is particularly useful for characterizing thermally-labile and involatile nucleosides or nucleotides. Excretion of DEN was rapid and high. Exposure of trout (and other fish) to various ethylating agents will be discussed

Revisiting the stability of endo/exo Diels-Alder adducts between cyclopentadiene and 1,4-benzoquinone

International Nuclear Information System (INIS)

Tormena, Claudio F.; Lacerda Junior, Valdemar; Oliveira, Kleber T. de

2010-01-01

In this work it is presented a detailed theoretical analysis of the relative stability of endo/exo Diels-Alder adducts formed by the reaction between cyclopentadiene (1) and 1,4-benzoquinone (2). The intrinsic reaction coordinate (IRC) showed the existence of only one transition state for the reaction studied, for both endo 3 and exo 4 adducts. The energies of both adducts were obtained at high level of theory (CBS-Q) confirming that the endo adduct is more stable than exo, which is in the opposite way to the observed in reactions that usually follow Alder's rule. An electronic structure analysis was performed through NBO methodology, indicating that the attractive delocalization interaction predominates over the steric repulsive interaction in the endo adducts. In summary, for the studied cycloaddition reaction the endo adduct is the thermodynamic and kinetic product, which can be also confirmed by experimental data mentioned in this work. (author)

Activation of dihaloalkanes by glutathione conjugation and formation of DNA adducts

International Nuclear Information System (INIS)

Guengerich, F.P.; Peterson, L.A.; Cmarik, J.L.; Koga, N.; Inskeep, P.B.

1987-01-01

Ethylene dibromide (1,2-dibromoethane, EDB) can be activated to electrophilic species by either oxidative metabolism or conjugation with glutathione. Although conjugation is generally a route of detoxication, in this case it leads to genetic damage. The major DNA adduct has been identified as S-[2-(N 7 -guanyl)ethyl]glutathione, which is believed to arise via half-mustard and episulfonium ion intermediates. The adduct has a half-life of about 70 to 100 hr and does not appear to migrate to other DNA sites. Glutathione-dependent DNA damage by EDB was also demonstrated in human hepatocyte preparations. The possible relevance of this DNA adduct to genetic damage is discussed

DNA adduct quantification in Eisenia fetida after subchronic exposures to creosote contaminated soils

Energy Technology Data Exchange (ETDEWEB)

Charrois, J.W.A.; McGill, W.B. [Alberta Univ., Dept. of Renewable Resources, Edmonton, AB (Canada)

1999-07-01

Within soil ecosystems contaminant toxicity can vary from acute and chronic, depending on the time of exposure. Due to the long times involved chronic toxicity is difficult to determine. DNA adducts fall into the category of biochemical markers that act as an early warning system in environmental monitoring. It has been proposed that they could be used as a sensitive method to determine environmental exposures to compounds such as polycyclic aromatic hydrocarbons (PAHs), which can occur, although not exclusively, in creosote. In this connection, Benzo[a]pyrene (BaP) is a PAH that can be transformed into an electrophilic metabolite, which ultimately results in DNA adduct formation. Use was made of a 32P postlabeling method to quantify the number of DNA adducts occurring in the earthworm Eisenia fetida after exposure to weathered creosote contaminated- and biotreated-soils with and without additions of extra BaP. DNA adducts can be measured in earthworms exposed to creosote contaminated- and biotreated-soils. E. fetida exposed to weathered creosote contaminated soils had significantly more DNA adducts than those exposed to a pristine control soil. Exposures to creosote contaminated soils with additional BaP (1000 mg/kg) or biotreatment did not yield statistically significant increases in DNA adducts compared to the pristine control. (Abstract only)

Theoretical investigations on the formation of nitrobenzanthrone-DNA adducts.

Science.gov (United States)

Arlt, Volker M; Phillips, David H; Reynisson, Jóhannes

2011-09-07

3-Nitrobenzanthrone (3-NBA) is a potent mutagen and suspected human carcinogen identified in diesel exhaust. The thermochemical formation cascades were calculated for six 3-NBA-derived DNA adducts employing its arylnitrenium ion as precursor using density functional theory (DFT). Clear exothermic pathways were found for four adducts, i.e., 2-(2'-deoxyadenosin-N(6)-yl)-3-aminobenzanthrone, 2-(2'-deoxyguanosin-N(2)-yl)-3-aminobenzanthrone, N-(2'-deoxyguanosin-8-yl)-3-aminobenzanthrone and 2-(2'-deoxyguanosin-8-yl)-3-aminobenzanthrone. All four have been observed to be formed in cell-free experimental systems. The formation of N-(2'-deoxyadenosin-8-yl)-3-aminobenzanthrone is predicted to be not thermochemically viable explaining its absence in either in vitro or in vivo model systems. However, 2-(2'-deoxyadenosin-8-yl)-3-aminobenzanthrone, can be formed, albeit not as a major product, and is a viable candidate for an unknown adenine adduct observed experimentally. 2-nitrobenzanthrone (2-NBA), an isomer of 3-NBA, was also included in the calculations; it has a higher abundance in ambient air than 3-NBA, but a much lower genotoxic potency. Similar thermochemical profiles were obtained for the calculated 2-NBA-derived DNA adducts. This leads to the conclusion that enzymatic activation as well as the stability of its arylnitrenium ion are important determinants of 2-NBA genotoxicity.

Mass spectrometric analyses of organophosphate insecticide oxon protein adducts.

Science.gov (United States)

Thompson, Charles M; Prins, John M; George, Kathleen M

2010-01-01

Organophosphate (OP) insecticides continue to be used to control insect pests. Acute and chronic exposures to OP insecticides have been documented to cause adverse health effects, but few OP-adducted proteins have been correlated with these illnesses at the molecular level. Our aim was to review the literature covering the current state of the art in mass spectrometry (MS) used to identify OP protein biomarkers. We identified general and specific research reports related to OP insecticides, OP toxicity, OP structure, and protein MS by searching PubMed and Chemical Abstracts for articles published before December 2008. A number of OP-based insecticides share common structural elements that result in predictable OP-protein adducts. The resultant OP-protein adducts show an increase in molecular mass that can be identified by MS and correlated with the OP agent. Customized OP-containing probes have also been used to tag and identify protein targets that can be identified by MS. MS is a useful and emerging tool for the identification of proteins that are modified by activated organophosphate insecticides. MS can characterize the structure of the OP adduct and also the specific amino acid residue that forms the key bond with the OP. Each protein that is modified in a unique way by an OP represents a unique molecular biomarker that with further research can lead to new correlations with exposure.

DNA adduct formation among workers in a Thai industrial estate and nearby residents

International Nuclear Information System (INIS)

Peluso, Marco; Srivatanakul, Petcharin; Munnia, Armelle; Jedpiyawongse, Adisorn; Meunier, Aurelie; Sangrajrang, Suleeporn; Piro, Sara; Ceppi, Marcello; Boffetta, Paolo

2008-01-01

The genotoxic effects of air pollutant exposures have been studied in people living and working in Map Ta Phut, Rayong province, Thailand, a site where is located the Map Ta Phut Industrial Estate (MIE) one of the largest steel, refinery and petrochemical complex in the South-Eastern Asia. This was done by the conduction of a transversal study aimed to compare the prevalence of bulky DNA adducts in groups of subjects experiencing various degree of air pollution. DNA adduct analysis was performed in the leukocytes of 201 volunteers by the 32 P-postlabelling assay: 79 were workers in the MIE complex, including 24 refinery workers, 40 steel workers and 15 tinplate workers, 72 were people residing downwind in the MIE area and 50 were residents in a control district of the same Rayong province but without industrial exposures. The groups of workers were analyzed separately to evaluate if DNA adduct formation differs by the type of industry. The levels of bulky DNA adducts were 1.17 ± 0.17 (SE) adducts/10 8 nucleotides in refinery workers, 1.19 ± 0.19 (SE) in steel workers, 0.87 ± 0.17 (SE) in tinplate workers, 0.85 ± 0.07 (SE) in MIE residents and 0.53 ± 0.05 (SE) in district controls. No effects of smoking habits on DNA adducts was found. The multivariate regression analysis shows that the levels of DNA adducts were significantly increased among the individuals living near the MIE industrial complex in respect to those resident in a control district (p < 0.05). In the groups of occupationally exposed workers, the highest levels of DNA adducts were found among the workers experiencing an occupational exposure to polycyclic aromatic hydrocarbons, e.g. the steel factory and refinery workers. When we have evaluated if the levels of DNA adducts of the PAH exposed workers were different from those of the MIE residents, a statistical significantly difference was found (p < 0.05). Our present study indicates that people living near point sources of industrial air

Probabilistic estimation of future emissions of isoprene and surface oxidant chemistry associated with land-use change in response to growing food needs

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C. J. Hardacre

2013-06-01

Full Text Available We quantify the impact of land-use change, determined by our growing demand for food and biofuel production, on isoprene emissions and subsequent atmospheric oxidant chemistry in 2015 and 2030, relative to 1990, ignoring compound climate change effects over that period. We estimate isoprene emissions from an ensemble (n = 1000 of land-use change realizations from 1990–2050, broadly guided by the IPCC AR4/SRES scenarios A1 and B1. We also superimpose land-use change required to address projected biofuel usage using two scenarios: (1 assuming that world governments make no changes to biofuel policy after 2009, and (2 assuming that world governments develop biofuel policy with the aim of keeping equivalent atmospheric CO2 at 450 ppm. We present the median and interquartile range (IQR statistics of the ensemble and show that land-use change between −1.50 × 1012 m2 to +6.06 × 1012 m2 was found to drive changes in the global isoprene burden of −3.5 to +2.8 Tg yr−1 in 2015 and −7.7 to +6.4 Tg yr−1 in 2030. We use land-use change realizations corresponding to the median and IQR of these emission estimates to drive the GEOS-Chem global 3-D chemistry transport model to investigate the perturbation to global and regional surface concentrations of isoprene, nitrogen oxides (NO+NO2, and the atmospheric concentration and deposition of ozone (O3. We show that across subcontinental regions the monthly surface O3 increases by 0.1–0.8 ppb, relative to a zero land-use change calculation, driven by increases (decreases in surface isoprene in high (low NOx environments. At the local scale (4° × 5° we find that surface O3 increases by 5–12 ppb over temperate North America, China and boreal Eurasia, driven by large increases in isoprene emissions from short-rotation coppice crop cultivation for biofuel production.

Stomatal uptake and stomatal deposition of ozone in isoprene and monoterpene emitting plants.

Science.gov (United States)

Fares, S; Loreto, F; Kleist, E; Wildt, J

2008-01-01

Volatile isoprenoids were reported to protect plants against ozone. To understand whether this could be the result of a direct scavenging of ozone by these molecules, the stomatal and non-stomatal uptake of ozone was estimated in plants emitting isoprene or monoterpenes. Ozone uptake by holm oak (Quercus ilex, a monoterpene emitter) and black poplar (Populus nigra, an isoprene emitter) was studied in whole plant enclosures (continuously stirred tank reactors, CSTR). The ozone uptake by plants was estimated measuring ozone concentration at the inlet and outlet of the reactors, after correcting for the uptake of the enclosure materials. Destruction of ozone at the cuticle or at the plant stems was found to be negligible compared to the ozone uptake through the stomata. For both plant species, a relationship between stomatal conductance and ozone uptake was found. For the poplar, the measured ozone losses were explained by the uptake of ozone through the stomata only, and ozone destruction by gas phase reactions with isoprene was negligible. For the oak, gas phase reactions of ozone with the monoterpenes emitted by the plants contributed significantly to ozone destruction. This was confirmed by two different experiments showing a) that in cases of high stomatal conductance but under low CO(2) concentration, a reduction of monoterpene emission was still associated with reduced O(3) uptake; and b) that ozone losses due to the gas phase reactions only can be measured when using the exhaust from a plant chamber to determine the gas phase reactivity in an empty reaction chamber. Monoterpenes can therefore relevantly scavenge ozone at leaf level contributing to protection against ozone.

Revisiting the stability of endo/exo Diels-Alder adducts between cyclopentadiene and 1,4-benzoquinone

Energy Technology Data Exchange (ETDEWEB)

Tormena, Claudio F. [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Inst. de Quimica. Dept. de Quimica Organica; Lacerda Junior, Valdemar [Universidade Federal do Espirito Santo (UFES), Vitoria, ES (Brazil). Centro de Ciencias Exatas. Dept. de Quimica; Oliveira, Kleber T. de [Universidade Federal do ABC (UFABC), Santo Andre, SP (Brazil). Centro de Ciencias Naturais e Humanas

2010-07-01

In this work it is presented a detailed theoretical analysis of the relative stability of endo/exo Diels-Alder adducts formed by the reaction between cyclopentadiene (1) and 1,4-benzoquinone (2). The intrinsic reaction coordinate (IRC) showed the existence of only one transition state for the reaction studied, for both endo 3 and exo 4 adducts. The energies of both adducts were obtained at high level of theory (CBS-Q) confirming that the endo adduct is more stable than exo, which is in the opposite way to the observed in reactions that usually follow Alder's rule. An electronic structure analysis was performed through NBO methodology, indicating that the attractive delocalization interaction predominates over the steric repulsive interaction in the endo adducts. In summary, for the studied cycloaddition reaction the endo adduct is the thermodynamic and kinetic product, which can be also confirmed by experimental data mentioned in this work. (author)

DNA Adducts aand Human Atherosclerotis Lesions

Czech Academy of Sciences Publication Activity Database

Strejc, Přemysl; Boubelík, O.; Stávková, Zdena; Chvátalová, Irena; Šrám, Radim

2001-01-01

Roč. 42, - (2001), s. 662 ISSN 0008-5472. [Annual Meeting of Proceedings /92./. 24.03.2001-28.03.2001, New Orleans] R&D Projects: GA MZd NM10 Keywords : DNA adducts * LDL cholesterol Subject RIV: DN - Health Impact of the Environment Quality

Direct antioxidant properties of methotrexate: Inhibition of malondialdehyde-acetaldehyde-protein adduct formation and superoxide scavenging

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Matthew C. Zimmerman

2017-10-01

Full Text Available Methotrexate (MTX is an immunosuppressant commonly used for the treatment of autoimmune diseases. Recent observations have shown that patients treated with MTX also exhibit a reduced risk for the development of cardiovascular disease (CVD. Although MTX reduces systemic inflammation and tissue damage, the mechanisms by which MTX exerts these beneficial effects are not entirely known. We have previously demonstrated that protein adducts formed by the interaction of malondialdehyde (MDA and acetaldehyde (AA, known as MAA-protein adducts, are present in diseased tissues of individuals with rheumatoid arthritis (RA or CVD. In previously reported studies, MAA-adducts were shown to be highly immunogenic, supporting the concept that MAA-adducts not only serve as markers of oxidative stress but may have a direct role in the pathogenesis of inflammatory diseases. Because MAA-adducts are commonly detected in diseased tissues and are proposed to mitigate disease progression in both RA and CVD, we tested the hypothesis that MTX inhibits the generation of MAA-protein adducts by scavenging reactive oxygen species. Using a cell free system, we found that MTX reduces MAA-adduct formation by approximately 6-fold, and scavenges free radicals produced during MAA-adduct formation. Further investigation revealed that MTX directly scavenges superoxide, but not hydrogen peroxide. Additionally, using the Nrf2/ARE luciferase reporter cell line, which responds to intracellular redox changes, we observed that MTX inhibits the activation of Nrf2 in cells treated with MDA and AA. These studies define previously unrecognized mechanisms by which MTX can reduce inflammation and subsequent tissue damage, namely, scavenging free radicals, reducing oxidative stress, and inhibiting MAA-adduct formation.

Potential use of DNA adducts to detect mutagenic compounds in soil

International Nuclear Information System (INIS)

Hua Guoxiong; Lyons, Brett; Killham, Ken; Singleton, Ian

2009-01-01

In this study, three different soils with contrasting features, spiked with 300 mg benzo[a]pyrene (BaP)/kg dry soil, were incubated at 20 deg. C and 60% water holding capacity for 540 days. At different time points, BaP and DNA were extracted and quantified, and DNA adducts were quantified by 32 P-postlabelling. After 540 days incubation, 69.3, 81.6 and 83.2% of initial BaP added remained in Cruden Bay, Boyndie and Insch soils, respectively. Meanwhile, a significantly different amount of DNA-BaP adducts were found in the three soils exposed to BaP over time. The work demonstrates the concept that DNA adducts can be detected on DNA extracted from soil. Results suggest the technique is not able to directly reflect bioavailability of BaP transformation products. However, this new method provides a potential way to detect mutagenic compounds in contaminated soil and to assess the outcomes of soil remediation. - A novel DNA adduct assay may provide a potential technique to detect mutagenic compounds in contaminated soil

Development of methods to measure hemoglobin adducts by gel electrophoresis - Preliminary results

International Nuclear Information System (INIS)

Sun, J.D.; McBride, S.M.

1988-01-01

Chemical adducts formed on blood hemoglobin may be a useful biomarker for assessing human exposures to these compounds. This paper reports preliminary results in the development of methods to measure such adducts that may be generally applicable for a wide variety of chemicals. Male F344/N rats were intraperitoneally injected with 14 C-BaP dissolved in corn oil. Twenty-four hours later, the rats were sacrificed. Blood samples were collected and globin was isolated. Globin protein was then cleaved into peptide fragments using cyanogen bromide and the fragments separated using 2-dimensional gel electrophoresis. The results showed that the adducted 14 C-globin fragments migrated to different areas of the gel than did unadducted fragments. Further research is being conducted to develop methods that will allow quantitation of separated adducted globin fragments from human blood samples without the use of a radiolabel. (author)

Selective Production of Toluene from Biomass-Derived Isoprene and Acrolein.

Science.gov (United States)

Dai, Tao; Li, Changzhi; Zhang, Bo; Guo, Haiwei; Pan, Xiaoli; Li, Lin; Wang, Aiqin; Zhang, Tao

2016-12-20

Toluene is a basic chemical that is currently produced from petroleum resources. In this paper, we report a new route for the effective synthesis of toluene from isoprene and acrolein, two reactants readily available from biomass, through a simple two-step reaction. The process includes Diels-Alder cycloaddition of isoprene and acrolein in a Zn-containing ionic liquid at room temperature to produce methylcyclohex-3-enecarbaldehydes (MCHCAs) as intermediates, followed by M (M=Pt, Pd, Rh)/Al 2 O 3 -catalyzed consecutive dehydrogenation-decarbonylation of the MCHCAs at 573 K to generate toluene with an overall yield up to 90.7 %. Model reactions indicated that a synergistic inductive effect of the C=C double bond and the aldehyde group in MCHCA plays a key role in initiating the consecutive dehydrogenation-decarbonylation, and that methyl benzaldehydes are the key intermediates in the gas-phase transformation of MCHCAs. Microcalorimetric adsorption of CO on different catalysts showed that decarbonylation of the substrate occurs more likely on the strong adsorption sites. To the best of our knowledge, it is the first report of Pt/Al 2 O 3 -catalyzed consecutive dehydrogenation-decarbonylation of a given compound in one reactor. This work provides a highly efficient and environmental friendly route to toluene by utilizing two compounds that can be prepared from biomass. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sensitivity to grid resolution in the ability of a chemical transport model to simulate observed oxidant chemistry under high-isoprene conditions

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K. Yu

2016-04-01

Full Text Available Formation of ozone and organic aerosol in continental atmospheres depends on whether isoprene emitted by vegetation is oxidized by the high-NOx pathway (where peroxy radicals react with NO or by low-NOx pathways (where peroxy radicals react by alternate channels, mostly with HO2. We used mixed layer observations from the SEAC4RS aircraft campaign over the Southeast US to test the ability of the GEOS-Chem chemical transport model at different grid resolutions (0.25°  ×  0.3125°, 2°  ×  2.5°, 4°  ×  5° to simulate this chemistry under high-isoprene, variable-NOx conditions. Observations of isoprene and NOx over the Southeast US show a negative correlation, reflecting the spatial segregation of emissions; this negative correlation is captured in the model at 0.25°  ×  0.3125° resolution but not at coarser resolutions. As a result, less isoprene oxidation takes place by the high-NOx pathway in the model at 0.25°  ×  0.3125° resolution (54 % than at coarser resolution (59 %. The cumulative probability distribution functions (CDFs of NOx, isoprene, and ozone concentrations show little difference across model resolutions and good agreement with observations, while formaldehyde is overestimated at coarse resolution because excessive isoprene oxidation takes place by the high-NOx pathway with high formaldehyde yield. The good agreement of simulated and observed concentration variances implies that smaller-scale non-linearities (urban and power plant plumes are not important on the regional scale. Correlations of simulated vs. observed concentrations do not improve with grid resolution because finer modes of variability are intrinsically more difficult to capture. Higher model resolution leads to decreased conversion of NOx to organic nitrates and increased conversion to nitric acid, with total reactive nitrogen oxides (NOy changing little across model resolutions. Model concentrations in the

Selective measurements of isoprene and 2-methyl-3-buten-2-ol based on NO+ ionization mass spectrometry

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W. Jud

2012-12-01

Full Text Available Biogenic VOC emissions are often dominated by 2-methyl-1,3-butadiene (isoprene and 2-methyl-3-buten-2-ol (232 MBO. Here we explore the possibility to selectively distinguish these species using NO+ as a primary ion in a conventional PTR-MS equipped with an SRI unit. High purity of NO+ (>90% as a primary ion was utilized in laboratory and field experiments using a conventional PTR-TOF-MS. Isoprene is ionized via charge transfer leading to the major product ion C5H8+ (>99% (e.g. Spanel and Smith, 1998. 232 MBO undergoes a hydroxide ion transfer reaction resulting in the major product ion channel C5H9+ (>95% (e.g. Amelynck et al., 2005. We show that both compounds are ionized with little fragmentation (>5% under standard operating conditions. Typical sensitivities of 11.1 ± 0.1 (isoprene and 12.9 ± 0.1 (232 MBO ncps ppbv−1 were achieved, which correspond to limit of detections of 18 and 15 pptv respectively for a 10 s integration time. Sensitivities decreased at higher collisional energies. Calibration experiments showed little humidity dependence. We tested the setup at a field site in Colorado dominated by ponderosa pine, a 232 MBO emitting plant species. Our measurements confirm 232 MBO as the dominant biogenic VOC at this site, exhibiting typical average daytime concentrations between 0.2–1.4 ppbv. The method is able to detect the presence of trace levels of isoprene at this field site (90–250 ppt without any interference from 232 MBO, which would not be feasible using H3O+ ionization chemistry, and which currently also remains a challenge for other analytical techniques (e.g. gas chromatographic methods.

Determination of the hydrogen positions in the novel barium boroarsenate Ba[B{sub 2}As{sub 2}O{sub 8}(OH){sub 2}] by combined single crystal X-ray and powder neutron investigations

Energy Technology Data Exchange (ETDEWEB)

Lieb, Alexandra [School of Chemistry, University of Southampton (United Kingdom); Fakultaet fuer Verfahrens- und Systemtechnik, Lehrstuhl fuer Technische Chemie, Otto-von-Guericke-Universitaet, Magdeburg (Germany); Weller, Mark T. [School of Chemistry, University of Southampton (United Kingdom); Department of Chemistry, University of Bath (United Kingdom)

2017-11-17

The boroarsenate Ba[B{sub 2}As{sub 2}O{sub 8}(OH){sub 2}] was obtained by the reaction of NH{sub 4}H{sub 2}AsO{sub 4}, B(OH){sub 3} and BaBr{sub 2}.2H{sub 2}O in the melt. Ba[B{sub 2}As{sub 2}O{sub 8}(OH){sub 2}] was obtained as thin colorless needles, together with spherical crystals of BAsO{sub 4} as by-product, grown on a pellet of Ba[BAsO{sub 5}]. The products could be separated mechanically. For neutron scattering experiments a sample was prepared with {sup 11}B(OH){sub 3} as a starting material. The crystal structure of Ba[B{sub 2}As{sub 2}O{sub 8}(OH){sub 2}] was determined by single-crystal X-ray diffraction and exhibits a layer structure with an unprecedented layer topology. The exact positions of the hydrogen atoms were determined using combined single-crystal X-ray and powder neutron diffraction investigations. Ba[B{sub 2}As{sub 2}O{sub 8}(OH){sub 2}] was further characterized by IR spectroscopy and EDX analysis. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

γIrradiation induced formation of PCB-solvent adducts in aliphatic solvents

International Nuclear Information System (INIS)

Lepine, F.; Milot, S.; Gagne, N.

1990-01-01

γIrradiation induced formation of PCB-solvent adducts was investigated as a model for PCB residues in irradiated food. Formation of cyclohexyl adducts of PCBs was found to be significant when pure PCB congeners and Aroclor mixture were irradiated in cyclohexane and cyclohexene. Reaction pathways were investigated, and the effects of oxygen and electron scavenger were studied

Pyrrolizidine alkaloid-derived DNA adducts as a common biological biomarker of pyrrolizidine alkaloid-induced tumorigenicity.

Science.gov (United States)

Xia, Qingsu; Zhao, Yuewei; Von Tungeln, Linda S; Doerge, Daniel R; Lin, Ge; Cai, Lining; Fu, Peter P

2013-09-16

Pyrrolizidine alkaloid-containing plants are the most common poisonous plants affecting livestock, wildlife, and humans. The U.S. National Toxicology Program (NTP) classified riddelliine, a tumorigenic pyrrolizidine alkaloid, as "reasonably anticipated to be a human carcinogen" in the NTP 12th Report on Carcinogens in 2011. We previously determined that four DNA adducts were formed in rats dosed with riddelliine. The structures of the four DNA adducts were elucidated as (i) a pair of epimers of 7-hydroxy-9-(deoxyguanosin-N(2)-yl)dehydrosupinidine adducts (termed as DHP-dG-3 and DHP-dG-4) as the predominant adducts; and (ii) a pair of epimers of 7-hydroxy-9-(deoxyadenosin-N(6)-yl)dehydrosupinidine adducts (termed as DHP-dA-3 and DHP-dA-4 adducts). In this study, we selected a nontumorigenic pyrrolizidine alkaloid, platyphylliine, a pyrrolizidine alkaloid N-oxide, riddelliine N-oxide, and nine tumorigenic pyrrolizidine alkaloids (riddelliine, retrorsine, monocrotaline, lycopsamine, retronecine, lasiocarpine, heliotrine, clivorine, and senkirkine) for study in animals. Seven of the nine tumorigenic pyrrolizidine alkaloids, with the exception of lycopsamine and retronecine, are liver carcinogens. At 8-10 weeks of age, female F344 rats were orally gavaged for 3 consecutive days with 4.5 and 24 μmol/kg body weight test article in 0.5 mL of 10% DMSO in water. Twenty-four hours after the last dose, the rats were sacrificed, livers were removed, and liver DNA was isolated for DNA adduct analysis. DHP-dG-3, DHP-dG-4, DHP-dA-3, and DHP-dA-4 adducts were formed in the liver of rats treated with the individual seven hepatocarcinogenic pyrrolizidine alkaloids and riddelliine N-oxide. These DNA adducts were not formed in the liver of rats administered retronecine, the nontumorigenic pyrrolizidine alkaloid, platyphylliine, or vehicle control. These results indicate that this set of DNA adducts, DHP-dG-3, DHP-dG-4, DHP-dA-3, and DHP-dA-4, is a common biological biomarker of

The fate of H atom adducts to 3'-uridine monophosphate.

Science.gov (United States)

Wang, Ran; Zhang, Ru Bo; Eriksson, Leif A

2010-07-29

The stabilities of the adducts deriving from H free radical addition to the O2, O4, and C5 positions of 3'-uridine monophosphate (3'UMP) are studied by the hybrid density functional B3LYP approach. Upon H atom addition at the O2 position, a concerted low-barrier proton-transfer process will initially occur, followed by the potential ruptures of the N-glycosidic or beta-phosphate bonds. The rupture barriers are strongly influenced by the rotational configuration of the phosphate group at the 3' terminal, and are influenced by bulk solvation effects. The O4-H adduct has the highest thermal stability, as the localization of the unpaired electron does not enable cleavage of either the C1'-N1 or the C3'-O(P) bonds. For the most stable adduct, with H atom added to the C5 position, the rate-controlled step is the H2'a abstraction by the C6 radical site, after which the subsequent strand rupture reactions proceed with low barriers. The main unpaired electron densities are presented for the transient species. Combined with previous results, it is concluded that the H atom adducts are more facile to drive the strand scission rather than N-glycosidic bond ruptures within the nucleic acid bases.

High-performance liquid chromatography/electrospray mass spectrometry for the analysis of modified bases in DNA: 7-(2-hydroxyethyl)guanine, the major ethylene oxide-DNA adduct.

Science.gov (United States)

Leclercq, L; Laurent, C; De Pauw, E

1997-05-15

A method was developed for the analysis of 7-(2-hydroxyethyl)guanine (7HEG), the major DNA adduct formed after exposure to ethylene oxide (EO). The method is based on DNA neutral thermal hydrolysis, adduct micro-concentration, and final characterization and quantification by HPLC coupled to single-ion monitoring electrospray mass spectrometry (HPLC/SIR-ESMS). The method was found to be selective, sensitive, and easy to handle with no need for enzymatic digestion or previous sample derivatization. Detection limit was found to be close to 1 fmol of adduct injected (10(-10) M), thus allowing the detection of approximately three modified bases on 10(8) intact nucleotides in blood sample analysis. Quantification results are shown for 7HEG after calf thymus DNA and blood exposure to various doses of EO, in both cases obtaining clear dose-response relationships.

Pyrrolizidine alkaloid-derived DNA adducts are common toxicological biomarkers of pyrrolizidine alkaloid N-oxides.

Science.gov (United States)

He, Xiaobo; Xia, Qingsu; Woodling, Kellie; Lin, Ge; Fu, Peter P

2017-10-01

There are 660 pyrrolizidine alkaloids (PAs) and PA N-oxides present in the plants, with approximately half being possible carcinogens. We previously reported that a set of four PA-derived DNA adducts is formed in the liver of rats administered a series of hepatocarcinogenic PAs and a PA N-oxide. Based on our findings, we hypothesized that this set of DNA adducts is a common biological biomarker of PA-induced liver tumor formation. In this study, we determined that rat liver microsomal metabolism of five hepatocarcinogenic PAs (lasiocarpine, retrorsine, riddelliine, monocrotaline, and heliotrine) and their corresponding PA N-oxides produced the same set of DNA adducts. Among these compounds, lasiocarpine N-oxide, retrorsine N-oxide, monocrotaline N-oxide, and heliotrine N-oxide are for first time shown to be able to produce these DNA adducts. These results further support the role of these DNA adducts as potential common biomarkers of PA-induced liver tumor initiation. Copyright © 2017. Published by Elsevier B.V.

Pyrrolizidine alkaloid-derived DNA adducts are common toxicological biomarkers of pyrrolizidine alkaloid N-oxides

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Xiaobo He

2017-10-01

Full Text Available There are 660 pyrrolizidine alkaloids (PAs and PA N-oxides present in the plants, with approximately half being possible carcinogens. We previously reported that a set of four PA-derived DNA adducts is formed in the liver of rats administered a series of hepatocarcinogenic PAs and a PA N-oxide. Based on our findings, we hypothesized that this set of DNA adducts is a common biological biomarker of PA-induced liver tumor formation. In this study, we determined that rat liver microsomal metabolism of five hepatocarcinogenic PAs (lasiocarpine, retrorsine, riddelliine, monocrotaline, and heliotrine and their corresponding PA N-oxides produced the same set of DNA adducts. Among these compounds, lasiocarpine N-oxide, retrorsine N-oxide, monocrotaline N-oxide, and heliotrine N-oxide are for first time shown to be able to produce these DNA adducts. These results further support the role of these DNA adducts as potential common biomarkers of PA-induced liver tumor initiation.

Effect of gamma irradiation conditions on the radiation-induced degradation of isobutylene-isoprene rubber

Energy Technology Data Exchange (ETDEWEB)

Sen, M. E-mail: msen@hacettepe.edu.tr; Uzun, C.; Kantoglu, Oe.; Erdogan, S.M.; Deniz, V.; Gueven, O

2003-08-01

The effect of gamma irradiation conditions on the radiation-induced degradation of uncrosslinked, commercial isobutylene-isoprene rubbers has been investigated in this study. Influence of dose rate and irradiation atmosphere on the degradation of butyl rubber has been followed by viscosimetric and chromatographic analyses. Limiting viscosity number of all butyl rubbers decreased sharply up to 100 kGy and leveled off at around the same molecular weight, independent of dose rate. Slightly higher decrease in viscosity was observed for samples irradiated in air than in nitrogen especially at low dose rate irradiation. Cross-linking G(X), and chain scission G(S) yields of butyl rubbers were calculated by using weight- and number-average molecular weights of irradiated rubber determined by Size Exclusion Chromatography analyses. G-value results showed that chain scission reactions in isobutylene-isoprene rubber in air atmosphere are more favorable than in nitrogen atmosphere, and that lower dose rate enhances chain scission over cross-linking.

Aqueous-Phase Reactions of Isoprene with Sulfoxy Radical Anions as a way of Wet Aerosol Formation in the Atmosphere

Science.gov (United States)

Kuznietsova, I.; Rudzinski, K. J.; Szmigielski, R.; Laboratory of the Environmental Chemistry

2011-12-01

Atmospheric aerosols exhibit an important role in the environment. They have implications on human health and life, and - in the larger scale - on climate, the Earth's radiative balance and the cloud's formation. Organic matter makes up a significant fraction of atmospheric aerosols (~35% to ~90%) and may originate from direct emissions (primary organic aerosol, POA) or result from complex physico-chemical processes of volatile organic compounds (secondary organic aerosol, SOA). Isoprene (2-methyl-buta-1,3-diene) is one of the relevant volatile precursor of ambient SOA in the atmosphere. It is the most abundant non-methane hydrocarbon emitted to the atmosphere as a result of living vegetation. According to the recent data, the isoprene emission rate is estimated to be at the level of 500 TgC per year. While heterogeneous transformations of isoprene have been well documented, aqueous-phase reactions of this hydrocarbon with radical species that lead to the production of new class of wet SOA components such as polyols and their sulfate esters (organosulfates), are still poorly recognized. The chain reactions of isoprene with sulfoxy radical-anions (SRA) are one of the recently researched route leading to the formation of organosulfates in the aqueous phase. The letter radical species originate from the auto-oxidation of sulfur dioxide in the aqueous phase and are behind the phenomenon of atmospheric acid rain formation. This is a complicated chain reaction that is catalyzed by transition metal ions, such as manganese(II), iron(III) and propagated by sulfoxy radical anions . The presented work addresses the chemical interaction of isoprene with sulfoxy radical-anions in the water solution in the presence of nitrite ions and nitrous acid, which are important trace components of the atmosphere. We showed that nitrite ions and nitrous acid significantly altered the kinetics of the auto-oxidation of SO2 in the presence of isoprene at different solution acidity from 2 to 8

Acetaldehyde Adducts in Alcoholic Liver Disease

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Mashiko Setshedi

2010-01-01

Full Text Available Chronic alcohol abuse causes liver disease that progresses from simple steatosis through stages of steatohepatitis, fibrosis, cirrhosis, and eventually hepatic failure. In addition, chronic alcoholic liver disease (ALD, with or without cirrhosis, increases risk for hepatocellular carcinoma (HCC. Acetaldehyde, a major toxic metabolite, is one of the principal culprits mediating fibrogenic and mutagenic effects of alcohol in the liver. Mechanistically, acetaldehyde promotes adduct formation, leading to functional impairments of key proteins, including enzymes, as well as DNA damage, which promotes mutagenesis. Why certain individuals who heavily abuse alcohol, develop HCC (7.2–15% versus cirrhosis (15–20% is not known, but genetics and co-existing viral infection are considered pathogenic factors. Moreover, adverse effects of acetaldehyde on the cardiovascular and hematologic systems leading to ischemia, heart failure, and coagulation disorders, can exacerbate hepatic injury and increase risk for liver failure. Herein, we review the role of acetaldehyde adducts in the pathogenesis of chronic ALD and HCC.

8-Hydroxy-2'-deoxyguanosine (8-OH-dG): A biomarker of oxidative damage in yellow bullheads chronically exposed to low-level radiation

International Nuclear Information System (INIS)

McCreedy, C.D.; Glickman, L.T.

1995-01-01

8-hydroxy-2'-deoxyguanosine (8-OH-dG), an oxidation product of the nucleotide deoxyguanosine (dG) was used as a biomarker to assess oxidative damage in brain and gill tissues of yellow bullhead catfish (Ameiurus natalis; n = 18) inhabiting an abandoned reactor reservoir contaminated with low levels of d137 Cs (Pond B, Savannah River Site, SC). DNA was isolated by chloroform-isoamyl extraction, enzymatically digested with Nuclease P1/Calf Intestinal Phosphatase, and analyzed by HPLC with electrochemical detection.Length, weight, age, condition and muscle 137 Cs activity of each fish were also determined. Concentrations of 8-OH-dG were greater in brain than in gill tissues. 8-OH-dG in gill tissues decreased as condition of fish increased, but as age increased, the effect of condition declined. Brain 8-OH-dG concentration was not related to age or condition of fish, but was greater in females and the interaction between gender and 137 Cs was significant. Brain 8-OH-dG was positively associated with muscle 137 Cs concentration among females, but was unrelated to 137 Cs concentration in males. At lower 137 Cs concentrations, females tended to have fewer oxidative DNA adducts in brian than did males. Deposition of somatic lipids into eggs may provide females some anti-oxidant benefit by diminishing the contribution of lipid peroxidation to DNA damage. 8-OH-dG is a sensitive biomarker of low-level radiation exposure, however, its application in fish requires consideration of factors such as gender, age, body-condition, and the tissue type sampled

Origin of the OH vibrational blue shift in the LiOH crystal.

Science.gov (United States)

Hermansson, Kersti; Gajewski, Grzegorz; Mitev, Pavlin D

2008-12-25

The O-H vibrational frequency in crystalline hydroxides is either upshifted or downshifted by its crystalline surroundings. In the LiOH crystal, the experimental gas-to-solid O-H frequency upshift ("blue shift") is approximately +115 cm(-1). Here plane-wave DFT calculations for the isotope-isolated LiOH crystal have been performed and we discuss the origin of the OH frequency upshift, and the nature of the OH group and the interlayer interactions. We find that (1) the vibrational frequency upshift originates from interactions within the LiOH layer; this OH upshift is slightly lessened by the interlayer interactions; (2) the interlayer O-H - - - H-O interaction is largely electrostatic in character (but there is no hydrogen bonding); (3) the gas-to-solid vibrational shift for OH in LiOH(s) and its subsystems qualitatively adheres to a parabola-like "frequency vs electric field strength" correlation curve, which has a maximum for a positive electric field, akin to the correlation curve earlier found in the literature for an isolated OH(-) ion in an electric field.

DNA adduct formation in B6C3F1 mice and Fischer-344 rats exposed to 1,2,3-trichloropropane.

Science.gov (United States)

La, D K; Lilly, P D; Anderegg, R J; Swenberg, J A

1995-06-01

1,2,3-Trichloropropane (TCP) is a multispecies, multisite carcinogen which has been found to be an environmental contaminant. In this study, we have characterized and measured DNA adducts formed in vivo following exposure to TCP. [14C]TCP was administered to male B6C3F1 mice and Fischer-344 rats by gavage at doses used in the NTP carcinogenesis bioassay. Both target and nontarget organs were examined for the formation of DNA adducts. Adducts were hydrolyzed from DNA by neutral thermal or mild acid hydrolysis, isolated by HPLC, and detected and quantitated by measurement of radioactivity. The HPLC elution profile of radioactivity suggested that one major DNA adduct was formed. To characterize this adduct, larger yields were induced in rats by intraperitoneal administration of TCP (300 mg/kg). The DNA adduct was isolated by HPLC based on coelution with the radiolabeled adduct, and compared to previously identified adducts. The isolated adduct coeluted with S-[1-(hydroxymethyl)-2-(N7-guanyl)-ethyl]glutathione, an adduct derived from the structurally related carcinogen 1,2-dibromo-3-chloropropane (DBCP). Analysis by electrospray mass spectrometry suggested that the TCP-induced adduct and the DBCP-derived adduct were identical. The 14C-labeled DNA adduct was distributed widely among the organs examined. Adduct levels varied depending on species, organ, and dose. In rat organs, adduct concentrations for the low dose ranged from 0.8 to 6.6 mumol per mol guanine and from 7.1 to 47.6 mumol per mol guanine for the high dose. In the mouse, adduct yields ranged from 0.32 to 28.1 mumol per mol guanine for the low dose and from 12.2 to 208.1 mumol per mol guanine for the high dose. The relationship between DNA adduct formation and organ-specific tumorigenesis was unclear. Although relatively high concentrations of DNA adducts were detected in target organs, several nontarget sites also contained high adduct levels. Our data suggest that factors in addition to adduct formation

Determination of albumin adducts of 4,4'-methylenediphenyl diisocyanate after specific inhalative challenge tests in workers.

Science.gov (United States)

Sabbioni, Gabriele; Dongari, Nagaraju; Kumar, Anoop; Baur, Xaver

2016-10-17

4,4'-Methylenediphenyl diisocyanate (MDI) is the most important isocyanate used in the industry. Lung sensitization with bronchial asthma is the main disorder in exposed workers. Albumin adducts of MDI might be involved in specific immunological reactions. MDI adducts with lysine (MDI-Lys) of albumin have been found in MDI-workers and construction workers. MDI-Lys is an isocyanate-specific adduct of MDI with albumin. In the present study, we report MDI-adducts in workers undergoing diagnostic MDI challenge tests. The workers were exposed for 2h to 5ppb of MDI. The adduct levels increase significantly after the exposure to MDI in the challenge chamber. About 0.6% of the dose was bound to albumin. So far, only urinary metabolites of MDI were measured to monitor isocyanate workers. However, such urinary metabolites are not isocyanate specific. Therefore, we propose to measure albumin adducts for monitoring MDI exposed subjects. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Managing OHS

DEFF Research Database (Denmark)

Hull Kristensen, Peer

2011-01-01

Contrary to a widely held view, rather than seeing the certification of Occupational Health and Safety (OHS) as a barrier to increasing employee participation, this article views new ways of structuring participation as a necessary step towards making improvements in OHS management systems....... The article first considers how work organization has changed and then in a similar way traces how bargaining has shifted from being distributive to become integrative to create a fundamental change in the negotiation regime. Finally, by analyzing an OHS-certified firm in greater depth, the article shows how...... solutions for improvements in OHS management and notable bottom-up formulations of OHS benchmarks may help us discover how the organizational form of firms with high-performance work organization can be developed through new participatory structures....

ACCUMULATION OF M1DG DNA ADDUCTS AFTER CHRONIC EXPOSURE TO PCBS, BUT NOT FROM ACUTE EXPOSURE TO DIOXIN-LIKE COMPOUNDS

Science.gov (United States)

ABSTRACT: Oxidative DNA damage is one of the key events leading to mutation and cancer. The present study examined the accumulation of M1dG DNA adducts, 3-(2’-deoxy-β-D-erythro-pentofuranosyl)-pyrimido[1,2-a]-purin-10(3H)-one, after single or yearly exposur...

Benzo(a)pyrene-DNA adduct formation in cells: time-dependent differences in the benzo(a)pyrene-DNA adducts present

International Nuclear Information System (INIS)

Baird, W.M.; Dumaswala, R.U.

1980-01-01

Procedures involving isolation of the DNA from tritium labelled hydrocarbon-treated cells are discussed. Enzymatic degradation of the DNA to deoxyribonucleosides, and chromatography of the adducts on columns of water gradients were covered as well

Oxidation of cinnamic acid derivatives: A pulse radiolysis and theoretical study

International Nuclear Information System (INIS)

Yadav, Pooja; Mohan, Hari; Maity, Dilip Kumar; Suresh, Cherumuttathu H.; Rao, B.S. Madhav

2008-01-01

Second order rate constants in the range of (k = 1.6-4.5) x 10 9 dm 3 mol -1 s -1 were obtained for the · OH induced oxidation of nitro- and methoxycinnamic acid derivatives in neutral solutions using pulse radiolysis. The transient absorption spectra exhibited a broad peak around 360-410 nm in o-methoxy, o- and p-nitrocinnamates or two peaks around 310-330 and 370-410 nm in other isomers. Quantum chemical calculations revealed that addition of · OH to olefinic moiety yielded considerably more stable structures than ring addition products and the para system among the latter is the most stable. Spin density analysis suggested that olefinic adducts retained the aromaticity in contrast to its loss in ring · OH adducts. An excellent linear correlation between the relative stabilities of the · OH adducts (after accounting for the aromatic stabilization in olefinic adducts) and the maximum S d values is also obtained

40 CFR 721.3700 - Fatty acid, ester with styrenated phenol, ethylene oxide adduct.

Science.gov (United States)

2010-07-01

... phenol, ethylene oxide adduct. 721.3700 Section 721.3700 Protection of Environment ENVIRONMENTAL..., ethylene oxide adduct. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as fatty acid, ester with styrenated phenol, ethylene oxide...

Bulky DNA adducts in white blood cells: a pooled analysis of 3,600 subjects

DEFF Research Database (Denmark)

Ricceri, Fulvio; Godschalk, Roger W; Peluso, Marco

2010-01-01

Bulky DNA adducts are markers of exposure to genotoxic aromatic compounds, which reflect the ability of an individual to metabolically activate carcinogens and to repair DNA damage. Polycyclic aromatic hydrocarbons (PAHs) represent a major class of carcinogens that are capable of forming such add...... such adducts. Factors that have been reported to be related to DNA adduct levels include smoking, diet, body mass index (BMI), genetic polymorphisms, the season of collection of biologic material, and air pollutants....

Determination of isocyanate specific albumin-adducts in workers exposed to toluene diisocyanates.

Science.gov (United States)

Sabbioni, Gabriele; Gu, Qi; Vanimireddy, Lakshiminiranjan Reddy

2012-03-01

Toluene diisocyanates (2,4-TDI and 2,6-TDI) are important intermediates in the chemical industry. Among the main damages after low levels of TDI exposure are lung sensitization and asthma. It is therefore necessary to have sensitive and specific methods to monitor isocyanate exposure of workers. Urinary metabolites or protein adducts have been used as biomarkers in workers exposed to TDI. However, with these methods it was not possible to determine if the biomarkers result from exposure to TDI or to the corresponding toluene diamines (TDA). This work presents a new procedure for the determination of isocyanate-specific albumin adducts. Isotope dilution mass spectrometry was used to measure the adducts in albumin present in workers exposed to TDI. 2,4-TDI and 2,6-TDI formed adducts with lysine: N(ϵ)-[({3-amino-4-methylphenyl}amino)carbonyl]-lysine, N(ϵ)-[({5-amino-2-methylphenyl}amino)carbonyl]-lysine, and N(ϵ)- [({3-amino-2-methylphenyl}amino)carbonyl]-lysine. In future studies, this new method can be applied to measure TDI-exposures in workers.

Ethene, propene, butene and isoprene emissions from a ponderosa pine forest measured by relaxed eddy accumulation

Science.gov (United States)

Rhew, Robert C.; Deventer, Malte Julian; Turnipseed, Andrew A.; Warneke, Carsten; Ortega, John; Shen, Steve; Martinez, Luis; Koss, Abigail; Lerner, Brian M.; Gilman, Jessica B.; Smith, James N.; Guenther, Alex B.; de Gouw, Joost A.

2017-11-01

Alkenes are reactive hydrocarbons that influence local and regional atmospheric chemistry by playing important roles in the photochemical production of tropospheric ozone and in the formation of secondary organic aerosols. The simplest alkene, ethene (ethylene), is a major plant hormone and ripening agent for agricultural commodities. The group of light alkenes (C2-C4) originates from both biogenic and anthropogenic sources, but their biogenic sources are poorly characterized, with limited field-based flux observations. Here we report net ecosystem fluxes of light alkenes and isoprene from a semiarid ponderosa pine forest in the Rocky Mountains of Colorado, USA using the relaxed eddy accumulation (REA) technique during the summer of 2014. Ethene, propene, butene and isoprene emissions have strong diurnal cycles, with median daytime fluxes of 123, 95, 39 and 17 µg m-2 h-1, respectively. The fluxes were correlated with each other, followed general ecosystem trends of CO2 and water vapor, and showed similar sunlight and temperature response curves as other biogenic VOCs. The May through October flux, based on measurements and modeling, averaged 62, 52, 24 and 18 µg m-2 h-1 for ethene, propene, butene and isoprene, respectively. The light alkenes contribute significantly to the overall biogenic source of reactive hydrocarbons: roughly 18 % of the dominant biogenic VOC, 2-methyl-3-buten-2-ol. The measured ecosystem scale fluxes are 40-80 % larger than estimates used for global emissions models for this type of ecosystem.

Amino acid-based dithiazines: synthesis and photofragmentation of their benzaldehyde adducts.

Science.gov (United States)

Kurchan, Alexei N; Kutateladze, Andrei G

2002-11-14

Alpha-amino acids and GABA are functionalized with dithiazine rings via reaction with sodium hydrosulfide in aqueous formaldehyde. The resulting dithiazines are lithiated at -78 degrees C and reacted with benzaldehyde furnishing amino acid-based 2,5-bis-substituted dithiazines. These adducts undergo externally sensitized photofragmentation with quantum efficiency comparable to that of the parent dithiane adducts, thus offering a novel approach to amino acid-based photolabile tethers. [reaction: see text

7-Alkylguanine adduct levels in urine, lungs and liver of mice exposed to styrene by inhalation

International Nuclear Information System (INIS)

Vodicka, Pavel Erik; Linhart, Igor; Novak, Jan; Koskinen, Mikko; Vodickova, Ludmila; Hemminki, Kari

2006-01-01

This study describes urinary excretion of two nucleobase adducts derived from styrene 7,8-oxide (SO), i.e., 7-(2-hydroxy-1-phenylethyl)guanine (N7αG) and 7-(2-hydroxy-2-phenylethyl)guanine (N7βG), as well as a formation of N7-SO-guanine adducts in lungs and liver of two month old male NMRI mice exposed to styrene by inhalation in a 3-week subacute study. Strikingly higher excretion of both isomeric nucleobase adducts in the first day of exposure was recorded, while the daily excretion of nucleobase adducts in following time intervals reached the steady-state level at 4.32 + 1.14 and 6.91 + 1.17 pmol/animal for lower and higher styrene exposure, respectively. β-SO-guanine DNA adducts in lungs increased with exposure in a linear way (F = 13.7 for linearity and 0.17 for non-linearity, respectively), reaching at the 21st day the level of 23.0 adducts/10 8 normal nucleotides, i.e., 0.74 fmol/μg DNA of 7-alkylguanine DNA adducts for the concentration of 1500 mg/m 3 , while no 7-SO-guanine DNA adducts were detected in the liver after 21 days of inhalation exposure to both of styrene concentrations. A comparison of 7-alkylguanines excreted in urine with 7-SO-guanines in lungs (after correction for depurination and for missing α-isomers) revealed that persisting 7-SO-guanine DNA adducts in lungs account for about 0.5% of the total alkylation at N7 of guanine. The total styrene-specific 7-guanine alkylation accounts for about 1.0 x 10 -5 % of the total styrene uptake, while N1-adenine alkylation contributes to this percentage only negligibly

Gender differences in the knee adduction moment after anterior cruciate ligament reconstruction surgery.

Science.gov (United States)

Webster, Kate E; McClelland, Jodie A; Palazzolo, Simon E; Santamaria, Luke J; Feller, Julian A

2012-04-01

The external knee adduction moment during gait has previously been associated with knee pain and osteoarthritis (OA). Recently, the knee adduction moment has been shown to be increased following anterior cruciate ligament (ACL) reconstruction surgery and has been suggested as a potential mechanism for the progression of early onset knee OA in this population. No study has investigated the gender differences in gait biomechanics following ACL reconstruction. To examine gender differences in gait biomechanics following ACL reconstruction surgery. 36 subjects (18 females, 18 males) who had previously undergone ACL reconstruction surgery (mean time since surgery 20 months) underwent gait analysis at a self-selected walking speed. Males and females were well matched for age, time since surgery and walking speed. Maximum flexion and adduction angles and moments were recorded during the stance phase of level walking and compared between the male and female groups. The knee adduction moment was 23% greater in the female compared with the male ACL group. No gender differences were seen in the sagittal plane. No differences were seen between the reconstructed and contralateral limb. The higher knee adduction moment seen in females compared with males may suggest an increased risk for the development of OA in ACL-reconstructed females.

Metal-isonitrile adducts for preparing radionuclide complexes

International Nuclear Information System (INIS)

Carpenter, A.P.; Linder, K.E.; Maheu, L.J.; Patz, M.A.; Thompson, J.S.; Tulip, T.H.; Subramanyam, V.

1988-01-01

An method for preparing a coordination complex of isonitrile ligand and a radioisotope of Te, Ru, Co, Pt, Re, Os, Ir, W, Re, Cr, Mo, Mn, Ni, Rh, Nb and Ta from a non-radioactive metal adduct of the isonitrile

Synthesis and characterization of the 1.1 adducts of copper(1) halides with bidentatate N,N-bis(benzophenone)-1,2-diiminoethane Schiff bases: Crystal structures of [Cu(bz2en)2][CuX2](X=Br,l) complexes

NARCIS (Netherlands)

Kia, Reza; Mirkhani, Valiollah; Harkema, Sybolt; van Hummel, G.J.

2007-01-01

1:1 adducts of N,N′-bis(benzophenone)-1,2-diiminoethane (bz2en) with copper(I) chloride, bromide and iodide, [Cu(bz2en)2][CuX2] (X = Cl, Br, and I), have been synthesized and the structures of the solid bromide and iodide adducts were determined by X-ray crystallography from single-crystal data. The

Protein tyrosine adduct in humans self-poisoned by chlorpyrifos

International Nuclear Information System (INIS)

Li, Bin; Eyer, Peter; Eddleston, Michael; Jiang, Wei; Schopfer, Lawrence M.; Lockridge, Oksana

2013-01-01

Studies of human cases of self-inflicted poisoning suggest that chlorpyrifos oxon reacts not only with acetylcholinesterase and butyrylcholinesterase but also with other blood proteins. A favored candidate is albumin because in vitro and animal studies have identified tyrosine 411 of albumin as a site covalently modified by organophosphorus poisons. Our goal was to test this proposal in humans by determining whether plasma from humans poisoned by chlorpyrifos has adducts on tyrosine. Plasma samples from 5 self-poisoned humans were drawn at various time intervals after ingestion of chlorpyrifos for a total of 34 samples. All 34 samples were analyzed for plasma levels of chlorpyrifos and chlorpyrifos oxon (CPO) as a function of time post-ingestion. Eleven samples were analyzed for the presence of diethoxyphosphorylated tyrosine by mass spectrometry. Six samples yielded diethoxyphosphorylated tyrosine in pronase digests. Blood collected as late as 5 days after chlorpyrifos ingestion was positive for CPO-tyrosine, consistent with the 20-day half-life of albumin. High plasma CPO levels did not predict detectable levels of CPO-tyrosine. CPO-tyrosine was identified in pralidoxime treated patients as well as in patients not treated with pralidoxime, indicating that pralidoxime does not reverse CPO binding to tyrosine in humans. Plasma butyrylcholinesterase was a more sensitive biomarker of exposure than adducts on tyrosine. In conclusion, chlorpyrifos oxon makes a stable covalent adduct on the tyrosine residue of blood proteins in humans who ingested chlorpyrifos. - Highlights: • Chlorpyrifos-poisoned patients have adducts on protein tyrosine. • Diethoxyphosphate-tyrosine does not lose an alkyl group. • Proteins in addition to AChE and BChE are modified by organophosphates

Protein tyrosine adduct in humans self-poisoned by chlorpyrifos

Energy Technology Data Exchange (ETDEWEB)

Li, Bin, E-mail: binli@unmc.edu [Eppley Institute, University of Nebraska Medical Center, Omaha, NE 68198-5950 (United States); Eyer, Peter, E-mail: peter.eyer@lrz.uni-muenchen.de [Walther-Straub-Institut Für Pharmakologie und Toxikologie, Ludwig-Maximilians-Universität München, 80336 München (Germany); Eddleston, Michael, E-mail: M.Eddleston@ed.ac.uk [Clinical Pharmacology Unit, University of Edinburgh, Edinburgh (United Kingdom); Jiang, Wei, E-mail: wjiang@unmc.edu [Eppley Institute, University of Nebraska Medical Center, Omaha, NE 68198-5950 (United States); Schopfer, Lawrence M., E-mail: lmschopf@unmc.edu [Eppley Institute, University of Nebraska Medical Center, Omaha, NE 68198-5950 (United States); Lockridge, Oksana, E-mail: olockrid@unmc.edu [Eppley Institute, University of Nebraska Medical Center, Omaha, NE 68198-5950 (United States)

2013-06-15

Studies of human cases of self-inflicted poisoning suggest that chlorpyrifos oxon reacts not only with acetylcholinesterase and butyrylcholinesterase but also with other blood proteins. A favored candidate is albumin because in vitro and animal studies have identified tyrosine 411 of albumin as a site covalently modified by organophosphorus poisons. Our goal was to test this proposal in humans by determining whether plasma from humans poisoned by chlorpyrifos has adducts on tyrosine. Plasma samples from 5 self-poisoned humans were drawn at various time intervals after ingestion of chlorpyrifos for a total of 34 samples. All 34 samples were analyzed for plasma levels of chlorpyrifos and chlorpyrifos oxon (CPO) as a function of time post-ingestion. Eleven samples were analyzed for the presence of diethoxyphosphorylated tyrosine by mass spectrometry. Six samples yielded diethoxyphosphorylated tyrosine in pronase digests. Blood collected as late as 5 days after chlorpyrifos ingestion was positive for CPO-tyrosine, consistent with the 20-day half-life of albumin. High plasma CPO levels did not predict detectable levels of CPO-tyrosine. CPO-tyrosine was identified in pralidoxime treated patients as well as in patients not treated with pralidoxime, indicating that pralidoxime does not reverse CPO binding to tyrosine in humans. Plasma butyrylcholinesterase was a more sensitive biomarker of exposure than adducts on tyrosine. In conclusion, chlorpyrifos oxon makes a stable covalent adduct on the tyrosine residue of blood proteins in humans who ingested chlorpyrifos. - Highlights: • Chlorpyrifos-poisoned patients have adducts on protein tyrosine. • Diethoxyphosphate-tyrosine does not lose an alkyl group. • Proteins in addition to AChE and BChE are modified by organophosphates.

Biomass Burning and Natural Emissions in the Brazilian Amazon Rainforest: Chemical Composition and Impact on the Oxidative Capacity of the Atmosphere

Science.gov (United States)

dos Santos, F. C.; Longo, K.; Guenther, A. B.; Gu, D.; Kim, S.; Freitas, S.; Moreira, D. S.; Flávio, L.; Braz, R.; Brito, J.; Oram, D.; Foster, G.; Lee, J. D.

2017-12-01

Emitted by vegetation, isoprene (2-methyl-1,3-butadiene) is the most abundant non-methane hydrocarbons, with an annual global emission calculated ranging from 440 to 660Tg carbon, depending on the driving variables like temperature, solar radiation, LAI and PFT. The natural compounds like isoprene and terpenes present in the troposphere are about 90% and 50%, respectively, removed from the atmosphere by oxidation performed by hydroxyl radical (OH). Considering the importance of these emissions and the hydroxyl radical reaction in the atmosphere, the SAMBBA (South American Biomass Burning Analysis) experiment, which occurred during the dry season (September 2012) in the Brazilian Amazon Rainforest, provided information about the chemical composition of the atmosphere through airborne observations. Although primarily focused on biomass burning flights, the SAMBBA project carried out flights in pristine environment. In this study, we determine the ambient distribution of CO, NOx and O3, and evaluate the oxidative capacity of the Amazon rainforest in different chemical regimes, using the ratio [MVK + MACR]/[Isoprene]. Beyond that, we proposed an improvement on the formulation of indirect OH density calculation, using the photochemical aging [O3]/[CO] as a parameter. Balancing numerical modeling and direct observations, the numerical model BRAMS was coupled to MEGAN emission model to get a better result for isoprene and OH in the atmosphere, representing the observations during SAMBBA field campaign. In relation to OH estimation, we observed an improvement in the concentration values using the modified sequential reaction model, for both biomass burning regimes and background environment. We also detected a long-range transport events of O3, considering the high levels of O3 in aged plumes at high altitudes (5,500 - 6,500 m), and the detection of an O3 inflow in the Amazon basin from Africa. These findings support the importance of long-range transport events as a

Investigating causality in the association between 25(OH)D and schizophrenia.

Science.gov (United States)

Taylor, Amy E; Burgess, Stephen; Ware, Jennifer J; Gage, Suzanne H; Richards, J Brent; Davey Smith, George; Munafò, Marcus R

2016-05-24

Vitamin D deficiency is associated with increased risk of schizophrenia. However, it is not known whether this association is causal or what the direction of causality is. We performed two sample bidirectional Mendelian randomization analysis using single nucleotide polymorphisms (SNPs) robustly associated with serum 25(OH)D to investigate the causal effect of 25(OH)D on risk of schizophrenia, and SNPs robustly associated with schizophrenia to investigate the causal effect of schizophrenia on 25(OH)D. We used summary data from genome-wide association studies and meta-analyses of schizophrenia and 25(OH)D to obtain betas and standard errors for the SNP-exposure and SNP-outcome associations. These were combined using inverse variance weighted fixed effects meta-analyses. In 34,241 schizophrenia cases and 45,604 controls, there was no clear evidence for a causal effect of 25(OH)D on schizophrenia risk. The odds ratio for schizophrenia per 10% increase in 25(OH)D conferred by the four 25(OH)D increasing SNPs was 0.992 (95% CI: 0.969 to 1.015). In up to 16,125 individuals with measured serum 25(OH)D, there was no clear evidence that genetic risk for schizophrenia causally lowers serum 25(OH)D. These findings suggest that associations between schizophrenia and serum 25(OH)D may not be causal. Therefore, vitamin D supplementation may not prevent schizophrenia.

Molybdenum(V, germanium(IV, aluminum(III and nickel(II adducts with ethyleneurea, ethylenethiourea and propyleneurea: some empirical correlations involving TG and IR data

Directory of Open Access Journals (Sweden)

ROBSON F. DE FARIAS

2006-03-01

Full Text Available The adducts MoCl5·2eu, MoCl5·2pu, GeCl4·2etu, AlCl3·2pu, AlCl3·3pu, NiCl2·2etu and NiCl2·4etu (eu = ethyleneurea, etu = ethylenethiourea and pu =propyleneurea were synthesized and characterized by elemental analysis (C, H, N, infrared spectroscopy (IR and thermogravimetry (TG. IR Results show that eu and pu coordinate through oxygen, whereas etu coordinates through nitrogen. For all investigated adducts, a single mass loss step associated with the release of ligand molecules is observed. Empirical correlations involving TG and IR data are established.

DNA adduct formation and mutation induction by aristolochic acid in rat kidney and liver

International Nuclear Information System (INIS)

Mei, Nan; Arlt, Volker M.; Phillips, David H.; Heflich, Robert H.; Chen, Tao

2006-01-01

Aristolochic acid (AA) is a potent nephrotoxin and carcinogen and is the causative factor for Chinese herb nephropathy. AA has been associated with the development of urothelial cancer in humans, and kidney and forestomach tumors in rodents. To investigate the molecular mechanisms responsible for the tumorigenicity of AA, we determined the DNA adduct formation and mutagenicity of AA in the liver (nontarget tissue) and kidney (target tissue) of Big Blue rats. Groups of six male rats were gavaged with 0, 0.1, 1.0 and 10.0 mg AA/kg body weight five times/week for 3 months. The rats were sacrificed 1 day after the final treatment, and the livers and kidneys were isolated. DNA adduct formation was analyzed by 32 P-postlabeling and mutant frequency (MF) was determined using the λ Select-cII Mutation Detection System. Three major adducts (7-[deoxyadenosin-N 6 -yl]-aristolactam I, 7-[deoxyadenosin-N 6 -yl]-aristolactam II and 7-[deoxyguanosin-N 2 -yl]-aristolactam I) were identified. There were strong linear dose-responses for AA-induced DNA adducts in treated rats, ranging from 25 to 1967 adducts/10 8 nucleotides in liver and 95-4598 adducts/10 8 nucleotides in kidney. A similar trend of dose-responses for mutation induction also was found, the MFs ranging from 37 to 666 x 10 -6 in liver compared with the MFs of 78-1319 x 10 -6 that we previously reported for the kidneys of AA-treated rats. Overall, kidneys had at least two-fold higher levels of DNA adducts and MF than livers. Sequence analysis of the cII mutants revealed that there was a statistically significant difference between the mutation spectra in both kidney and liver of AA-treated and control rats, but there was no significant difference between the mutation spectra in AA-treated livers and kidneys. A:T → T:A transversion was the predominant mutation in AA-treated rats; whereas G:C → A:T transition was the main type of mutation in control rats. These results indicate that the AA treatment that eventually

DNA adduct formation and mutation induction by aristolochic acid in rat kidney and liver

Energy Technology Data Exchange (ETDEWEB)

Mei, Nan [Division of Genetic and Reproductive Toxicology, National Center for Toxicological Research, FDA, Jefferson, AR 72079 (United States)]. E-mail: nan.mei@fda.hhs.gov; Arlt, Volker M. [Section of Molecular Carcinogenesis, Institute of Cancer Research, Cotswold Road, Sutton, Surrey SM2 5NG (United Kingdom); Phillips, David H. [Section of Molecular Carcinogenesis, Institute of Cancer Research, Cotswold Road, Sutton, Surrey SM2 5NG (United Kingdom); Heflich, Robert H. [Division of Genetic and Reproductive Toxicology, National Center for Toxicological Research, FDA, Jefferson, AR 72079 (United States); Chen, Tao [Division of Genetic and Reproductive Toxicology, National Center for Toxicological Research, FDA, Jefferson, AR 72079 (United States)

2006-12-01

Aristolochic acid (AA) is a potent nephrotoxin and carcinogen and is the causative factor for Chinese herb nephropathy. AA has been associated with the development of urothelial cancer in humans, and kidney and forestomach tumors in rodents. To investigate the molecular mechanisms responsible for the tumorigenicity of AA, we determined the DNA adduct formation and mutagenicity of AA in the liver (nontarget tissue) and kidney (target tissue) of Big Blue rats. Groups of six male rats were gavaged with 0, 0.1, 1.0 and 10.0 mg AA/kg body weight five times/week for 3 months. The rats were sacrificed 1 day after the final treatment, and the livers and kidneys were isolated. DNA adduct formation was analyzed by {sup 32}P-postlabeling and mutant frequency (MF) was determined using the {lambda} Select-cII Mutation Detection System. Three major adducts (7-[deoxyadenosin-N {sup 6}-yl]-aristolactam I, 7-[deoxyadenosin-N {sup 6}-yl]-aristolactam II and 7-[deoxyguanosin-N {sup 2}-yl]-aristolactam I) were identified. There were strong linear dose-responses for AA-induced DNA adducts in treated rats, ranging from 25 to 1967 adducts/10{sup 8} nucleotides in liver and 95-4598 adducts/10{sup 8} nucleotides in kidney. A similar trend of dose-responses for mutation induction also was found, the MFs ranging from 37 to 666 x 10{sup -6} in liver compared with the MFs of 78-1319 x 10{sup -6} that we previously reported for the kidneys of AA-treated rats. Overall, kidneys had at least two-fold higher levels of DNA adducts and MF than livers. Sequence analysis of the cII mutants revealed that there was a statistically significant difference between the mutation spectra in both kidney and liver of AA-treated and control rats, but there was no significant difference between the mutation spectra in AA-treated livers and kidneys. A:T {sup {yields}} T:A transversion was the predominant mutation in AA-treated rats; whereas G:C {sup {yields}} A:T transition was the main type of mutation in control

Electrophilic properties of patulin. Adduct structures and reaction pathways with 4-bromothiophenol and other model nucleophiles.

Science.gov (United States)

Fliege, R; Metzler, M

2000-05-01

The mycotoxin patulin (PAT) is believed to exert its cytotoxic and chromosome-damaging effects by forming covalent adducts with essential cellular thiols. Since the chemical structures of such adducts are unknown to date, we have studied the reaction of PAT and its O-acetylated derivative with the monofunctional thiol model compound 4-bromothiophenol (BTP), which was chosen due to analytical advantages. By means of analytical and preparative high-performance liquid chromatography, 16 adducts of PAT and 3 adducts of acetyl-PAT were isolated and their chemical structures elucidated by (1)H and (13)C NMR, IR, and UV spectroscopy. Time course studies and analysis of daughter product formation from isolated intermediate adducts led to a detailed scheme for the reaction of PAT with BTP. The structures of adducts of PAT formed with other model nucleophiles, e. g., the aliphatic thiol 2-mercaptoethanol and the aromatic amine 4-bromoaniline, were also elucidated and found to corroborate the reaction scheme. In addition, one further reaction pathway was observed with 2-mercaptoethanol, which appears to be independent from those found for BTP. Our study with model nucleophiles provides insights into the electrophilic reactivity of PAT and proved to be useful for the structure elucidation of PAT adducts with biological nucleophiles of toxicological relevance, as will be reported by Fliege and Metzler [(2000) Chem. Res. Toxicol. 13, 373-381].

Capturing Labile Sulfenamide and Sulfinamide Serum Albumin Adducts of Carcinogenic Arylamines by Chemical Oxidation

Science.gov (United States)

Peng, Lijuan; Turesky, Robert J.

2013-01-01

Aromatic amines and heterocyclic aromatic amines (HAAs) are a class of structurally related carcinogens that are formed during the combustion of tobacco or during the high temperature cooking of meats. These procarcinogens undergo metabolic activation by N-oxidation of the exocyclic amine group to produce N-hydroxylated metabolites, which are critical intermediates implicated in toxicity and DNA damage. The arylhydroxylamines and their oxidized arylnitroso derivatives can also react with cysteine (Cys) residues of glutathione or proteins to form, respectively, sulfenamide and sulfinamide adducts. However, sulfur-nitrogen linked adducted proteins are often difficult to detect because they are unstable and undergo hydrolysis during proteolytic digestion. Synthetic N-oxidized intermediates of 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), a carcinogenic HAA produced in cooked meats, and 4-aminobiphenyl, a carcinogenic aromatic amine present in tobacco smoke were reacted with human serum albumin (SA) and formed labile sulfenamide or sulfinamide adducts at the Cys34 residue. Oxidation of the carcinogen-modified SA with m-chloroperoxybenzoic acid (m-CPBA) produced the arylsulfonamide adducts, which were stable to heat and the chemical reduction conditions employed to denature SA. The sulfonamide adducts of PhIP and 4-ABP were identified, by liquid chromatography/mass spectrometry, in proteolytic digests of denatured SA. Thus, selective oxidation of arylamine-modified SA produces stable arylsulfonamide-SA adducts, which may serve as biomarkers of these tobacco and dietary carcinogens. PMID:23240913

Exposure to meat-derived carcinogens and bulky DNA adduct levels in normal-appearing colon mucosa.

Science.gov (United States)

Ho, Vikki; Brunetti, Vanessa; Peacock, Sarah; Massey, Thomas E; Godschalk, Roger W L; van Schooten, Frederik J; Ashbury, Janet E; Vanner, Stephen J; King, Will D

2017-09-01

Meat consumption is a risk factor for colorectal cancer. This research investigated the relationship between meat-derived carcinogen exposure and bulky DNA adduct levels, a biomarker of DNA damage, in colon mucosa. Least squares regression was used to examine the relationship between meat-derived carcinogen exposure (PhIP and meat mutagenicity) and bulky DNA adduct levels in normal-appearing colon tissue measured using 32 P-postlabelling among 202 patients undergoing a screening colonoscopy. Gene-diet interactions between carcinogen exposure and genetic factors relevant to biotransformation and DNA repair were also examined. Genotyping was conducting using the MassARRAY ® iPLEX ® Gold SNP Genotyping assay. PhIP and higher meat mutagenicity exposures were not associated with levels of bulky DNA adducts in colon mucosa. The XPC polymorphism (rs2228001) was found to associate with bulky DNA adduct levels, whereby genotypes conferring lower DNA repair activity were associated with higher DNA adduct levels than the normal activity genotype. Among individuals with genotypes associated with lower DNA repair (XPD, rs13181 and rs1799179) or detoxification activity (GSTP1, rs1695), higher PhIP or meat mutagenicity exposures were associated with higher DNA adduct levels. Significant interactions between the XPC polymorphism (rs2228000) and both dietary PhIP and meat mutagenicity on DNA adduct levels was observed, but associations were inconsistent with the a priori hypothesized direction of effect. Exposure to meat-derived carcinogens may be associated with increased DNA damage occurring directly in the colon among genetically susceptible individuals. Copyright © 2017 Elsevier B.V. All rights reserved.

PAH-DNA adducts in environmentally exposed population in relation to metabolic and DNA repair gene polymorphisms

Energy Technology Data Exchange (ETDEWEB)

Binkova, Blanka [Laboratory of Genetic Ecotoxicology, Institute of Experimental Medicine AS CR and Health Institute of Central Bohemia, Videnska 1083, 14220 Prague (Czech Republic); Chvatalova, Irena [Laboratory of Genetic Ecotoxicology, Institute of Experimental Medicine AS CR and Health Institute of Central Bohemia, Videnska 1083, 14220 Prague (Czech Republic); Lnenickova, Zdena [Laboratory of Genetic Ecotoxicology, Institute of Experimental Medicine AS CR and Health Institute of Central Bohemia, Videnska 1083, 14220 Prague (Czech Republic); Milcova, Alena [Laboratory of Genetic Ecotoxicology, Institute of Experimental Medicine AS CR and Health Institute of Central Bohemia, Videnska 1083, 14220 Prague (Czech Republic); Tulupova, Elena [Laboratory of Genetic Ecotoxicology, Institute of Experimental Medicine AS CR and Health Institute of Central Bohemia, Videnska 1083, 14220 Prague (Czech Republic); Cancer Biomarkers and Prevention Group, Biocentre, University of Leicester (United Kingdom); Farmer, Peter B. [Cancer Biomarkers and Prevention Group, Biocentre, University of Leicester (United Kingdom); Sram, Radim J. [Laboratory of Genetic Ecotoxicology, Institute of Experimental Medicine AS CR and Health Institute of Central Bohemia, Videnska 1083, 14220 Prague (Czech Republic)]. E-mail: sram@biomed.cas.cz

2007-07-01

Epidemiologic studies indicate that prolonged exposure to particulate air pollution may be associated with increased risk of cardiovascular diseases and cancer in general population. These effects may be attributable to polycyclic aromatic hydrocarbons (PAHs) adsorbed to respirable air particles. It is expected that metabolic and DNA repair gene polymorphisms may modulate individual susceptibility to PAH exposure. This study investigates relationships between exposure to PAHs, polymorphisms of these genes and DNA adducts in group of occupationally exposed policemen (EXP, N = 53, males, aged 22-50 years) working outdoors in the downtown area of Prague and in matched 'unexposed' controls (CON, N = 52). Personal exposure to eight carcinogenic PAHs (c-PAHs) was evaluated by personal samplers during working shift prior to collection of biological samples. Bulky-aromatic DNA adducts were analyzed in lymphocytes by {sup 32}P-postlabeling assay. Polymorphisms of metabolizing (GSTM1, GSTP1, GSTT1, EPHX1, CYP1A1-MspI) and DNA repair (XRCC1, XPD) genes were determined by PCR-based RFLP assays. As potential modifiers and/or cofounders, urinary cotinine levels were analyzed by radioimmunoassay, plasma levels of vitamins A, C, E and folates by HPLC, cholesterol and triglycerides using commercial kits. During the sampling period ambient particulate air pollution was as follows: PM10 32-55 {mu}g/m{sup 3}, PM2.5 27-38 {mu}g/m{sup 3}, c-PAHs 18-22 ng/m{sup 3}; personal exposure to c-PAHs: 9.7 ng/m{sup 3} versus 5.8 ng/m{sup 3} (P < 0.01) for EXP and CON groups, respectively. The total DNA adduct levels did not significantly differ between EXP and CON groups (0.92 {+-} 0.28 adducts/10{sup 8} nucleotides versus 0.82 {+-} 0.23 adducts/10{sup 8} nucleotides, P = 0.065), whereas the level of the B[a]P-'like' adduct was significantly higher in exposed group (0.122 {+-} 0.036 adducts/10{sup 8} nucleotides versus 0.099 {+-} 0.035 adducts/10{sup 8} nucleotides, P = 0

Production of extremely low volatile organic compounds from biogenic emissions: Measured yields and atmospheric implications.

Science.gov (United States)

Jokinen, Tuija; Berndt, Torsten; Makkonen, Risto; Kerminen, Veli-Matti; Junninen, Heikki; Paasonen, Pauli; Stratmann, Frank; Herrmann, Hartmut; Guenther, Alex B; Worsnop, Douglas R; Kulmala, Markku; Ehn, Mikael; Sipilä, Mikko

2015-06-09

Oxidation products of monoterpenes and isoprene have a major influence on the global secondary organic aerosol (SOA) burden and the production of atmospheric nanoparticles and cloud condensation nuclei (CCN). Here, we investigate the formation of extremely low volatility organic compounds (ELVOC) from O3 and OH radical oxidation of several monoterpenes and isoprene in a series of laboratory experiments. We show that ELVOC from all precursors are formed within the first minute after the initial attack of an oxidant. We demonstrate that under atmospherically relevant concentrations, species with an endocyclic double bond efficiently produce ELVOC from ozonolysis, whereas the yields from OH radical-initiated reactions are smaller. If the double bond is exocyclic or the compound itself is acyclic, ozonolysis produces less ELVOC and the role of the OH radical-initiated ELVOC formation is increased. Isoprene oxidation produces marginal quantities of ELVOC regardless of the oxidant. Implementing our laboratory findings into a global modeling framework shows that biogenic SOA formation in general, and ELVOC in particular, play crucial roles in atmospheric CCN production. Monoterpene oxidation products enhance atmospheric new particle formation and growth in most continental regions, thereby increasing CCN concentrations, especially at high values of cloud supersaturation. Isoprene-derived SOA tends to suppress atmospheric new particle formation, yet it assists the growth of sub-CCN-size primary particles to CCN. Taking into account compound specific monoterpene emissions has a moderate effect on the modeled global CCN budget.

Synthesis, crystal growth and characterization of bioactive material: 2-amino-1H-benzo[d]imidazol-3-ium salicylate single crystal-a proton transfer molecular complex

Science.gov (United States)

Fathima, K. Saiadali; Anitha, K.

2017-05-01

The 1:1 molecular adducts 2-aminobenzimidazolium salicylate (ABIS) single crystal was synthesized and grown from 2-aminobenzimidazole (ABI) as a donor and salicylic acid (SA) as an acceptor. The cell parameter was determined using single crystal X-Ray diffraction method and the complex ABIS belongs to monoclinic system. The spectroscopic studies showed that ABIS crystal was an ion pair complex. The FTIR and Raman spectra showed that the presence of O-H, C=N, C=O vibration which confirms the proton transfer from SA to ABI. The UV-Vis spectrum exhibited a visible band at 359nm for ABIS due to the salicylate anion of the molecule. Further the antimicrobial activity of ABIS complex against Staphylococcus aureus, klebsiella pneumonia, Pseudomonas eruginos and E.coli pathogens was investigated. So the complex molecule inhibits both Gram positive and Gram negative bacterial. It is found that benzimidazole with aminogroup at position 2 increases the general antimicrobial activities of ABIS crystal.

Sequence distribution of acetaldehyde-derived N2-ethyl-dG adducts along duplex DNA.

Science.gov (United States)

Matter, Brock; Guza, Rebecca; Zhao, Jianwei; Li, Zhong-ze; Jones, Roger; Tretyakova, Natalia

2007-10-01

Acetaldehyde (AA) is the major metabolite of ethanol and may be responsible for an increased gastrointestinal cancer risk associated with alcohol beverage consumption. Furthermore, AA is one of the most abundant carcinogens in tobacco smoke and induces tumors of the respiratory tract in laboratory animals. AA binding to DNA induces Schiff base adducts at the exocyclic amino group of dG, N2-ethylidene-dG, which are reversible on the nucleoside level but can be stabilized by reduction to N2-ethyl-dG. Mutagenesis studies in the HPRT reporter gene and in the p53 tumor suppressor gene have revealed the ability of AA to induce G-->A transitions and A-->T transversions, as well as frameshift and splice mutations. AA-induced point mutations are most prominent at 5'-AGG-3' trinucleotides, possibly a result of sequence specific adduct formation, mispairing, and/or repair. However, DNA sequence preferences for the formation of acetaldehyde adducts have not been previously examined. In the present work, we employed a stable isotope labeling-HPLC-ESI+-MS/MS approach developed in our laboratory to analyze the distribution of acetaldehyde-derived N2-ethyl-dG adducts along double-stranded oligodeoxynucleotides representing two prominent lung cancer mutational "hotspots" and their surrounding DNA sequences. 1,7,NH 2-(15)N-2-(13)C-dG was placed at defined positions within DNA duplexes derived from the K-ras protooncogene and the p53 tumor suppressor gene, followed by AA treatment and NaBH 3CN reduction to convert N2-ethylidene-dG to N2-ethyl-dG. Capillary HPLC-ESI+-MS/MS was used to quantify N2-ethyl-dG adducts originating from the isotopically labeled and unlabeled guanine nucleobases and to map adduct formation along DNA duplexes. We found that the formation of N2-ethyl-dG adducts was only weakly affected by the local sequence context and was slightly increased in the presence of 5-methylcytosine within CG dinucleotides. These results are in contrast with sequence

DNA adduct measurements in zebra mussels, Dreissena polymorpha, Pallas. Potential use for genotoxicant biomonitoring of fresh water ecosystems.

Science.gov (United States)

Le Goff, J; Gallois, J; Pelhuet, L; Devier, M H; Budzinski, H; Pottier, D; André, V; Cachot, J

2006-08-12

The purpose of this study was to examine PAH accumulation and bulky DNA adduct formation in the digestive gland of zebra mussels exposed in their habitat or in controlled laboratory conditions to complex mixture of PAH. DNA adducts were measured using a 32P-postlabelling protocol with nuclease P1 enrichment adapted from Reddy and Randerath [Reddy, M.V., Randerath, K., 1986. Nuclease P1-mediated enhancement of sensitivity of 32P-postlabelling test for structurally diverse DNA adducts. Carcinogenesis 7, 1543-1551]. Specimens collected in the upper part of the Seine estuary were shown to accumulate higher levels of PAH (up to 1.6 microg g(-1) dry weight) in comparison to individuals from the reference site (0.053 microg g(-1) dry weight). The former exhibited elevated levels of DNA adducts (up to 4.0/10(8) nucleotides) and higher diversity of individual adducts with five distinct spots being specifically detected in individuals originating from the Seine estuary. Zebra mussels exposed for 5 days to 0.01% (v/v) of organic extract of sediment from the Seine estuary were shown to accumulate high amounts of PAH (up to 138 microg g(-1) dry weight) but exhibited relatively low levels of DNA adducts. Exposure to benzo[a]pyrene led to a dose-dependent accumulation of B[a]P (up to 7063 microg g(-1) dry weight) and a clear induction of DNA adduct formation in the digestive gland of mussels (up to 1.13/10(8) nucleotides). Comparisons with other bivalves exposed to the same model PAH, revealed similar levels of adducts and comparable adduct profiles with a main adduct spot and a second faint one. This study clearly demonstrated that zebra mussels are able to biotransform B[a]P and probably other PAH into reactive metabolites with DNA-binding activity. This work also demonstrated the applicability of the nuclease P1 enhanced 32P-postlabelling method for bulky adduct detection in the digestive gland of zebra mussels. DNA adduct measurement in zebra mussels could be a suitable

Pulse radiolysis study on oxidation reactions of gallic acid

International Nuclear Information System (INIS)

Dwibedy, P.; Dey, G.R.; Naik, D.B.; Kishore, Kamal

1998-01-01

Reactions of OH . /O - and other oxidising radicals viz. N 3 . , Br 2 .- , Cl 2 .- with gallic acid (GA) have been studied at various pHs. At pH 6.8, OH . radicals react with GA giving an adduct which in turn reacts with the parent GA to give a dimeric species. At pH 9.7, the initial OH adduct formed is able to oxidize GA to give a semi-oxidised species. At pH 12 and ∼ 13.6, OH . /O .- radicals directly bring about oxidation of GA. (author)

Polycyclic aromatic hydrocarbon-DNA adducts in cervix of women infected with carcinogenic human papillomavirus types: An immunohistochemistry study

International Nuclear Information System (INIS)

Pratt, M. Margaret; Sirajuddin, Paul; Poirier, Miriam C.; Schiffman, Mark; Glass, Andrew G.; Scott, David R.; Rush, Brenda B.; Olivero, Ofelia A.; Castle, Philip E.

2007-01-01

Among women infected with carcinogenic human papillomavirus (HPV), there is a two- to five-fold increased risk of cervical precancer and cancer in women who smoke compared to those who do not smoke. Because tobacco smoke contains carcinogenic polycyclic aromatic hydrocarbons (PAHs), it was of interest to examine human cervical tissue for PAH-DNA adduct formation. Here, we measured PAH-DNA adduct formation in cervical biopsies collected in follow-up among women who tested positive for carcinogenic HPV at baseline. A semi-quantitative immunohistochemistry (IHC) method using antiserum elicited against DNA modified with r7,t8-dihydroxy-t-9,10-oxy-7,8,9,10-tetrahydrobenzo[a]pyrene (BPDE) was used to measure nuclear PAH-DNA adduct formation. Cultured human cervical keratinocytes exposed to 0, 0.153, or 0.331 μM BPDE showed dose-dependent increases in r7,t8,t9-trihydroxy-c-10-(N 2 deoxyguanosyl)-7,8,9, 10-tetrahydro-benzo[a]pyrene (BPdG) adducts. For BPdG adduct analysis, paraffin-embedded keratinocytes were stained by IHC with analysis of nuclear color intensity by Automated Cellular Imaging System (ACIS) and, in parallel cultures, extracted DNA was assayed by quantitative BPDE-DNA chemiluminescence immunoassay (CIA). For paraffin-embedded samples from carcinogenic HPV-infected women, normal-appearing cervical squamous epithelium suitable for scoring was found in samples from 75 of the 114 individuals, including 29 cases of cervical precancer or cancer and 46 controls. With a lower limit of detection of 20 adducts/10 8 nucleotides, detectable PAH-DNA adduct values ranged from 25 to 191/10 8 nucleotides, with a median of 75/10 8 nucleotides. PAH-DNA adduct values above 150/10 8 nucleotides were found in eight samples, and in three samples adducts were non-detectable. There was no correlation between PAH-DNA adduct formation and either smoking or case status. Therefore, PAH-DNA adduct formation as measured by this methodology did not appear related to the increased risk

Polycyclic aromatic hydrocarbon-DNA adducts in cervix of women infected with carcinogenic human papillomavirus types: An immunohistochemistry study

Energy Technology Data Exchange (ETDEWEB)

Pratt, M. Margaret [Carcinogen-DNA Interactions Section, LCBG, Center for Cancer Research, National Cancer Institute, NIH, Bethesda, MD (United States)], E-mail: prattm@mail.nih.gov; Sirajuddin, Paul; Poirier, Miriam C. [Carcinogen-DNA Interactions Section, LCBG, Center for Cancer Research, National Cancer Institute, NIH, Bethesda, MD (United States); Schiffman, Mark [Hormonal and Reproductive Epidemiology Branch, Division of Cancer Epidemiology and Genetics, National Cancer Institute, NIH, Bethesda, MD (United States); Glass, Andrew G.; Scott, David R.; Rush, Brenda B. [Northwest Kaiser Permanente, Portland, OR (United States); Olivero, Ofelia A. [Carcinogen-DNA Interactions Section, LCBG, Center for Cancer Research, National Cancer Institute, NIH, Bethesda, MD (United States); Castle, Philip E. [Hormonal and Reproductive Epidemiology Branch, Division of Cancer Epidemiology and Genetics, National Cancer Institute, NIH, Bethesda, MD (United States)

2007-11-01

Among women infected with carcinogenic human papillomavirus (HPV), there is a two- to five-fold increased risk of cervical precancer and cancer in women who smoke compared to those who do not smoke. Because tobacco smoke contains carcinogenic polycyclic aromatic hydrocarbons (PAHs), it was of interest to examine human cervical tissue for PAH-DNA adduct formation. Here, we measured PAH-DNA adduct formation in cervical biopsies collected in follow-up among women who tested positive for carcinogenic HPV at baseline. A semi-quantitative immunohistochemistry (IHC) method using antiserum elicited against DNA modified with r7,t8-dihydroxy-t-9,10-oxy-7,8,9,10-tetrahydrobenzo[a]pyrene (BPDE) was used to measure nuclear PAH-DNA adduct formation. Cultured human cervical keratinocytes exposed to 0, 0.153, or 0.331 {mu}M BPDE showed dose-dependent increases in r7,t8,t9-trihydroxy-c-10-(N{sup 2}deoxyguanosyl)-7,8,9, 10-tetrahydro-benzo[a]pyrene (BPdG) adducts. For BPdG adduct analysis, paraffin-embedded keratinocytes were stained by IHC with analysis of nuclear color intensity by Automated Cellular Imaging System (ACIS) and, in parallel cultures, extracted DNA was assayed by quantitative BPDE-DNA chemiluminescence immunoassay (CIA). For paraffin-embedded samples from carcinogenic HPV-infected women, normal-appearing cervical squamous epithelium suitable for scoring was found in samples from 75 of the 114 individuals, including 29 cases of cervical precancer or cancer and 46 controls. With a lower limit of detection of 20 adducts/10{sup 8} nucleotides, detectable PAH-DNA adduct values ranged from 25 to 191/10{sup 8} nucleotides, with a median of 75/10{sup 8} nucleotides. PAH-DNA adduct values above 150/10{sup 8} nucleotides were found in eight samples, and in three samples adducts were non-detectable. There was no correlation between PAH-DNA adduct formation and either smoking or case status. Therefore, PAH-DNA adduct formation as measured by this methodology did not appear

Vibrational spectroscopic study of poldervaartite CaCa[SiO3(OH)(OH)

Science.gov (United States)

Frost, Ray L.; López, Andrés; Scholz, Ricardo; Lima, Rosa Malena Fernandes

2015-02-01

We have studied the mineral poldervaartite CaCa[SiO3(OH)(OH)] which forms a series with its manganese analogue olmiite CaMn[SiO3(OH)](OH) using a range of techniques including scanning electron microscopy, thermogravimetric analysis, Raman and infrared spectroscopy. Chemical analysis shows the mineral is reasonably pure and contains only calcium and manganese with low amounts of Al and F. Thermogravimetric analysis proves the mineral decomposes at 485 °C with a mass loss of 7.6% compared with the theoretical mass loss of 7.7%. A strong Raman band at 852 cm-1 is assigned to the SiO stretching vibration of the SiO3(OH) units. Two Raman bands at 914 and 953 cm-1 are attributed to the antisymmetric vibrations. Intense prominent peaks observed at 3487, 3502, 3509, 3521 and 3547 cm-1 are assigned to the OH stretching vibration of the SiO3(OH) units. The observation of multiple OH bands supports the concept of the non-equivalence of the OH units. Vibrational spectroscopy enables a detailed assessment of the molecular structure of poldervaartite.

Analysis of hemoglobin adducts from acrylamide, glycidamide, and ethylene oxide in paired mother/cord blood samples from Denmark

DEFF Research Database (Denmark)

von Stedingk, Hans; Vikström, Anna C; Rydberg, Per

2011-01-01

The knowledge about fetal exposure to acrylamide/glycidamide from the maternal exposure through food is limited. Acrylamide, glycidamide, and ethylene oxide are electrophiles and form adducts with hemoglobin (Hb), which could be used for in vivo dose measurement. In this study, a method.......20-0.73) for glycidamide, and 0.43 (range 0.17-1.34) for ethylene oxide. In vitro studies with acrylamide and glycidamide showed a lower (0.38-0.48) rate of adduct formation with Hb in cord blood than with Hb in maternal blood, which is compatible with the structural differences in fetal and adult Hb. Together...... for analysis of Hb adducts by liquid chromatography-mass spectrometry, the adduct FIRE procedure, was applied to measurements of adducts from these compounds in maternal blood samples (n = 87) and umbilical cord blood samples (n = 219). The adduct levels from the three compounds, acrylamide, glycidamide...

PAH-DNA adducts in environmentally exposed population in relation to metabolic and DNA repair gene polymorphisms

International Nuclear Information System (INIS)

Binkova, Blanka; Chvatalova, Irena; Lnenickova, Zdena; Milcova, Alena; Tulupova, Elena; Farmer, Peter B.; Sram, Radim J.

2007-01-01

Epidemiologic studies indicate that prolonged exposure to particulate air pollution may be associated with increased risk of cardiovascular diseases and cancer in general population. These effects may be attributable to polycyclic aromatic hydrocarbons (PAHs) adsorbed to respirable air particles. It is expected that metabolic and DNA repair gene polymorphisms may modulate individual susceptibility to PAH exposure. This study investigates relationships between exposure to PAHs, polymorphisms of these genes and DNA adducts in group of occupationally exposed policemen (EXP, N = 53, males, aged 22-50 years) working outdoors in the downtown area of Prague and in matched 'unexposed' controls (CON, N = 52). Personal exposure to eight carcinogenic PAHs (c-PAHs) was evaluated by personal samplers during working shift prior to collection of biological samples. Bulky-aromatic DNA adducts were analyzed in lymphocytes by 32 P-postlabeling assay. Polymorphisms of metabolizing (GSTM1, GSTP1, GSTT1, EPHX1, CYP1A1-MspI) and DNA repair (XRCC1, XPD) genes were determined by PCR-based RFLP assays. As potential modifiers and/or cofounders, urinary cotinine levels were analyzed by radioimmunoassay, plasma levels of vitamins A, C, E and folates by HPLC, cholesterol and triglycerides using commercial kits. During the sampling period ambient particulate air pollution was as follows: PM10 32-55 μg/m 3 , PM2.5 27-38 μg/m 3 , c-PAHs 18-22 ng/m 3 ; personal exposure to c-PAHs: 9.7 ng/m 3 versus 5.8 ng/m 3 (P 8 nucleotides versus 0.82 ± 0.23 adducts/10 8 nucleotides, P = 0.065), whereas the level of the B[a]P-'like' adduct was significantly higher in exposed group (0.122 ± 0.036 adducts/10 8 nucleotides versus 0.099 ± 0.035 adducts/10 8 nucleotides, P = 0.003). A significant difference in both the total (P < 0.05) and the B[a]P-'like' DNA adducts (P < 0.01) between smokers and nonsmokers within both groups was observed. A significant positive association between DNA adduct and cotinine

Photochemical Reaction of 7,12-Dimethylbenz[a]anthracene (DMBA and Formation of DNA Covalent Adducts

Directory of Open Access Journals (Sweden)

Peter P. Fu

2005-04-01

Full Text Available DMBA, 7,12-dimethylbenz[a]anthracene, is a widely studied polycyclic aromatic hydrocarbon that has long been recognized as a probable human carcinogen. It has been found that DMBA is phototoxic in bacteria as well as in animal or human cells and photomutagenic in Salmonella typhimurium strain TA102. This article tempts to explain the photochemistry and photomutagenicity mechanism. Light irradiation converts DMBA into several photoproducts including benz[a]anthracene-7,12-dione, 7-hydroxy-12-keto-7-methylbenz[a]anthracene, 7,12-epidioxy-7,12-dihydro-DMBA, 7-hydroxymethyl-12-methylbenz[a]anthracene and 12-hydroxymethyl-7-methylbenz[a]anthracene. Structures of these photoproducts have been identified by either comparison with authentic samples or by NMR/MS. At least four other photoproducts need to be assigned. Photo-irradiation of DMBA in the presence of calf thymus DNA was similarly conducted and light-induced DMBA-DNA adducts were analyzed by 32P-postlabeling/TLC, which indicates that multiple DNA adducts were formed. This indicates that formation of DNA adducts might be the source of photomutagenicity of DMBA. Metabolites obtained from the metabolism of DMBA by rat liver microsomes were reacted with calf thymus DNA and the resulting DNA adducts were analyzed by 32P-postlabeling/TLC under identical conditions. Comparison of the DNA adduct profiles indicates that the DNA adducts formed from photo-irradiation are different from the DNA adducts formed due to the reaction of DMBA metabolites with DNA. These results suggest that photo-irradiation of DMBA can lead to genotoxicity through activation pathways different from those by microsomal metabolism of DMBA.

OH vibrational activation and decay dynamics of CH4-OH entrance channel complexes

International Nuclear Information System (INIS)

Wheeler, Martyn D.; Tsiouris, Maria; Lester, Marsha I.; Lendvay, Gyoergy

2000-01-01

Infrared spectroscopy has been utilized to examine the structure and vibrational decay dynamics of CH 4 -OH complexes that have been stabilized in the entrance channel to the CH 4 +OH hydrogen abstraction reaction. Rotationally resolved infrared spectra of the CH 4 -OH complexes have been obtained in the OH fundamental and overtone regions using an IR-UV (infrared-ultraviolet) double-resonance technique. Pure OH stretching bands have been identified at 3563.45(5) and 6961.98(4) cm-1 (origins), along with combination bands involving the simultaneous excitation of OH stretching and intermolecular bending motions. The infrared spectra exhibit extensive homogeneous broadening arising from the rapid decay of vibrationally activated CH 4 -OH complexes due to vibrational relaxation and/or reaction. Lifetimes of 38(5) and 25(3) ps for CH 4 -OH prepared with one and two quanta of OH excitation, respectively, have been extracted from the infrared spectra. The nascent distribution of the OH products from vibrational predissociation has been evaluated by ultraviolet probe laser-induced fluorescence measurements. The dominant inelastic decay channel involves the transfer of one quantum of OH stretch to the pentad of CH 4 vibrational states with energies near 3000 cm-1. The experimental findings are compared with full collision studies of vibrationally excited OH with CH 4 . In addition, ab initio electronic structure calculations have been carried out to elucidate the minimum energy configuration of the CH 4 -OH complex. The calculations predict a C 3v geometry with the hydrogen of OH pointing toward one of four equivalent faces of the CH 4 tetrahedron, consistent with the analysis of the experimental infrared spectra. (c) 2000 American Institute of Physics

Overview of VOC emissions and chemistry from PTR-TOF-MS measurements during the SusKat-ABC campaign: high acetaldehyde, isoprene and isocyanic acid in wintertime air of the Kathmandu Valley

Directory of Open Access Journals (Sweden)

C. Sarkar

2016-03-01

( ∼  1 ppb to be among the highest reported to date. Two "new" ambient compounds, namely formamide (m ∕ z  =  46.029 and acetamide (m ∕ z  =  60.051, which can photochemically produce isocyanic acid in the atmosphere, are reported in this study along with nitromethane (a tracer for diesel exhaust, which has only recently been detected in ambient studies. Two distinct periods were selected during the campaign for detailed analysis: the first was associated with high wintertime emissions of biogenic isoprene and the second with elevated levels of ambient acetonitrile, benzene and isocyanic acid from biomass burning activities. Emissions from biomass burning and biomass co-fired brick kilns were found to be the dominant sources for compounds such as propyne, propene, benzene and propanenitrile, which correlated strongly with acetonitrile (r2 > 0.7, a chemical tracer for biomass burning. The calculated total VOC OH reactivity was dominated by acetaldehyde (24.0 %, isoprene (20.2 % and propene (18.7 %, while oxygenated VOCs and isoprene collectively contributed to more than 68 % of the total ozone production potential. Based on known secondary organic aerosol (SOA yields and measured ambient concentrations in the Kathmandu Valley, the relative SOA production potential of VOCs were benzene  >  naphthalene  >  toluene  >  xylenes  >  monoterpenes  >  trimethylbenzenes  >  styrene  >  isoprene. The first ambient measurements from any site in South Asia of compounds with significant health effects such as isocyanic acid, formamide, acetamide, naphthalene and nitromethane have been reported in this study. Our results suggest that mitigation of intense wintertime biomass burning activities, in particular point sources such biomass co-fired brick kilns, would be important to reduce the emission and formation of toxic VOCs (such as benzene and isocyanic acid in the Kathmandu Valley.

Adducts of rare earth tris-acetylacetonates with dimethyl sulfoxide

International Nuclear Information System (INIS)

Dzyubenko, N.G.; Kalenichenko, Yu.V.; Martynenko, L.I.

1988-01-01

Adducts of rare earth and yttrium (r.e.e., M) acetylacetonates with dimethyl sulfoxide (DMSO), MA 3 xnDMSO are synthesized. The acetylacetonates of light r.e.e. (M=La-Tb) are shown by different physico-chemical methods to form diadducts of the MA 3 x2DMSOxH 2 O composition, where A - -acetylacetonate-ion, and the acetyl-acetonates of heavy r.e.e. (M=Dy-Lu, Y)-monoadducts MA 3 xDMSO. The estimation of adduct thermal stability is carried out using the values of seeming activation energy of their thermal degradation. Monoadducts are shown to give volatile forms of rare earth acetylacetonates during heating in vacuum, and diadducts do not form volatile forms of acetylacetonates

Barrierless Reactions with Loose Transition States Govern the Yields and Lifetimes of Organic Nitrates Derived from Isoprene

Science.gov (United States)

The chemical reaction mechanism of NO addition to two β and δ isoprene hydroxy–peroxy radical isomers is examined in detail using density functional theory, coupled cluster methods, and the energy resolved master equation formalism to provide estimates of rate co...

Characterization of model peptide adducts with reactive metabolites of naphthalene by mass spectrometry.

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Nathalie T Pham

Full Text Available Naphthalene is a volatile polycyclic aromatic hydrocarbon generated during combustion and is a ubiquitous chemical in the environment. Short term exposures of rodents to air concentrations less than the current OSHA standard yielded necrotic lesions in the airways and nasal epithelium of the mouse, and in the nasal epithelium of the rat. The cytotoxic effects of naphthalene have been correlated with the formation of covalent protein adducts after the generation of reactive metabolites, but there is little information about the specific sites of adduction or on the amino acid targets of these metabolites. To better understand the chemical species produced when naphthalene metabolites react with proteins and peptides, we studied the formation and structure of the resulting adducts from the incubation of model peptides with naphthalene epoxide, naphthalene diol epoxide, 1,2-naphthoquinone, and 1,4-naphthoquinone using high resolution mass spectrometry. Identification of the binding sites, relative rates of depletion of the unadducted peptide, and selectivity of binding to amino acid residues were determined. Adduction occurred on the cysteine, lysine, and histidine residues, and on the N-terminus. Monoadduct formation occurred in 39 of the 48 reactions. In reactions with the naphthoquinones, diadducts were observed, and in one case, a triadduct was detected. The results from this model peptide study will assist in data interpretation from ongoing work to detect peptide adducts in vivo as markers of biologic effect.

Raman spectra from very concentrated aqueous NaOH and from wet and dry, solid, and anhydrous molten, LiOH, NaOH, and KOH.

Science.gov (United States)

Walrafen, George E; Douglas, Rudolph T W

2006-03-21

High-temperature, high-pressure Raman spectra were obtained from aqueous NaOH solutions up to 2NaOHH2O, with X(NaOH)=0.667 at 480 K. The spectra corresponding to the highest compositions, X(NaOH)> or =0.5, are dominated by H3O2-. An IR xi-function dispersion curve for aqueous NaOH, at 473 K and 1 kbar, calculated from the data of Franck and Charuel indicates that the OH- ion forms H3O2- by preferential H bonding with nonhydrogen-bonded OH groups. Raman spectra from wet to anhydrous, solid LiOH, NaOH, and KOH yield sharp, symmetric OH- stretching peaks at 3664, 3633, and 3596 cm(-1), respectively, plus water-related, i.e., H3O2-, peaks near LiOH, 3562 cm(-1), NaOH, 3596 cm(-1), and, KOH, 3500 cm(-1). Absence of H3O2- peaks from the solid assures that the corresponding melt is anhydrous. Raman spectra from the anhydrous melts yield OH- stretching peak frequencies: LiOH, 3614+/-4 cm(-1), 873 K; NaOH, 3610+/-2 cm(-1), 975 K; and, KOH, 3607+/-2 cm(-1), 773 K, but low-frequency asymmetry due to ion-pair interactions is present which is centered near 3550 cm(-1). The ion-pair-related asymmetry corresponds to the sole IR maximum near 3550 cm(-1) from anhydrous molten NaOH, at 623 K. Bose-Einstein correction of published low-frequency Raman data from molten LiOH revealed an acoustic phonon, near 205 cm(-1), related to restricted translation of OH- versus Li+, and an optical phonon, at 625 cm(-1) and tau approximately 0.05 ps, due to protonic precession and/or pendular motion. Strong H bonding between water and the O atom of OH- forms H3O2-, but the proton of OH- does not bond with H significantly. Large Raman bandwidths (aqueous solutions) are explained in terms of inhomogeneous broadening due to proton transfer in a double well. Vibrational assignments are presented for H3O2-.

Formation of 7-hydroxymethyl-12-methylbenz(a)anthracene-DNA adducts from 7,12-dimethylbenz(a)anthracene in mouse epidermis

International Nuclear Information System (INIS)

DiGiovanni, J.; Nebzydoski, A.P.; Decina, P.C.

1983-01-01

The formation of DNA adducts from [ 3 H]-7-hydroxymethyl-12-methylbenz(a)anthracene (7-OHM-12-MBA) and [ 3 H]-7,12-dimethylbenz(a)anthracene (DMBA) in the epidermis of Sencar mice was analyzed. Comparison of Sephadex LH-20 chromatographic profiles of DNA samples isolated from mice treated with DMBA or 7-OHM-12-MBA suggested that the DMBA-treated animals contained DNA adduct(s) derived from the further metabolism of 7-OHM-12-MBA. Further analysis of DNA samples from DMBA-treated mice by high-pressure liquid chromatography demonstrated the presence of 5 DNA adducts which were chromatographically indistinguishable from the DNA adducts formed in 7-OHM-12-MBA-treated mice. Epidermal homogenates were utilized to catalyze the covalent binding of [ 3 H]DMBA and [ 3 H]-7-OHM-12-MBA to calf thymus DNA in vitro. Under conditions of limiting concentrations of [ 3 H]DMBA, the majority of the DNA adducts formed chromatographed in regions where 7-OHM-12-MBA-DNA adducts eluted. A major DMBA-DNA adduct formed in this in vitro system eluted with the same retention time as did the major 7-OHM-12-MBA-DNA adduct formed in mouse skin in vivo. These results when coupled with the in vivo data suggest that 7-OHM-12-MBA is an intermediate for at least some of the binding of DMBA to epidermal DNA in Sencar mice

Concentration- and time-dependent genotoxicity profiles of isoprene monoepoxides and diepoxide, and the cross-linking potential of isoprene diepoxide in cells

Directory of Open Access Journals (Sweden)

Yan Li

2014-01-01

Full Text Available Isoprene, a possible carcinogen, is a petrochemical and a natural product being primarily produced by plants. It is biotransformed to 2-ethenyl-2-methyloxirane (IP-1,2-O and 2-(1-methylethenyloxirane (IP-3,4-O, both of which can be further metabolized to 2-methyl-2,2′-bioxirane (MBO. MBO is mutagenic, but IP-1,2-O and IP-3,4-O are not. While IP-1,2-O has been reported being genotoxic, the genotoxicity of IP-3,4-O and MBO, and the cross-linking potential of MBO have not been examined. In the present study, we used the comet assay to investigate the concentration- and time-dependent genotoxicity profiles of the three metabolites and the cross-linking potential of MBO in human hepatocyte L02 cells. For the incubation time of 1 h, all metabolites showed positive concentration-dependent profiles with a potency rank order of IP-3,4-O > MBO > IP-1,2-O. In human hepatocellular carcinoma (HepG2 and human leukemia (HL60 cells, IP-3,4-O was still more potent in inducing DNA breaks than MBO at high concentrations (>200 μM, although at low concentrations (≤200 μM IP-3,4-O exhibited slightly lower or similar potency to MBO. Interestingly, their time-dependent genotoxicity profiles (0.5–4 h in L02 cells were different from each other: IP-1,2-O and MBO (200 μM exhibited negative and positive profiles, respectively, with IP-3,4-O lying in between, namely, IP-3,4-O-caused DNA breaks did not change over the exposure time. Further experiments demonstrated that hydrolysis of IP-1,2-O contributed to the negative profile and MBO induced cross-links at high concentrations and long incubation times. Collectively, the results suggested that IP-3,4-O might play a significant role in the toxicity of isoprene.

Bulky carcinogen-DNA adducts and exposure to environmental and occupational sources of polycyclic aromatic hydrocarbons. Influence of susceptibility genotypes on adduct level

International Nuclear Information System (INIS)

Sabro Nielsen, P.

1996-01-01

PAH exposure, whether it is of occupational or environmental origin, is thought to result in an elevated risk of cancer especially in the lungs. DNA damage is considered an important step in the carcinogenic effect of PAH. Hence, methods that elucidate the steps in the carcinogenic process are important to understand the action of PAH. It may prove useful in the exposure assessment and in combination with classical epidemiological methods give better basis for risk estimation. The objective in this thesis was to evaluate the feasibility of the 32 P-postlabeling method to detect carcinogen-DNA adducts for assessing exposure to DNA damaging compounds in different occupationally and environmentally exposed groups. The studies included groups, that have an elevated cancer risk due to occupational exposure to PAH. Exposure levels were supposed to be relatively low according to reports on occupational and environmental air quality programs. Another aim was to evaluate the influence of polymorphisms in metabolizing enzyme genes on DNA adduct levels. A third objective was to establish some kind of baseline DNA adduct level for individuals with supposed low exposure, and compare it to the more exposed groups. A fourth aim in these studies was to examine if biomarkers of genotoxic exposure could be useful in epidemiological studies to identify groups at risk and thereby contribute with better exposure estimates in the study of PAH related cancer risk. (EG)

Bulky carcinogen-DNA adducts and exposure to environmental and occupational sources of polycyclic aromatic hydrocarbons. Influence of susceptibility genotypes on adduct level

Energy Technology Data Exchange (ETDEWEB)

Sabro Nielsen, P

1997-12-31

PAH exposure, whether it is of occupational or environmental origin, is thought to result in an elevated risk of cancer especially in the lungs. DNA damage is considered an important step in the carcinogenic effect of PAH. Hence, methods that elucidate the steps in the carcinogenic process are important to understand the action of PAH. It may prove useful in the exposure assessment and in combination with classical epidemiological methods give better basis for risk estimation. The objective in this thesis was to evaluate the feasibility of the {sup 32}P-postlabeling method to detect carcinogen-DNA adducts for assessing exposure to DNA damaging compounds in different occupationally and environmentally exposed groups. The studies included groups, that have an elevated cancer risk due to occupational exposure to PAH. Exposure levels were supposed to be relatively low according to reports on occupational and environmental air quality programs. Another aim was to evaluate the influence of polymorphisms in metabolizing enzyme genes on DNA adduct levels. A third objective was to establish some kind of baseline DNA adduct level for individuals with supposed low exposure, and compare it to the more exposed groups. A fourth aim in these studies was to examine if biomarkers of genotoxic exposure could be useful in epidemiological studies to identify groups at risk and thereby contribute with better exposure estimates in the study of PAH related cancer risk. (EG).

Bulky carcinogen-DNA adducts and exposure to environmental and occupational sources of polycyclic aromatic hydrocarbons. Influence of susceptibility genotypes on adduct level

Energy Technology Data Exchange (ETDEWEB)

Sabro Nielsen, P.

1996-12-31

PAH exposure, whether it is of occupational or environmental origin, is thought to result in an elevated risk of cancer especially in the lungs. DNA damage is considered an important step in the carcinogenic effect of PAH. Hence, methods that elucidate the steps in the carcinogenic process are important to understand the action of PAH. It may prove useful in the exposure assessment and in combination with classical epidemiological methods give better basis for risk estimation. The objective in this thesis was to evaluate the feasibility of the {sup 32}P-postlabeling method to detect carcinogen-DNA adducts for assessing exposure to DNA damaging compounds in different occupationally and environmentally exposed groups. The studies included groups, that have an elevated cancer risk due to occupational exposure to PAH. Exposure levels were supposed to be relatively low according to reports on occupational and environmental air quality programs. Another aim was to evaluate the influence of polymorphisms in metabolizing enzyme genes on DNA adduct levels. A third objective was to establish some kind of baseline DNA adduct level for individuals with supposed low exposure, and compare it to the more exposed groups. A fourth aim in these studies was to examine if biomarkers of genotoxic exposure could be useful in epidemiological studies to identify groups at risk and thereby contribute with better exposure estimates in the study of PAH related cancer risk. (EG).

Forefoot Adduction Is a Risk Factor for Jones Fracture.

Science.gov (United States)

Fleischer, Adam E; Stack, Rebecca; Klein, Erin E; Baker, Jeffrey R; Weil, Lowell; Weil, Lowell Scott

Jones fractures are among the most common fractures of the foot; however, much remains unknown about their etiology. The purpose of the present study was to further examine the risk factors of forefoot and hindfoot alignment on Jones fractures using an epidemiologic study design. We used a retrospective, matched, case-control study design. Cases consisted of patients with acute, isolated Jones fractures confirmed on plain film radiographs seen at our institute from January 2009 to December 2013. Patients presenting with pain unrelated to metatarsal fractures served as controls. Controls were matched to cases by age (±2 years), gender, and year of presentation. Weightbearing foot radiographs were assessed for 13 angular relationships by a single rater. Conditional multivariable logistic regression was used to identify important risk factors. Fifty patients with acute Jones fractures and 200 controls were included. The only significant variables in the final multivariable model were the metatarsus adductus angle (odds ratio [OR] 1.16, 95% confidence interval [CI] 1.08 to 1.25) and fourth/fifth intermetatarsal angle (OR 0.69, 95% CI 0.57 to 0.83)-both measures of static forefoot adduction. The presence of metatarsus adductus (defined as >15°) on foot radiographs was associated with a 2.4 times greater risk of a Jones fracture (adjusted OR 2.4, 95% CI 1.2 to 4.8). We have concluded that the risk of Jones fracture increases with an adducted forefoot posture. In our population, which consisted primarily of patients presenting after a fall (10 of 50; 20%) or misstep/inversion injury (19 of 50; 38%), the hindfoot alignment appeared to be a less important factor. Copyright © 2017 American College of Foot and Ankle Surgeons. Published by Elsevier Inc. All rights reserved.

Synthesis, spectral and thermal studies of pyridyl adducts of Zn(II) and Cd(II) dithiocarbamates, and their use as single source precursors for ZnS and CdS nanoparticles.

Science.gov (United States)

Onwudiwe, Damian C; Strydom, Christien A; Oluwafemi, Oluwatobi S; Hosten, Eric; Jordaan, Anine

2014-06-21

The synthesis, spectroscopic characterisation, and thermal studies of pyridyl adducts of Zn(II) and Cd(II) complexes of N-ethyl-N-phenyl dithiocarbamate, represented as [ZnL2py] and [CdL2py2], are reported. Single-crystal X-ray structural analysis of the Zn compound showed that it is five-coordinate with four sulphurs from dithiocarbamate and one nitrogen from pyridine in a distorted square pyramidal geometry. The thermogravimetric studies indicate that the zinc and cadmium compounds undergo fast weight loss, and the temperature at maximum rate of decomposition is at 277 °C and 265 °C respectively, to give the metal (Zn or Cd) sulphide residues. These compounds were used as single molecule precursors to produce nanocrystalline MS (M = Zn, Cd) after thermolysis in hexadecylamine. The morphological and optical properties of the resulting MS nanocrystallites were investigated using transmission electron microscopy (TEM), scanning electron microscopy (SEM), UV-Vis absorption and photoluminescence (PL) spectroscopy, and powdered X-ray diffraction (XRD). By varying the growth time, the temporal evolution of the optical properties and morphology of the nanocrystals were investigated.

Bis(phenolate)amine-supported lanthanide borohydride complexes for styrene and trans-1,4-isoprene (co-)polymerisations

NARCIS (Netherlands)

Bonnet, Fanny; Dyer, Hellen E.; El Kinani, Yassine; Dietz, Carin; Roussel, Pascal; Bria, Marc; Visseaux, Marc; Zinck, Philippe; Mountford, Philip

2015-01-01

New bis(phenolate)amine-supported neodymium borohydride complexes and their previously reported samarium analogues were tested as catalysts for the polymerisation of styrene and isoprene. Reaction of Na2O2NL (L = py, OMe, NMe2) with Nd(BH4)3(THF)3 afforded the borohydride complexes

Nuclear magnetic resonance at the picomole level of a DNA adduct.

Science.gov (United States)

Kautz, Roger; Wang, Poguang; Giese, Roger W

2013-10-21

We investigate the limit of detection for obtaining NMR data of a DNA adduct using modern microscale NMR instrumentation, once the adduct has been isolated at the picomole level. Eighty nanograms (130 pmol) of a DNA adduct standard, N-(2'-deoxyguanosin-8-yl)-2-acetylaminofluorene 5'-monophosphate (AAF-dGMP), in 1.5 μL of D₂O with 10% methanol-d₄, in a vial, was completely picked up as a droplet suspended in a fluorocarbon liquid and loaded efficiently into a microcoil probe. This work demonstrates a practical manual method of droplet microfluidic sample loading, previously demonstrated using automated equipment, which provides a severalfold advantage over conventional flow injection. Eliminating dilution during injection and confining the sample to the observed volume produce the full theoretical mass sensitivity of a microcoil, comparable to that of a microcryo probe. With 80 ng, an NMR spectrum acquired over 40 h showed all of the resonances seen in a standard spectrum of AAF-dGMP, with a signal-to-noise ratio of at least 10, despite broadening due to previously noted effects of conformational exchange. Even with this broadening to 5 Hz, a two-dimensional total correlation spectroscopy spectrum was acquired on 1.6 μg in 18 h. This work helps to define the utility of NMR in combination with other analytical methods for the structural characterization of a small amount of a DNA adduct.

Interaction between OHS regulation and OHS certification in Denmark

DEFF Research Database (Denmark)

Hendriksen, Kåre; Jørgensen, Kirsten; Jørgensen, Ulrik

2010-01-01

In 2001, the Danish Parliament approved a law on OHS certification that provided economic support to enterprises/organizations that were certified according to one of the two national OHS standards. These certified enterprises/organizations were also exempt from the initial inspection by the Danish...... Working Environment Authority, which they would otherwise be required to pay for. In practice, this meant that inspection of the certified enterprises was transferred to the certification bodies unless a work accident or work-caused ailment or the like was reported. In 2005, the law was revised so...... certification has existed as a form of substitute inspection for almost 10 years, no systematic evaluation of the effects of OHS certification on the OHS, and thereby the validity of the certificate, has been made. In several cases, however, certified enterprises/organizations have received injunctions...

Molecular Modeling of the Major DNA Adduct Formed from Food Mutagen Ochratoxin A in NarI Two-Base Deletion Duplexes: Impact of Sequence Context and Adduct Ionization on Conformational Preference and Mutagenicity.

Science.gov (United States)

Kathuria, Preetleen; Sharma, Purshotam; Manderville, Richard A; Wetmore, Stacey D

2017-08-21

Exposure to ochratoxin A (OTA), a possible human carcinogen, leads to many different DNA mutations. As a first step toward understanding the structural basis of OTA-induced mutagenicity, the present work uses a robust computational approach and a slipped mutagenic intermediate model previously studied for C 8 -dG aromatic amine adducts to analyze the conformational features of postreplication two-base deletion DNA duplexes containing OT-dG, the major OTA lesion at the C 8 position of guanine. Specifically, a total of 960 ns of molecular dynamics simulations (excluding trial simulations) were carried out on four OT-dG ionization states in three sequence contexts within oligomers containing the NarI recognition sequence, a known hotspot for deletion mutations induced by related adducts formed from known carcinogens. Our results indicate that the structural properties and relative stability of the competing "major groove" and "stacked" conformations of OTA adducted two-base deletion duplexes depend on both the OTA ionization state and the sequence context, mainly due to conformation-dependent deviations in discrete local (hydrogen-bonding and stacking) interactions at the lesion site, as well as DNA bending. When the structural characteristics of the OT-dG adducted two-base deletion duplexes are compared to those associated with previously studied C 8 -dG adducts, a greater understanding of the effects of the nucleobase-carcinogen linkage, and size of the carcinogenic moiety on the conformational preferences of damaged DNA is obtained. Most importantly, our work predicts key structural features for OT-dG-adducted deletion DNA duplexes, which in turn allow us to develop hypotheses regarding OT-dG replication outcomes. Thus, our computational results are valuable for the design and interpretation of future biochemical studies on the potentially carcinogenic OT-dG lesion.

Growth regulating properties of isoprene and isoprenoid-based essential oils.

Science.gov (United States)

Jones, Andrew Maxwell P; Shukla, Mukund R; Sherif, Sherif M; Brown, Paula B; Saxena, Praveen K

2016-01-01

Essential oils have growth regulating properties comparable to the well-documented methyl jasmonate and may be involved in localized and/or airborne plant communication. Aromatic plants employ large amounts of resources to produce essential oils. Some essential oils are known to contain compounds with plant growth regulating activities. However, the potential capacity of essential oils as airborne molecules able to modulate plant growth/development has remained uninvestigated. Here, we demonstrate that essential oils from eight taxonomically diverse plants applied in their airborne state inhibited auxin-induced elongation of Pisum sativum hypocotyls and Avena sativa coleoptiles. This response was also observed using five monoterpenes commonly found in essential oils as well as isoprene, the basic building block of terpenes. Upon transfer to ambient conditions, A. sativa coleoptiles resumed elongation, demonstrating an antagonistic relationship rather than toxicity. Inclusion of essential oils, monoterpenes, or isoprene into the headspace of culture vessels induced abnormal cellular growth along hypocotyls of Arabidopsis thaliana. These responses were also elicited by methyl jasmonate (MeJA); however, where methyl jasmonate inhibited root growth essential oils did not. Gene expression studies in A. thaliana also demonstrated differences between the MeJA and isoprenoid responses. This series of experiments clearly demonstrate that essential oils and their isoprenoid components interact with endogenous plant growth regulators when applied directly or as volatile components in the headspace. The similarities between isoprenoid and MeJA responses suggest that they may act in plant defence signalling. While further studies are needed to determine the ecological and evolutionary significance, the results of this study and the specialized anatomy associated with aromatic plants suggest that essential oils may act as airborne signalling molecules.

Vaporization of GaI3Py adduct

International Nuclear Information System (INIS)

Timoshkina, A.Yu.; Grigor'ev, A.A.; Suvorov, A.V.

1995-01-01

Processes of GaI 3 Py complex vaporization have been studied by mass-spectrometric, tensimetric and calorimetric methods. It is shown that adduct transformation into vapour is accompanied by its thermal dissociation. Thermodynamic characteristics of evaporation and dissociation of GaI 3 Py complex have been obtained. 14 refs., 2 figs., 6 tabs

Chemical structure of the adducts formed by the oxidation of benzidine in the presence of phenols

International Nuclear Information System (INIS)

Josephy, P.D.; Mason, R.P.; Eling, T.

1982-01-01

Bioactivation of carcinogens by peroxidases has received increasing attention since the discovery of the oxidation of carcinogens by prostaglandin hydroperoxidase. Benzidine and 3,5,3',5'-tetramethylbenzidine are oxidized by horseradish peroxidase and prostaglandin synthase to two-electron oxidation products (di-imines). Di-imines readily react with the phenolic anti-oxidant butylated hydroxyanisole to form adducts. In this paper, we have studied the oxidation of benzidine by horseradish peroxidase in the presence of phenolic compounds and characterized the resultant benzidine/phenol adducts. A benzidine/2,6-dimethylphenol adduct was isolated and characterized by mass spectrometry and high field n.m.r. The reaction of [ 14 C]benzidine in the presence of horseradish peroxidase and phenol yielded only the benzidine/phenol adduct. Our results indicate that the benzidine/phenol adducts are analogous to the indoaniline dyes, differing only in substitution of a biphenyl group for a benzene ring. The reaction of benzidine di-imine with endogenous phenols may represent a new pathway for detoxication, removing potentially harmful metabolites of benzidine

Electronic structure and optical properties of Eu(III) tris-β-diketonate adducts with 1,10-phenanthroline

Science.gov (United States)

Shurygin, A. V.; Korochentsev, V. V.; Cherednichenko, A. I.; Mirochnik, A. G.; Kalinovskaya, I. V.; Vovna, V. I.

2018-03-01

Adducts of tris-β-diketonates of the rare earth metal Eu(III) with 1,10-phenanthroline are studied by photoelectron spectroscopy and quantum chemistry methods. The electronic structure, peculiarities of the nature of chemical bonds, and the geometric structure of the adducts are determined. The interpretation of UV photoelectron spectra of vapors and X-ray photoelectron spectra of solid is carried out with the chosen technique. DFT/TDDFT methods make it possible to study the 1,10-phenanthroline molecule influence on the adduct electronic structure and to analyze the electronic effects of substitution of methyl groups by trifluoromethyl groups in the ligands. At transition from the tris-β-diketonate complexes to the adducts, it is observed an increase of the absorption region and a decrease in the energy gap that contributes to the efficiency growth in electronic excitation energy transfer in the ligand-metal. Moreover, phenanthroline displaces water groups, that are luminescence quenchers, from the first coordination sphere, closes coordination in the adduct, and blocks their further attachment. Both factors contribute to an increase in the luminescence intensity.

Biomarkers for exposure to ambient air pollution - Comparison of carcinogen-DNA adduct levels with other exposure markers and markers for oxidative stress

DEFF Research Database (Denmark)

Autrup, Herman; Daneshvar, Bahram; Dragsted, Lars Ove

1999-01-01

Human exposure to genotoxic compounds present in ambient air has been studied using selected biomarkers in nonsmoking Danish bus drivers and postal workers. A large interindividual variation in biomarker levels was observed. Significantly higher levels of bulky carcinogen-DNA adducts (75.42 adducts...... correlations were observed between bulky carcinogen-DNA adduct and PAM-albumin levels (p = 0.005), and between DNA adduct and gamma-glutamyl semialdehyde (GGS) in hemoglobin (p = 0.11). Highly significant correlations were found between PAM-albumin adducts and AAS in plasma (r = 0.001) and GGS in hemoglobin (p...... in the combined group. A significant negative correlation was only observed between bulky carcinogen-DNA adducts and PAM-albumin adducts (p = 0.02) and between DNA adduct and urinary mutagenic activity (p = 0.02) in the GSTM1 null group, bur not in the workers who were homozygotes or heterozygotes for GSTM1. Our...

Recognition and repair of the CC-1065-(N3-Adenine)-DNA adduct by the UVRABC nuclease

International Nuclear Information System (INIS)

Tang, M.; Lee, C.S.; Doisy, R.; Ross, L.; Needham-VanDevanter, D.R.; Hurley, L.H.

1988-01-01

The recognition and repair of the helix-stabilizing and relatively nondistortive CC-1065-(N3-adenine)-DNA adduct by UVRABC nuclease has been investigated both in vivo with phi X174RFI DNA by a transfection assay and in vitro by a site-directed adduct in a 117 base pair fragment from M13mp1. CC-1065 is a potent antitumor antibiotic produced by Streptomyces zelensis which binds within the minor groove of DNA through N3 of adenine. In contrast to the helix-destabilizing and distortive modifications of DNA caused by ultraviolet light or N-acetoxy-2-(acetylamino)fluorene, CC-1065 increases the melting point of DNA and decreases the S1 nuclease activity. Using a viral DNA-Escherichia coli transfection system, the authors have found that the uvrA, uvrB, and uvrC genes, which code for the major excision repair proteins for UV- and NAAAF-induced DNA damage, are also involved in the repair of CC-1065-DNA adducts. In contrast, the uvrD gene product, which has been found to be involved in the repair of UV damage, has no effect in repairing CC-1065-DNA adducts. Purified UVRA, UVRB, and UVRC proteins must work in concert to incise the drug-modified phi X174RFI DNA. Using a site-directed and multiple CC-1065 modified (MspI-BstNI) 117 base pair fragment from M13mp1, they have found that UVRABC nuclease incises at the eight phosphodiester bond on the 5' side of the CC-1065-DNA adduct on the drug-modified strand. The enzymes do not cut the noncovalently modified strand. The DNA sequence and/or helix-stabilizing effect of multiple adducts may determine the recognition and/or incision of the drug-DNA adduct by UVRABC nuclease. These results are discussed in relation to the structure of the CC-1065-DNA adduct and the effect of drug binding on local DNA structure

Acetaminophen-induced liver damage in mice is associated with gender-specific adduction of peroxiredoxin-6

Directory of Open Access Journals (Sweden)

Isaac Mohar

2014-01-01

Full Text Available The mechanism by which acetaminophen (APAP causes liver damage evokes many aspects drug metabolism, oxidative chemistry, and genetic-predisposition. In this study, we leverage the relative resistance of female C57BL/6 mice to APAP-induced liver damage (AILD compared to male C57BL/6 mice in order to identify the cause(s of sensitivity. Furthermore, we use mice that are either heterozygous (HZ or null (KO for glutamate cysteine ligase modifier subunit (Gclm, in order to titrate the toxicity relative to wild-type (WT mice. Gclm is important for efficient de novo synthesis of glutathione (GSH. APAP (300 mg/kg, ip or saline was administered and mice were collected at 0, 0.5, 1, 2, 6, 12, and 24 h. Male mice showed marked elevation in serum alanine aminotransferase by 6 h. In contrast, female WT and HZ mice showed minimal toxicity at all time points. Female KO mice, however, showed AILD comparable to male mice. Genotype-matched male and female mice showed comparable APAP–protein adducts, with Gclm KO mice sustaining significantly greater adducts. ATP was depleted in mice showing toxicity, suggesting impaired mitochondria function. Indeed, peroxiredoxin-6, a GSH-dependent peroxiredoxin, was preferentially adducted by APAP in mitochondria of male mice but rarely adducted in female mice. These results support parallel mechanisms of toxicity where APAP adduction of peroxiredoxin-6 and sustained GSH depletion results in the collapse of mitochondria function and hepatocyte death. We conclude that adduction of peroxiredoxin-6 sensitizes male C57BL/6 mice to toxicity by acetaminophen.

Clumped isotope effects during OH and Cl oxidation of methane

DEFF Research Database (Denmark)

Whitehill, Andrew R.; Joelsson, Lars Magnus T.; Schmidt, Johan Albrecht

2017-01-01

A series of experiments were carried out to determine the clumped (13CH3D) methane kinetic isotope effects during oxidation of methane by OH and Cl radicals, the major sink reactions for atmospheric methane. Experiments were performed in a 100 L quartz photochemical reactor, in which OH was produ......A series of experiments were carried out to determine the clumped (13CH3D) methane kinetic isotope effects during oxidation of methane by OH and Cl radicals, the major sink reactions for atmospheric methane. Experiments were performed in a 100 L quartz photochemical reactor, in which OH...... effects for singly substituted species were consistent with previous experimental studies. For doubly substituted methane, 13CH3D, the observed kinetic isotope effects closely follow the product of the kinetic isotope effects for the 13C and deuterium substituted species (i.e., 13,2KIE = 13KIE × 2KIE...... reactions. In a closed system, however, this effect is overtaken by the large D/H isotope effect, which causes the residual methane to become anti-clumped relative to the initial methane. Based on these results, we demonstrate that oxidation of methane by OH, the predominant oxidant for tropospheric methane...

Synthesis and Characterization of the Adducts of Morpholinedithioccarbamate Complexes of Oxovanadium (IV, Nickel(II, and Copper(II with Piperidine and Morpholine

Directory of Open Access Journals (Sweden)

Mousami Sharma

2012-01-01

Full Text Available A series of 1:1 adducts of bis(morpholinedithiocarbamato complex of VO(IV, 1:1 and 1:2 adducts of bis(morpholinedithiocarbamato complexes of Ni(II and Cu(II with piperidine and morpholine have been synthesized and characterized by elemental analysis, molar conductance, magnetic susceptibility, IR, UV-Vis, and TGA/DTA techniques. Analytical data reveals that VO(IV complex forms only 1:1 adducts with the formula [VO(morphdtc2L].H2O while Ni(II and Cu(II complexes form both 1:1 and 1:2 adducts with 1:1 adducts having general formula Ni(morphdtc2.L and Cu(morphdtc2.L and 1:2 adducts having general formula Ni(morphdtc2.L2 and Cu(morphdtc2.L2 (morphdtc = morpholinedithiocarbamate, L = morpholine and piperidine. Antifungal activity of some complexes has been carried out against the fungal strain Fusarium oxysporium. Thermal studies indicate a continuous weight loss. A square pyramidal geometry has been proposed for the 1:1 adducts of Ni(II and Cu(II complexes while an octahedral geometry has been proposed for the 1:1 adducts of VO(IV and for the 1:2 adducts of Ni(II and Cu(II complexes.

Volatile Organic Compounds and Oxidation Capacity of the Atmosphere in the Brazilian Amazon during the GoAmazon2014/5 Campaign

Science.gov (United States)

Seco, R.; Jeong, D.; Kim, S.; Park, J. H.; Sjostedt, S. J.; Guenther, A. B.; Smith, J. N.; Liu, Y.; Gu, D.; Bustillos, J. O. V.; Tota, J.; Souza, R. A. F. D.; Martin, S. T.

2015-12-01

Atmospheric volatile organic compounds (VOCs) have key environmental and biological roles, and can influence atmospheric chemistry, secondary aerosol formation, and also regional climate. The GoAmazon2014/5 campaign included measurements of VOCs in pristine to polluted air of the Amazon basin, depending upon the influences from the pollution plumes originating in the city of Manaus, Brazil. Observations at the T3 site in Manacapuru during the second Intensive Operating Period (dry season, August-October 2014) using a Switchable Reagent Ion (SRI)-ToF-MS will be presented to investigate isoprene oxidation processes in a wide spectrum of anthropogenic influences. The SRI capability was utilized to quantify ratios of Methyl Vinyl Ketone (MVK) to Methacrolein (MACR) in order to assess photochemical age of air masses at T3 and examine isoprene peroxy radical reaction pathways as a function of NO levels. Given recently identified ISOPOOH interference to MVK and MACR measurements, the current analysis focus on high NOx conditions when the contribution of ISOPOOH was small. In addition, the results will be critically compared with previously reported relationships between MVK, MACR and isoprene to explore potential systematic analytical interferences that may affect regional OH level estimations. These OH estimates will be evaluated using in-situ OH observations.

Adduct formation of ionic and nanoparticular silver with amino acids and glutathione

International Nuclear Information System (INIS)

Blaske, Franziska; Stork, Lisa; Sperling, Michael; Karst, Uwe

2013-01-01

To investigate the interaction of ionic and nanoparticular silver with amino acids and small peptides, an electrospray ionization time-of-flight mass spectrometry method was developed. Monomeric and oligomeric silver adducts were formed with amino acids including cysteine (Cys), methionine, histidine, lysine, or the tripeptide glutathione (GSH). The obtained spectra for ionic silver show clusters in different ratios between Ag + and the reaction partners (X) including [Ag n X m − (n + 1)H] − (n = 1–4, m = 1–3). Regarding Cys, adduct clusters up to n = 5 and m = 4 were observed as well. Considering silver–GSH interactions, even doubly charged oligomers occur generating [Ag (a+1) GSH a − (a + 3)H] 2− (a = 5–7) and [Ag b GSH b − (b + 2)H] 2− (b = 4–8) ions. 1 H NMR data of free GSH compared to that after treatment with Ag + confirm sulfur–metal interactions due to changing chemical shifts for the protons located adjacent to the thiol group. Density functional theory calculations for silver–GSH clusters may explain the formation of experimentally recorded large clusters due to cooperative effects between silver and carboxylic acid side chains. Both sets of experiments indicate the presence of these adducts in the liquid phase. For silver nanoparticles, the respective data confirm the release of silver ions and the subsequent adduct formation

Adduct formation of ionic and nanoparticular silver with amino acids and glutathione

Science.gov (United States)

Blaske, Franziska; Stork, Lisa; Sperling, Michael; Karst, Uwe

2013-09-01

To investigate the interaction of ionic and nanoparticular silver with amino acids and small peptides, an electrospray ionization time-of-flight mass spectrometry method was developed. Monomeric and oligomeric silver adducts were formed with amino acids including cysteine (Cys), methionine, histidine, lysine, or the tripeptide glutathione (GSH). The obtained spectra for ionic silver show clusters in different ratios between Ag+ and the reaction partners (X) including [Ag n X m - ( n + 1)H]- ( n = 1-4, m = 1-3). Regarding Cys, adduct clusters up to n = 5 and m = 4 were observed as well. Considering silver-GSH interactions, even doubly charged oligomers occur generating [Ag( a + 1)GSH a - ( a + 3)H]2- ( a = 5-7) and [Ag b GSH b - ( b + 2)H]2- ( b = 4-8) ions. 1H NMR data of free GSH compared to that after treatment with Ag+ confirm sulfur-metal interactions due to changing chemical shifts for the protons located adjacent to the thiol group. Density functional theory calculations for silver-GSH clusters may explain the formation of experimentally recorded large clusters due to cooperative effects between silver and carboxylic acid side chains. Both sets of experiments indicate the presence of these adducts in the liquid phase. For silver nanoparticles, the respective data confirm the release of silver ions and the subsequent adduct formation.

Etheno-DNA adduct formation in rats gavaged with linoleic acid, oleic acid and coconut oil is organ- and gender specific

International Nuclear Information System (INIS)

Fang Qingming; Nair, Jagadeesan; Sun Xin; Hadjiolov, Dimiter; Bartsch, Helmut

2007-01-01

Intake of linoleic acid (LA) increased etheno-DNA adducts induced by lipid peroxidation (LPO) in white blood cells (WBC) of female but not of male volunteers [J. Nair, C.E. Vaca, I. Velic, M. Mutanen, L.M. Valsta, H. Bartsch, High dietary ω-6 polyunsaturated fatty acids drastically increase the formation of etheno-DNA adducts in white blood cells of female subjects, Cancer Epidemiol. Biomarkers Prev. 6 (1997) 597-601]. Etheno-adducts were measured in rats gavaged with LA, oleic acid (OA) and saturated fatty acid rich coconut oil for 30 days. DNA from organs and total WBC was analyzed for 1, N 6 -ethenodeoxyadenosine (εdA) and 3, N 4 -ethenodeoxycytidine (εdC) by immunoaffinity/ 32 P-postlabeling. Colon was the most affected target with LA-treatment, where etheno-adducts were significantly elevated in both sexes. In WBC both adducts were elevated only in LA-treated females. Unexpectedly, OA treatment enhanced etheno-adduct levels in prostate 3-9 fold. Our results in rodents confirm the gender-specific increase of etheno-adducts in WBC-DNA, likely due to LPO induced by redox-cycling of 4-hydroxyestradiol. Colon was a target for LPO-derived DNA-adducts in both LA-treated male and female rats, supporting their role in ω-6 PUFA induced colon carcinogenesis

OH+ IN DIFFUSE MOLECULAR CLOUDS

International Nuclear Information System (INIS)

Porras, A. J.; Federman, S. R.; Welty, D. E.; Ritchey, A. M.

2014-01-01

Near ultraviolet observations of OH + and OH in diffuse molecular clouds reveal a preference for different environments. The dominant absorption feature in OH + arises from a main component seen in CH + (that with the highest CH + /CH column density ratio), while OH follows CN absorption. This distinction provides new constraints on OH chemistry in these clouds. Since CH + detections favor low-density gas with small fractions of molecular hydrogen, this must be true for OH + as well, confirming OH + and H 2 O + observations with the Herschel Space Telescope. Our observed correspondence indicates that the cosmic ray ionization rate derived from these measurements pertains to mainly atomic gas. The association of OH absorption with gas rich in CN is attributed to the need for a high enough density and molecular fraction before detectable amounts are seen. Thus, while OH + leads to OH production, chemical arguments suggest that their abundances are controlled by different sets of conditions and that they coexist with different sets of observed species. Of particular note is that non-thermal chemistry appears to play a limited role in the synthesis of OH in diffuse molecular clouds

Direct reduction of N-acetoxy-PhIP by tea polyphenols: a possible mechanism for chemoprevention against PhIP-DNA adduct formation

International Nuclear Information System (INIS)

Lin Dongxin; Thompson, Patricia A.; Teitel, Candee; Chen Junshi; Kadlubar, Fred F.

2003-01-01

The chemopreventive effect of tea against 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP)-DNA adduct formation and its mechanism were studied. Rats were exposed to freshly prepared aqueous extracts of green tea (3% (w/v)) as the sole source of drinking water for 10 days prior to administration with a single dose of PhIP (10 mg/kg body weight) by oral gavage. PhIP-DNA adducts in the liver, colon, heart, and lung were measured using the 32 P-postlabelling technique. Rats pre-treated with tea and given PhIP 20 h before sacrifice had significantly reduced levels of PhIP-DNA adducts as compared with controls given PhIP alone. The possible mechanism of protective effect of tea on PhIP-DNA adduct formation was then examined in vitro. It was found that an aqueous extract of green and black tea, mixtures of green and black tea polyphenols, as well as purified polyphenols could strongly inhibit the DNA binding of N-acetoxy-PhIP, a putative ultimate carcinogen of PhIP formed in vivo via metabolic activation. Among these, epigallocatechin gallate was exceptionally potent. HPLC analyses of these incubation mixtures containing N-acetoxy-PhIP and the tea polyphenols each revealed the production of the parent amine, PhIP, indicating the involvement of a redox mechanism. In view of the presence of relatively high levels of tea polyphenols in rat and human plasma after ingestion of tea, this study suggests that direct reduction of the ultimate carcinogen N-acetoxy-PhIP by tea polyphenols is likely to be involved in the mechanism of chemoprotection of tea against this carcinogen

Lifestyle, Environmental, and Genetic Predictors of Bulky DNA Adducts in a Study Population Nested within a Prospective Danish Cohort

DEFF Research Database (Denmark)

Eriksen, K. T.; Sørensen, M.; Autrup, H.

2010-01-01

Danish cohort. At enrollment, blood samples were collected and information on lifestyle, including dietary and smoking habits, obtained. Previously, bulky DNA adducts were measured in 245 individuals who developed lung cancer and 255 control members of the cohort. Of these 500 individuals, data on 375...... of bulky DNA adduct levels were analyzed by univariate and multivariate regression analyses. Women tended to have higher adduct levels than men. Living in central Copenhagen and surface darkness of fried meat and fish were associated with quantitative higher adduct levels. No significant associations were...

Ionothermal synthesis, crystal structure, and magnetic study of Co2PO4OH isostructural with caminite.

Science.gov (United States)

Wang, Guangmei; Valldor, Martin; Spielberg, Eike T; Mudring, Anja-Verena

2014-03-17

A new framework cobalt(II) hydroxyl phosphate, Co2PO4OH, was prepared by ionothermal synthesis using 1-butyl-4-methyl-pyridinium hexafluorophosphate as the ionic liquid. As the formation of Co2PO4F competes in the synthesis, the synthesis conditions have to be judiciously chosen to obtain well-crystallized, single phase Co2PO4OH. Single-crystal X-ray diffraction analyses reveal Co2PO4OH crystallizes with space group I41/amd (a = b = 5.2713(7) Å, c = 12.907(3) Å, V = 358.63(10) Å(3), and Z = 4). Astonishingly, it does not crystallize isotypically with Co2PO4F but rather isotypically with the hydroxyl minerals caminite Mg1.33[SO4(OH)0.66(H2O)0.33] and lipscombite Fe(2–y)PO4(OH) (0 ≤ y ≤ 2/3). Phosphate tetrahedra groups interconnect four rod-packed face-sharing ∞(1){CoO(6/2)} octahedra chains to form a three-dimensional framework structure. The compound Co2PO4OH was further characterized by powder X-ray diffraction, Fourier transform–infrared, and ultraviolet–visible spectroscopy, confirming the discussed structure. The magnetic measurement reveals that Co2PO4OH undergoes a magnetic transition and presents at low temperatures a canted antiferromagnetic spin order in the ground state.

Scaling submillimeter single-cycle transients toward megavolts per centimeter field strength via optical rectification in the organic crystal OH1.

Science.gov (United States)

Ruchert, Clemens; Vicario, Carlo; Hauri, Christoph P

2012-03-01

We present the generation of high-power single-cycle terahertz (THz) pulses in the organic salt crystal 2-[3-(4-hydroxystyryl)-5.5-dimethylcyclohex-2-enylidene]malononitrile or OH1. Broadband THz radiation with a central frequency of 1.5 THz (λ(c)=200 μm) and high electric field strength of 440 kV/cm is produced by optical rectification driven by the signal of a powerful femtosecond optical parametric amplifier. A 1.5% pump to THz energy conversion efficiency is reported, and pulse energy stability better than 1% RMS is achieved. An approach toward the realization of higher field strength is discussed. © 2012 Optical Society of America

Etheno-DNA adduct formation in rats gavaged with linoleic acid, oleic acid and coconut oil is organ- and gender specific

Energy Technology Data Exchange (ETDEWEB)

Fang Qingming [Division of Toxicology and Cancer Risk Factors, German Cancer Research Center (DKFZ), Im Neuenheimer Feld 280 69120 Heidelberg (Germany); Nair, Jagadeesan [Division of Toxicology and Cancer Risk Factors, German Cancer Research Center (DKFZ), Im Neuenheimer Feld 280 69120 Heidelberg (Germany)], E-mail: j.nair@dkfz.de; Sun Xin [Division of Toxicology and Cancer Risk Factors, German Cancer Research Center (DKFZ), Im Neuenheimer Feld 280 69120 Heidelberg (Germany); Hadjiolov, Dimiter [National Oncological Centre, Sofia (Bulgaria); Bartsch, Helmut [Division of Toxicology and Cancer Risk Factors, German Cancer Research Center (DKFZ), Im Neuenheimer Feld 280 69120 Heidelberg (Germany)

2007-11-01

Intake of linoleic acid (LA) increased etheno-DNA adducts induced by lipid peroxidation (LPO) in white blood cells (WBC) of female but not of male volunteers [J. Nair, C.E. Vaca, I. Velic, M. Mutanen, L.M. Valsta, H. Bartsch, High dietary {omega}-6 polyunsaturated fatty acids drastically increase the formation of etheno-DNA adducts in white blood cells of female subjects, Cancer Epidemiol. Biomarkers Prev. 6 (1997) 597-601]. Etheno-adducts were measured in rats gavaged with LA, oleic acid (OA) and saturated fatty acid rich coconut oil for 30 days. DNA from organs and total WBC was analyzed for 1, N{sup 6}-ethenodeoxyadenosine ({epsilon}dA) and 3, N{sup 4}-ethenodeoxycytidine ({epsilon}dC) by immunoaffinity/{sup 32}P-postlabeling. Colon was the most affected target with LA-treatment, where etheno-adducts were significantly elevated in both sexes. In WBC both adducts were elevated only in LA-treated females. Unexpectedly, OA treatment enhanced etheno-adduct levels in prostate 3-9 fold. Our results in rodents confirm the gender-specific increase of etheno-adducts in WBC-DNA, likely due to LPO induced by redox-cycling of 4-hydroxyestradiol. Colon was a target for LPO-derived DNA-adducts in both LA-treated male and female rats, supporting their role in {omega}-6 PUFA induced colon carcinogenesis.

Electrochemical and computational studies, in protic medium, of Morita-Baylis-Hillman adducts and correlation with leishmanicidal activity

International Nuclear Information System (INIS)

Paiva, Yen G. de; Pinho Júnior, Waldomiro; Souza, Antonio A. de; Costa, Cícero O.; Silva, Fábio P.L.; Lima-Junior, Cláudio G.; Vasconcellos, Mario L.A.A.; Goulart, Marília O.F.

2014-01-01

Highlights: • Twelve Morita-Baylis-Hillman adducts (MBHA) with significant leishmanicidal activity were studied by electrochemical and computational techniques, in protic media. • Ortho compounds for each series showed more negative reduction potentials than their positional isomers. • Less stable hydroxylamines were formed for ortho derivatives. • There is an inverse correlation between electrochemical parameters and bioactivity. - Abstract: Enzymatic bioreduction of nitro groups plays an important role on the activity of biologically active nitroaromatic compounds. Electrochemical methods are useful tools to simulate in vivo metabolic processes. This work presents electrochemical studies, in protic media (EtOH + phosphate buffer 4:6), using cyclic voltammetry (CV) of twelve Morita-Baylis-Hillman adducts (MBHA) with significant leishmanicidal activity. To facilitate the analysis, the molecules were grouped in four classes according to their side chains. Cyclic voltammograms display, in all cases, only one cathodic wave related to the formation of the correspondent hydroxylamines, which suffer further oxidation generating the nitroso derivatives in a sequential cycle. Ortho compounds exhibit more negative reduction potentials compared to the other isomers, in the same chemical class. This phenomenon could be related not only to structural effects but also to the presence of solvation spheres during the electroreduction process and/or stabilization of the resulting hydroxylamine. A proposal to explain the higher leishmanicidal activity of the ortho compounds compared with the meta and para compounds was suggested based on theoretical calculations (HF/6-31 + G */PCM, water, as a calculation level) that indicated lower thermodynamic stability for the ortho, in comparison to the corresponding meta and para hydroxylamines, fact that may suggest the easier transformation of the electrogenerated compounds into reactive electrophilic intermediates or final products

Blood Pyrrole-Protein Adducts--A Biomarker of Pyrrolizidine Alkaloid-Induced Liver Injury in Humans.

Science.gov (United States)

Ruan, Jianqing; Gao, Hong; Li, Na; Xue, Junyi; Chen, Jie; Ke, Changqiang; Ye, Yang; Fu, Peter Pi-Cheng; Zheng, Jiang; Wang, Jiyao; Lin, Ge

2015-01-01

Pyrrolizidine alkaloids (PAs) induce liver injury (PA-ILI) and is very likely to contribute significantly to drug-induced liver injury (DILI). In this study we used a newly developed ultra-high performance liquid chromatography-triple quadrupole-mass spectrometry (UHPLC-MS)-based method to detect and quantitate blood pyrrole-protein adducts in DILI patients. Among the 46 suspected DILI patients, 15 were identified as PA-ILI by the identification of PA-containing herbs exposed. Blood pyrrole-protein adducts were detected in all PA-ILI patients (100%). These results confirm that PA-ILI is one of the major causes of DILI and that blood pyrrole-protein adducts quantitated by the newly developed UHPLC-MS method can serve as a specific biomarker of PA-ILI.

Chemical and biological studies of the major DNA adduct of cis-diamminedichloroplatinum(II), cis-[Pt(NH3)2/d(GpG)/], built into a specific site in a viral genome

International Nuclear Information System (INIS)

Naser, L.J.; Pinto, A.L.; Lippard, S.J.; Essigmann, J.M.

1988-01-01

A duplex Escherichia coli bacteriophage M13 genome was constructed containing a single cis-[Pt(NH 3 ) 2 /d(GpG)/] intrastrand cross-link, the major DNA adduct of the anticancer drug cis-diamminedichloroplatinum(II). The duplex dodecamer d(AGAAGGCCTAGA) x d(TCTAGGCCTTCT) was ligated into the HincII site of M13mp18 to produce an insertion mutant containing a unique StuI restriction enzyme cleavage site. A genome with a 12-base gap in the minus strand was created by hybridizing HincII-linearized M13mp18 duplex DNA with the single-stranded circular DNA of the 12-base insertion mutant. Characterization by pH-dependent 1 H NMR spectroscopy established that platinum binds to the N7 positions of the adjacent guanosines. The platinated oligonucleotide was phosphorylated in the presence of [γ- 32 P]ATP with bacteriophage T4 polynucleotide kinase and incorporated into the 12-base gap of the heteroduplex, thus situating the adduct specifically within the StuI site in the minus strand of the genome. The site of incorporation of the dodecamer was mapped to the expected 36-base region delimited by the recognition sites of XbaI and HindIII. Gradient denaturing gel electrophoresis of a 289-base-pair fragment encompassing the site of adduction revealed that the presence of the cis-[Pt(NH 3 ) 2 /d)GpG)/] cross-link induces localized weakening of the DNA double helix. Comparative studies revealed no difference in survival between platinated and unmodified double-stranded genomes. In contrast, survival of the single-stranded platinated genome was only 10-12% that of the corresponding unmodified single-stranded genome, indicating that the solitary cis-[Pt(NH 3 ) 2 /d(GpG)/] cross-link is lethal to the single-stranded bacteriophage

Induction of stable protein-deoxyribonucleic acid adducts in Chinese hamster cell chromatin by ultraviolet light

International Nuclear Information System (INIS)

Strniste, G.F.; Rall, S.C.

1976-01-01

Ultraviolet (uv)-light-mediated formation of protein-DNA adducts in Chinese hamster cell chromatin was investigated in an attempt to compare chromatin alterations induced in vitro with those observed in vivo. Three independent methods of analysis indicated stable protein-DNA associations: a membrane filter assay which retained DNA on the filter in the presence of high salt-detergent; a Sepharose 4B column assay in which protein eluted coincident with DNA; and a CsCl density gradient equilibrium assay which showed both protein and DNA banding at densities other than their respective native densities. Treatment of the irradiated chromatin with DNase provided further evidence that protein--DNA and not protein-protein adducts were being observed in the column assay. There is a fluence-dependent response of protein-DNA adduct formation when the chromatin is irradiated at low ionic strength and is linear for protein over the range studied. When the chromatin is exposed to differing conditions of pH, ionic strength, or divalent metal ion concentration, the quantity of adduct formed upon uv irradiation varies. Susceptibility to adduct formation can be partially explained in terms of the condensation state of the chromatin and other factors such as rearrangement, denaturation, and dissociation of the chromatin components. Besides providing information on the biological significance of these types of uv-induced lesions, this technique may be useful as a probe of chromatin structure

Thermal Effect on the phosphoric Acid Impregnated Activated Carbon Fiber and Adsorption Properties Toward Isoprene

Energy Technology Data Exchange (ETDEWEB)

Hwang, Taek Sung; Lee, Jin Hyok; Kang, Kyung suk [Department of Chemical Engineering, College of Engineering, Chungnam National University, Taejon (Korea); Kim, Kwang Young [Ace Lab. Co. Ltd. Taejon (Korea); Rhee, Moon Soo [Korea Ginseng and Tobacoo Research Institute, Taejon (Korea)

2001-05-01

To introduce chemisorption property and improve adsorption capacities for isoprene, ACF (Activated Carbon Fiber) was impregnated by phosphoric acid. As the impregnated ACF was dried by programmed temperature from 300 degree C to 500 degree C, degree of impregnation, surface area, thermal stability and adsorption properties for isoprene were observed. The degree of impregnation of the ACF, dried at the 400 degree C, was 12.7 w/w% and surface area was 1148 m{sup 2}/g. Over the temperature range of 450 degree C to 700 degree C, there was one-step thermal degradation by the thermal decomposition of phosphonyl group. The adsorption rate of phosphoric acid on the impregnated ACF, which was dried at 400 degree C, was the fastest. The breakthrough time of ACF that was dried at 400 degree C was 18 min., and its adsorption capacity improved roughly 7.2 times in comparison to the pure ACF. In addition, it was observed the adsorption properties persisted even after the regeneration. The adsorption efficiency of regenerated ACF was 66 percent compared to the unused impregnated ACF. 21 refs., 7 figs., 3 tabs.

Termination of DNA synthesis in vitro at apurinic sites but not at ethyl adducts of the template

Energy Technology Data Exchange (ETDEWEB)

Lockhart, M.L.; Deutsch, J.F.; Yamaura, I.; Cavalieri, L.F.; Rosenberg, B.H.

1982-01-01

The effects of DNA lesions produced by the carcinogenic alkylating agents ethylnitrosourea and diethylsulfate on the extent of DNA synthesis have been studied in a system utilizing circular single-stranded phi X174 DNA as template and a 392-base restriction fragment as primer with E. coli polymerase I (Klenow fragment). Apurinic sites produced by loss of unstable ethylated bases from the template terminate DNA synthesis at the first such site encountered, but ethyl adducts at most, if not all, locations permit readthrough. 22 references, 3 figures, 1 table.

Tomographic reconstruction of OH* chemiluminescence in two interacting turbulent flames

International Nuclear Information System (INIS)

Worth, Nicholas A; Dawson, James R

2013-01-01

The tomographic reconstruction of OH* chemiluminescence was performed on two interacting turbulent premixed bluff-body stabilized flames under steady flow conditions and acoustic excitation. These measurements elucidate the complex three-dimensional (3D) vortex–flame interactions which have previously not been accessible. The experiment was performed using a single camera and intensifier, with multiple views acquired by repositioning the camera, permitting calculation of the mean and phase-averaged volumetric OH* distributions. The reconstructed flame structure and phase-averaged dynamics are compared with OH planar laser-induced fluorescence and flame surface density measurements for the first time. The volumetric data revealed that the large-scale vortex–flame structures formed along the shear layers of each flame collide when the two flames meet, resulting in complex 3D flame structures in between the two flames. With a fairly simple experimental setup, it is shown that the tomographic reconstruction of OH* chemiluminescence in forced flames is a powerful tool that can yield important physical insights into large-scale 3D flame dynamics that are important in combustion instability. (paper)

Protein tyrosine adduct in humans self-poisoned by chlorpyrifos

Science.gov (United States)

Li, Bin; Eyer, Peter; Eddleston, Michael; Jiang, Wei; Schopfer, Lawrence M.; Lockridge, Oksana

2013-01-01

Studies of human cases of self-inflicted poisoning suggest that chlorpyrifos oxon reacts not only with acetylcholinesterase and butyrylcholinesterase but also with other blood proteins. A favored candidate is albumin because in vitro and animal studies have identified tyrosine 411 of albumin as a site covalently modified by organophosphorus poisons. Our goal was to test this proposal in humans by determining whether plasma from humans poisoned by chlorpyrifos has adducts on tyrosine. Plasma samples from 5 self-poisoned humans were drawn at various time intervals after ingestion of chlorpyrifos for a total of 34 samples. All 34 samples were analyzed for plasma levels of chlorpyrifos and chlorpyrifos oxon (CPO) as a function of time post-ingestion. Eleven samples were analyzed for the presence of diethoxyphosphorylated tyrosine by mass spectrometry. Six samples yielded diethoxyphosphorylated tyrosine in pronase digests. Blood collected as late as 5 days after chlorpyrifos ingestion was positive for CPO-tyrosine, consistent with the 20-day half-life of albumin. High plasma CPO levels did not predict detectable levels of CPO-tyrosine. CPO-tyrosine was identified in pralidoxime treated patients as well as in patients not treated with pralidoxime, indicating that pralidoxime does not reverse CPO binding to tyrosine in humans. Plasma butyrylcholinesterase was a more sensitive biomarker of exposure than adducts on tyrosine. In conclusion, chlorpyrifos oxon makes a stable covalent adduct on the tyrosine residue of blood proteins in humans who ingested chlorpyrifos. PMID:23566956