Scavenging ratios of polycyclic aromatic compounds in rain and snow in the Athabasca oil sands region

NASA Astrophysics Data System (ADS)

Zhang, L.; Cheng, I.; Muir, D.; Charland, J.-P.

2015-02-01

The Athabasca oil sands industry in northern Alberta, Canada, is a possible source of polycyclic aromatic compounds (PACs). Monitored PACs, including polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs, and dibenzothiophenes (DBTs), in precipitation and in air at three near-source sites in the Fort MacKay and Fort McMurray area during January 2011 to May 2012, were used to generate a database of scavenging ratios (Wt) for PACs scavenged by both snow and rain. Higher concentrations in precipitation and air were observed for alkylated PAHs and DBTs compared to the other PACs. The sums of the median precipitation concentrations over the period of data analyzed were 0.48 μ g L-1 for the 18 PAHs, 3.38 μ g L-1 for the 20 alkylated PAHs, and 0.94 μ g L-1 for the 5 DBTs. The sums of the median air concentrations for parent PAHs, alkylated PAHs, and DBTs were 8.37, 67.26, and 11.83 ng m-3, respectively. Median Wt over the measurement period were 6100 - 1.1 × 106 from snow scavenging and 350 - 2.3 × 105 from rain scavenging depending on the PAC species. Median Wt for parent PAHs were within the range of those observed at other urban and suburban locations, but Wt for acenaphthylene in snow samples were 2-7 times higher compared to other urban and suburban locations. Wt for some individual snow and rain samples exceeded literature values by a factor of 10. Wt for benzo(a)pyrene, dibenz(a,h)anthracene, and benzo(g,h,i)perylene in snow samples had reached 107, which is the maximum for PAH snow scavenging ratios reported in the literature. From the analysis of data subsets, Wt for particulate-phase dominant PACs were 14-20 times greater than gas-phase dominant PACs in snow samples and 7-20 times greater than gas-phase dominant PACs in rain samples. Wt from snow scavenging were ~ 9 times greater than from rain scavenging for particulate-phase dominant PACs and 4-9.6 times greater than from rain scavenging for gas-phase dominant PACs. Gas-particle fractions of each PAC, particle size distributions of particulate-phase dominant PACs, and the Henry's law constant of gas-phase dominant PACs explained, to a large extent, the different Wt values among the different PACs and precipitation types. The trend in Wt with increasing alkyl substitutions may be attributed to their physico-chemical properties, such as octanol-air and particle partition coefficients and subcooled vapor pressure, which increases gas-particle partitioning and, subsequently, the particulate mass fraction. This study verified findings from a previous study of Wang et al. (2014) that suggested that snow scavenging is more efficient than rain scavenging of particles for equivalent precipitation amounts, and also provided new knowledge of the scavenging of gas-phase PACs and alkylated PACs by snow and rain.

Comprehensive GC²/MS for the monitoring of aromatic tar oil constituents during biodegradation in a historically contaminated soil.

PubMed

Vasilieva, Viktoriya; Scherr, Kerstin E; Edelmann, Eva; Hasinger, Marion; Loibner, Andreas P

2012-02-20

The constituents of tar oil comprise a wide range of physico-chemically heterogeneous pollutants of environmental concern. Besides the sixteen polycyclic aromatic hydrocarbons defined as priority pollutants by the US-EPA (EPA-PAHs), a wide range of substituted (NSO-PAC) and alkylated (alkyl-PAC) aromatic tar oil compounds are gaining increased attention for their toxic, carcinogenic, mutagenic and/or teratogenic properties. Investigations on tar oil biodegradation in soil are in part hampered by the absence of an efficient analytical tool for the simultaneous analysis of this wide range of compounds with dissimilar analytical properties. Therefore, the present study sets out to explore the applicability of comprehensive two-dimensional gas chromatography (GC²/MS) for the simultaneous measurement of compounds with differing polarity or that are co-eluting in one-dimensional systems. Aerobic tar oil biodegradation in a historically contaminated soil was analyzed over 56 days in lab-scale bioslurry tests. Forty-three aromatic compounds were identified with GC²/MS in one single analysis. The number of alkyl chains on a molecule was found to prime over alkyl chain length in hampering compound biodegradation. In most cases, substitution of carbon with nitrogen and oxygen was related to increased compound degradation in comparison to unalkylated and sulphur- or unsubstituted PAH with a similar ring number.The obtained results indicate that GC²/MS can be employed for the rapid assessment of a large variety of structurally heterogeneous environmental contaminants. Its application can contribute to facilitate site assessment, development and control of microbial cleanup technologies for tar oil contaminated sites. Copyright © 2011 Elsevier B.V. All rights reserved.

Elemental carbon and polycyclic aromatic compounds in a 150-year sediment core from Lake Qinghai, Tibetan Plateau, China: influence of regional and local sources and transport pathways.

PubMed

Han, Y M; Wei, C; Bandowe, B A M; Wilcke, W; Cao, J J; Xu, B Q; Gao, S P; Tie, X X; Li, G H; Jin, Z D; An, Z S

2015-04-07

Elemental carbon (EC) and polycyclic aromatic compounds (PACs) are potential proxies for the reconstruction of change in human activities and the origin of air masses in historic times. In this study, the historic deposition of char and soot (the two subtypes of EC) and PACs in a 150-year sediment core from different topographic subbasins of Lake Qinghai on the Qinghai Tibetan Plateau (QTP) were reconstructed. The objective was to explore how the variations in the concentrations of EC and PACs, in the ratios of char to soot and of oxygenated polycyclic aromatic hydrocarbons (OPAHs) to parent PAHs, and in the composition of the PAC mixtures reflect historical changes in climate and human activity and the origin of air masses arriving at the QTP. The deposition fluxes of soot in the different subbasins were similar, averaging 0.18 (range of 0.15-0.25) and 0.16 (0.13-0.23) g m(-2) year(-1), respectively, but they varied for char (averaging 0.11 and 0.22 g m(-2) year(-1), respectively), suggesting ubiquitous atmospheric deposition of soot and local river inputs of char. The different vertical distributions of the char/soot ratios in the different subbasins can be interpreted in terms of the different transport mechanisms of char and soot. An abrupt increase in soot concentrations since 1980 coincides with results from the QTP ice cores that were interpreted to be indicative of soot transport from South Asia. Similar concentration patterns of PAHs with soot and 9,10-anthraquinone/anthracene (9,10-AQ/ANT) ratios all >2.0 suggest regional PAC sources. Increasing PAH/soot ratios and decreasing 9,10-AQ/ANT ratios since the beginning of the 1970s indicate increasing local emissions. The historical trends of these diagnostic ratios indicate an increase in the fossil-fuel contribution since the beginning of the 1970s. The increase of perylene concentrations with increasing core depth and the ratio of perylene to its penta-aromatic isomers indicate that perylene originates mainly from in situ biogenic diagenesis. We demonstrate that the concentrations of EC, char, soot, and PACs in sediments can be used to reconstruct local, regional, and remote sources and transport pathways of pollutants to the QTP.

Photoenhanced Toxicity of Petroleum to Aquatic Invertebrates and Fish: Review of State of the Science

EPA Science Inventory

Photoenhanced toxicity is a distinct mechanism of petroleum toxicity that is mediated by the interaction of solar radiation with specific polycyclic aromatic compounds (PACs) in oil. Phototoxicity is observed as a 2 to greater than 1000 fold increase in chemical toxicity to aqua...

Impact of Increased Thermokarst Activity on Polycyclic Aromatic Compound (PAC) Accumulation in Sediment of Lakes in the Hydrocarbon-Rich Uplands Adjacent to the Mackenzie Delta, NT, Canada

NASA Astrophysics Data System (ADS)

Eickmeyer, D.; Thienpont, J. R.; Blais, J. M.

2017-12-01

In ecologically sensitive, hydrocarbon-rich regions like the western Canadian Arctic, environmental monitoring of oil and gas development often focuses on both direct and unintentional consequences of increased exploration and extraction of hydrocarbon resources. However, proper assessments of impact from these activities could be confounded by natural petrogenic sources in permafrost-rich regions where increased thermokarst activity results in permafrost exposure and erosion of hydrocarbon-rich deposits. Using a paired-lake design in the tundra uplands adjacent to the Mackenzie Delta, NT, we examined 4 lakes with retrogressive thaw slump scars along their shores, and 4 nearby undisturbed reference lakes, focusing on polycyclic aromatic compound (PAC) deposition and composition in the sediment. Total organic carbon (TOC)-normalized concentrations for parent and alkylated PACs were higher in surface sediments of slump-affected lakes than the reference lakes. This followed the pattern previously observed for persistent organic pollutants in these lakes where presence of thaw slumps on the lake shore was associated with lower TOC content in the water column, resulting in a smaller pool of available organic carbon, leading to higher PAC concentrations. Diagnostic ratios of specific PACs also suggested the sediment of slump-affected lakes had greater influence from petroleum-based PAC sources than their reference counterparts. This interpretation was corroborated by a principle components analysis of the metal content in the sediment. Slump-affected lakes were enriched in metals related to shale-based, Quaternary deposits of the Mackenzie Basin (e.g. Ca, Sr, Mg) when compared to reference lakes where these surficial materials were not exposed by thermokarst activity. Higher PAC concentrations and composition indicative of petrogenic sources observed in sediment of slump-affected lakes were best explained as a combination of low TOC availability and increased inputs of previously bound hydrocarbons from the catchment due to permafrost erosion. These findings demonstrate that, to avoid misinterpreting the scale and nature of the impact of hydrocarbon development in northern landscapes, monitoring of sediment PACs must be assessed in the proper framework of these dynamic freshwater systems.

Monitoring system for the study of autotrophic biofilms in bioremediation of polyaromatic compounds

NASA Astrophysics Data System (ADS)

Alarie, Jean P.; Bruttig, A.; Miller, Gordon H.; Hill, Walter; Vo-Dinh, Tuan

1999-02-01

Bacterial and other natural materials such as plants and algae have received increasing interest for bioremediation efforts. The identificatIon of materials capable of biodegrading or sequestering environmental pollutants offers an attractive alternative to chemical or physical means of remediation. A number of bacteria capable of biodegrAding organic or reducing metal pollutants have received great interest. Similarly, the use of natural plants to absorb pollutants from soil anD liquid samples is another potential approach. Our interest lies in identification of naturally occurring algae and their ability to absorb polyaromatic compounds (PAC) from groundwater sources (i.e. streams). These algae could serve as natural water filters for streams contaminated with Polyaromatic hydrocarbons. Polycyclic aromatic compounds, which comprise a complex class of condensed multi-ring benzenoid compounds, are important environmental pollutants originating from a wide variety of natural and anthropogenic sources. PACs are generally formed during incomplete combustion or pyrolysis of organic matter containing carbon and hydrogen. Because combustion of organic materials is involved in countless natural processes or human activities, PACs are omnipresent and abundant pollutants in air, soil and water. Among energy-related products, fossil fuels are the major sources of PACs. The primary sources of airborne PACs are associated with combustion, coal coking, and petroleum catalytic cracking. Coal and shale conversion also contribute to production of PACs. Production, transportation and, use of synthetic fuels and petroleum products provide emission sources for PACs. In urban environments an significant source of PACs is diesel exhaust. Food cooking and cigarette smoking activities contribute to PAC occurrence in indoor environments. Chemical analysis of PACs is of great environmental and toxicological interest because many of them have been shown to be mutagens and/or potent carcinogens in laboratory animal assays. The parent homocyclic species, which contain only carbon and hydrogen, are the familiar polyaromatic hydrocarbon (PAH) compounds. In addition to the PAH compounds, there are thousands of substituted compounds that could have various substituent groups, such as alkyl, amino, chloro, cyano, hydroxy, oxy, or thio groups. In this study we investigate anthracene and pyrene as PAH model systems. A portable fiberoptic instrument capable of real-time measurements has been developed for field screening these PAHs in surface water and natural algae systems. Our preliminary studies investigated the detection limits of anthracene and pyrene and the adsorption properties of two algae using fluorescence monitoring. An exposure study of the algae to 5 ppb anthracene was performed to investigate the ability of the algae to adsorb PAHs.

Effect of mineral surface properties (alumina, kaolinite) on the sorptive fractionation mechanisms of soil fulvic acids: Molecular-scale ESI-MS studies

NASA Astrophysics Data System (ADS)

Fleury, Guillaume; Del Nero, Mirella; Barillon, Rémi

2017-01-01

We addressed the effects of mineral surface properties (kaolinite versus Al-oxide) on the sorption-driven fractionation of a soil fulvic acid (FA) at acidic pH, mainly by means of ESI(-)-FTMS analysis of initial and supernatant solutions of FA sorption batch experiments. The MS data provided clear molecular-scale evidence of distinct mechanisms and molecular parameters controlling the FA fractionation upon its sorption on clay and oxide surfaces, respectively. Identification of sorbing and not-sorbing FA compounds in kaolinite-solution systems revealed a weak fractionation among members of sbnd CO2 series of aliphatics or not-condensed aromatics (NCAs) at pH 3.8, and almost no sorption of poorly-oxygenated polycyclic aromatic compounds (PACs) and NCAs. This first molecular-scale description of a FA fractionation in a clay-solution system suggests that H-bonding with low affinity sites (aluminol/silanol) on the basal planes of the clay particles is the main mechanism of sorption. Due to the predominance of such weak and poorly-selective mechanism, the sorption of aliphatic and NCA molecules bearing oxygenated functionalities was prevented at pH 5, due to dissolved Al competing successfully for their coordination. In contrast, a strong FA fractionation was observed onto alumina, with a preferential retention of PACs and highly-oxygenated aliphatics and NCAs. The major part of the poorly oxygenated aliphatics was left in solution. The sorption degree of NCAs and aliphatics was strongly correlated with molecular acidity. For PACs and poorly-oxygenated NCAs, the sorption was driven by reactions of surface ligand exchange (for the most oxygenated compounds) or by hydrophobic interactions (for the least oxygenated compounds).

Has Alberta Oil Sands Development Altered Delivery of Polycyclic Aromatic Compounds to the Peace-Athabasca Delta?

PubMed Central

Hall, Roland I.; Wolfe, Brent B.; Wiklund, Johan A.; Edwards, Thomas W. D.; Farwell, Andrea J.; Dixon, D. George

2012-01-01

Background The extent to which Alberta oil sands mining and upgrading operations have enhanced delivery of bitumen-derived contaminants via the Athabasca River and atmosphere to the Peace-Athabasca Delta (200 km to the north) is a pivotal question that has generated national and international concern. Accounts of rare health disorders in residents of Fort Chipewyan and deformed fish in downstream ecosystems provided impetus for several recent expert-panel assessments regarding the societal and environmental consequences of this multi-billion-dollar industry. Deciphering relative contributions of natural versus industrial processes on downstream supply of polycyclic aromatic compounds (PACs) has been identified as a critical knowledge gap. But, this remains a formidable scientific challenge because loading from natural processes remains unknown. And, industrial activity occurs in the same locations as the natural bitumen deposits, which potentially confounds contemporary upstream-downstream comparisons of contaminant levels. Methods/Principal Findings Based on analyses of lake sediment cores, we provide evidence that the Athabasca Delta has been a natural repository of PACs carried by the Athabasca River for at least the past two centuries. We detect no measureable increase in the concentration and proportion of river-transported bitumen-associated indicator PACs in sediments deposited in a flood-prone lake since onset of oil sands development. Results also reveal no evidence that industrial activity has contributed measurably to sedimentary concentration of PACs supplied by atmospheric transport. Conclusions/Significance Findings suggest that natural erosion of exposed bitumen in banks of the Athabasca River and its tributaries is a major process delivering PACs to the Athabasca Delta, and the spring freshet is a key period for contaminant mobilization and transport. This baseline environmental information is essential for informed management of natural resources and human-health concerns by provincial and federal regulatory agencies and industry, and for designing effective long-term monitoring programs for the lower Athabasca River watershed. PMID:23049946

Comparing Urinary Biomarkers of Airborne and Dermal Exposure to Polycyclic Aromatic Compounds in Asphalt-Exposed Workers

PubMed Central

Sobus, Jon R.; McClean, Michael D.; Herrick, Robert F.; Waidyanatha, Suramya; Nylander-French, Leena A.; Kupper, Lawrence L.; Rappaport, Stephen M.

2009-01-01

When working with hot mix asphalt, road pavers are exposed to polycyclic aromatic hydrocarbons (PAHs) through the inhalation of vapors and particulate matter (PM) and through dermal contact with PM and contaminated surfaces. Several PAHs with four to six rings are potent carcinogens which reside in these particulate emissions. Since urinary biomarkers of large PAHs are rarely detectable in asphalt workers, attention has focused upon urinary levels of the more volatile and abundant two-ring and three-ring PAHs as potential biomarkers of PAH exposure. Here, we compare levels of particulate polycyclic aromatic compounds (P-PACs, a group of aromatic hydrocarbons containing PAHs and heterocyclic compounds with four or more rings) in air and dermal patch samples from 20 road pavers to the corresponding urinary levels of naphthalene (U-Nap) (two rings), phenanthrene (U-Phe) (three rings), monohydroxylated metabolites of naphthalene (OH-Nap) and phenanthrene (OH-Phe), and 1-hydroxypyrene (OH-Pyr) (four rings), the most widely used biomarker of PAH exposure. For each worker, daily breathing-zone air (n = 55) and dermal patch samples (n = 56) were collected on three consecutive workdays along with postshift, bedtime, and morning urine samples (n = 149). Measured levels of P-PACs and the urinary analytes were used to statistically model exposure–biomarker relationships while controlling for urinary creatinine, smoking status, age, body mass index, and the timing of urine sampling. Levels of OH-Phe in urine collected postshift, at bedtime, and the following morning were all significantly associated with levels of P-PACs in air and dermal patch samples. For U-Nap, U-Phe, and OH-Pyr, both air and dermal patch measurements of P-PACs were significant predictors of postshift urine levels, and dermal patch measurements were significant predictors of bedtime urine levels (all three analytes) and morning urine levels (U-Nap and OH-Pyr only). Significant effects of creatinine concentration were observed for all analytes, and modest effects of smoking status and body mass index were observed for U-Phe and OH-Pyr, respectively. Levels of OH-Nap were not associated with P-PAC measurements in air or dermal patch samples but were significantly affected by smoking status, age, day of sample collection, and urinary creatinine. We conclude that U-Nap, U-Phe, OH-Phe, and OH-Pyr can be used as biomarkers of exposure to particulate asphalt emissions, with OH-Phe being the most promising candidate. Indications that levels of U-Nap, U-Phe, and OH-Pyr were significantly associated with dermal patch measurements well into the evening after a given work shift, combined with the small ratios of within-person variance components to between-person variance components at bedtime, suggest that bedtime measurements may be useful for investigating dermal PAH exposures. PMID:19602502

Petroleum mineral oil refining and evaluation of cancer hazard.

PubMed

Mackerer, Carl R; Griffis, Larry C; Grabowski, John S; Reitman, Fred A

2003-11-01

Petroleum base oils (petroleum mineral oils) are manufactured from crude oils by vacuum distillation to produce several distillates and a residual oil that are then further refined. Aromatics including alkylated polycyclic aromatic compounds (PAC) are undesirable constituents of base oils because they are deleterious to product performance and are potentially carcinogenic. In modern base oil refining, aromatics are reduced by solvent extraction, catalytic hydrotreating, or hydrocracking. Chronic exposure to poorly refined base oils has the potential to cause skin cancer. A chronic mouse dermal bioassay has been the standard test for estimating carcinogenic potential of mineral oils. The level of alkylated 3-7-ring PAC in raw streams from the vacuum tower must be greatly reduced to render the base oil noncarcinogenic. The processes that can reduce PAC levels are known, but the operating conditions for the processing units (e.g., temperature, pressure, catalyst type, residence time in the unit, unit engineering design, etc.) needed to achieve adequate PAC reduction are refinery specific. Chronic dermal bioassays provide information about whether conditions applied can make a noncarcinogenic oil, but cannot be used to monitor current production for quality control or for conducting research or developing new processes since this test takes at least 78 weeks to conduct. Three short-term, non-animal assays all involving extraction of oil with dimethylsulfoxide (DMSO) have been validated for predicting potential carcinogenic activity of petroleum base oils: a modified Ames assay of a DMSO extract, a gravimetric assay (IP 346) for wt. percent of oil extracted into DMSO, and a GC-FID assay measuring 3-7-ring PAC content in a DMSO extract of oil, expressed as percent of the oil. Extraction with DMSO concentrates PAC in a manner that mimics the extraction method used in the solvent refining of noncarcinogenic oils. The three assays are described, data demonstrating the validation of the assays are shown, and test results of currently manufactured base oils are summarized to illustrate the general lack of cancer hazard for the base oils now being manufactured.

Peer consultation on relationship between PAC profile and toxicity of petroleum substances.

PubMed

Patterson, Jacqueline; Maier, Andrew; Kohrman-Vincent, Melissa; Dourson, Michael L

2013-11-01

An expert peer consultation panel reviewed a report by the PAC Analysis Task Group, which hypothesized that systemic, developmental, and reproductive toxicity observed in repeated-dose dermal toxicity studies was related to polycyclic aromatic compound (PAC) content. Peer consultations seek to solicit scientific and technical input from experts on the scientific basis and merits of the subject report. This peer consultation panel included nine scientists with expertise in petroleum chemistry, biostatistics, toxicology, risk assessment, structure activity, and reproductive and developmental toxicology. The panel evaluated the technical quality of the PAC report and provided recommendations for improving the statistical and biological approaches. The PAC report authors revised their methods and documentation, which are published elsewhere in this supplement. A review of the post peer consultation manuscripts confirmed that many of the key suggestions from expert panel members were considered and incorporated. In cases where the PAC report authors did not fully incorporate panel suggestions from the peer consultation, they have provided an explanation and support for their decision. This peer consultation demonstrates the value of formal engagement of peers in development of new scientific methods and approaches. Copyright © 2012 Elsevier Inc. All rights reserved.

Native oxy-PAHs, N-PACs, and PAHs in historically contaminated soils from Sweden, Belgium, and France: their soil-porewater partitioning behavior, bioaccumulation in Enchytraeus crypticus, and bioavailability.

PubMed

Arp, Hans Peter H; Lundstedt, Staffan; Josefsson, Sarah; Cornelissen, Gerard; Enell, Anja; Allard, Ann-Sofie; Kleja, Dan Berggren

2014-10-07

Soil quality standards are based on partitioning and toxicity data for laboratory-spiked reference soils, instead of real world, historically contaminated soils, which would be more representative. Here 21 diverse historically contaminated soils from Sweden, Belgium, and France were obtained, and the soil-porewater partitioning along with the bioaccumulation in exposed worms (Enchytraeus crypticus) of native polycyclic aromatic compounds (PACs) were quantified. The native PACs investigated were polycyclic aromatic hydrocarbons (PAHs) and, for the first time to be included in such a study, oxygenated-PAHs (oxy-PAHs) and nitrogen containing heterocyclic PACs (N-PACs). The passive sampler polyoxymethylene (POM) was used to measure the equilibrium freely dissolved porewater concentration, Cpw, of all PACs. The obtained organic carbon normalized partitioning coefficients, KTOC, show that sorption of these native PACs is much stronger than observed in laboratory-spiked soils (typically by factors 10 to 100), which has been reported previously for PAHs but here for the first time for oxy-PAHs and N-PACs. A recently developed KTOC model for historically contaminated sediments predicted the 597 unique, native KTOC values in this study within a factor 30 for 100% of the data and a factor 3 for 58% of the data, without calibration. This model assumes that TOC in pyrogenic-impacted areas sorbs similarly to coal tar, rather than octanol as typically assumed. Black carbon (BC) inclusive partitioning models exhibited substantially poorer performance. Regarding bioaccumulation, Cpw combined with liposome-water partition coefficients corresponded better with measured worm lipid concentrations, Clipid (within a factor 10 for 85% of all PACs and soils), than Cpw combined with octanol-water partition coefficients (within a factor 10 for 76% of all PACs and soils). E. crypticus mortality and reproducibility were also quantified. No enhanced mortality was observed in the 21 historically contaminated soils despite expectations from PAH spiked reference soils. Worm reproducibility weakly correlated to Clipid of PACs, though the contributing influence of metal concentrations and soil texture could not be taken into account. The good agreement of POM-derived Cpw with independent soil and lipid partitioning models further supports that soil risk assessments would improve by accounting for bioavailability. Strategies for including bioavailability in soil risk assessment are presented.

Time to Say Goodbye to the 16 EPA PAHs? Toward an Up-to-Date Use of PACs for Environmental Purposes

PubMed Central

Andersson, Jan T.; Achten, Christine

2015-01-01

The 16 EPA PAHs have played an exceptionally large role above all in environmental and analytical sciences in the last 40 years, but now there are good reasons to question their utility in many circumstances even though their use is so established and comfortable. Here we review the reasons why the list has been so successful and why sometimes it is seen as less relevant. Three groups of polycyclic aromatic compounds (PAC) are missing: larger and highly relevant PAHs, alkylated PACs, and compounds containing heteroatoms. Attempts to improve the situation for certain matrixes are known and here: (1) an updated list of PAHs (including the 16 EPA PAHs) for the evaluation of the toxicity in the environment (40 EnvPAHs); (2) a list of 23 NSO-heterocyclic compounds and 6 heterocyclic metabolites; and (3) lists of 10 oxy-PAHs and 10 nitro-PAHs are proposed for practical use in the future. A discussion in the scientific community about these lists is invited. Although the state of knowledge has improved dramatically since the introduction of the 16 EPA PAHs in the 1970s, this summary also shows that more research is needed about the toxicity, occurrence in the environment and chemical analysis, particularly of alkylated PAHs, higher molecular weight PAHs and substituted PACs such as amino-PAHs, cyano-PAHs, etc.. We also suggest that a long overdue discussion of an update of regulatory environmental PAH analysis is initiated. PMID:26823645

Effect of adsorbent addition on floc formation and clarification.

PubMed

Younker, Jessica M; Walsh, Margaret E

2016-07-01

Adding adsorbent into the coagulation process is an emerging treatment solution for targeting hard-to-remove dissolved organic compounds from both drinking water and industrial wastewater. The impact of adding powdered activated carbon (PAC) or organoclay (OC) adsorbents with ferric chloride (FeCl3) coagulant was investigated in terms of potential changes to the coagulated flocs formed with respect to size, structure, and breakage and regrowth properties. The ability of dissolved air flotation (DAF) and sedimentation (SED) clarification processes to remove hybrid adsorbent-coagulant flocs was also evaluated through clarified water quality analysis of samples collected in bench-scale jar test experiments. The jar tests were conducted using both a synthetic fresh water and oily wastewater test water spiked with dissolved aromatic compounds phenol and naphthalene. Results of the study demonstrated that addition of adsorbent reduced the median coagulated floc size by up to 50% but did not affect floc strength or regrowth potential after application of high shear. Experimental results in fresh water demonstrated that sedimentation was more effective than DAF for clarification of both FeCl3-PAC and FeCl3-OC floc aggregates. However, experimental tests performed on the synthetic oily wastewater showed that coagulant-adsorbent floc aggregates were effectively removed with both DAF and sedimentation treatment, with lower residual turbidity achieved in clarified water samples than with coagulation treatment alone. Addition of OC or PAC into the coagulation process resulted in removals of over half, or nearly all of the dissolved aromatics, respectively. Copyright © 2016 Elsevier Ltd. All rights reserved.

Biodegradation of crude oil in Arctic subsurface water from the Disko Bay (Greenland) is limited.

PubMed

Scheibye, Katrine; Christensen, Jan H; Johnsen, Anders R

2017-04-01

Biological degradation is the main process for oil degradation in a subsurface oil plume. There is, however, little information on the biodegradation potential of Arctic, marine subsurface environments. We therefore investigated oil biodegradation in microcosms at 2 °C containing Arctic subsurface seawater from the Disko Bay (Greenland) and crude oil at three concentrations of 2.5-10 mg/L. Within 71 days, the total petroleum hydrocarbon concentration decreased only by 18 ± 18% for an initial concentration of 5 mg/L. The saturated alkanes nC13-nC30 and the isoprenoids iC18-iC21 were biodegraded at all concentrations indicating a substantial potential for biodegradation of these compound classes. Polycyclic aromatic compounds (PACs) disappeared from the oil phase, but dissolution was the main process of removal. Analysis of diagnostic ratios indicated almost no PAC biodegradation except for the C1-naphthalenes. To conclude, the marine subsurface microorganisms from the Disko Bay had the potential for biodegradation of n-alkanes and isoprenoids while the metabolically complex and toxic PACs and their alkylated homologs remained almost unchanged. Copyright © 2016 Elsevier Ltd. All rights reserved.

The Gastrointestinal Tract as a Key Target Organ for the Health-Promoting Effects of Dietary Proanthocyanidins

PubMed Central

Cires, María José; Wong, Ximena; Carrasco-Pozo, Catalina; Gotteland, Martin

2017-01-01

Proanthocyanidins (PACs) are polymers of flavan-3-ols abundant in many vegetable foods and beverages widely consumed in the human diet. There is increasing evidence supporting the beneficial impact of dietary PACs in the prevention and nutritional management of non-communicable chronic diseases. It is considered that PACs with a degree of polymerization >3 remain unabsorbed in the gastrointestinal (GI) tract and accumulate in the colonic lumen. Accordingly, the GI tract may be considered as a key organ for the healthy-promoting effects of dietary PACs. PACs form non-specific complexes with salivary proteins in mouth, originating the sensation of astringency, and with dietary proteins, pancreatic enzymes, and nutrient transporters in the intestinal lumen, decreasing the digestion and absorption of carbohydrates, proteins, and lipids. They also exert antimicrobial activities, interfering with cariogenic or ulcerogenic pathogens in the mouth (Streptococcus mutans) and stomach (Helicobacter pylori), respectively. Through their antioxidant and antiinflammatory properties, PACs decrease inflammatory processes in animal model of gastric and colonic inflammation. Interestingly, they exert prebiotic activities, stimulating the growth of Lactobacillus spp. and Bifidobacterium spp. as well as some butyrate-producing bacteria in the colon. Finally, PACs are also metabolized by the gut microbiota, producing metabolites, mainly aromatic acids and valerolactones, which accumulate in the colon and/or are absorbed into the bloodstream. Accordingly, these compounds could display biological activities on the colonic epithelium or in extra-intestinal tissues and, therefore, contribute to part of the beneficial effects of dietary PACs. PMID:28097121

Development of a screening tool to prioritize testing for the carcinogenic hazard of residual aromatic extracts and related petroleum streams.

PubMed

Goyak, Katy O; Kung, Ming H; Chen, Min; Aldous, Keith K; Freeman, James J

2016-12-15

Residual aromatic extracts (RAE) are petroleum substances with variable composition predominantly containing aromatic hydrocarbons with carbon numbers greater than C25. Because of the high boiling nature of RAEs, the aromatics present are high molecular weight, with most above the range of carcinogenic polycyclic aromatic hydrocarbons (PAHs). However, refinery distillations are imperfect; some PAHs and their heteroatom-containing analogs (collectively referred to as polycyclic aromatic content or PAC) may remain in the parent stream and be extracted into the RAE, and overall PAC content is related to the carcinogenic potential of an RAE. We describe here a real-time analytical chemistry-based tool to assess the carcinogenic hazard of RAE via the development of a functional relationship between carcinogenicity and boiling point. Samples representative of steps along the RAE manufacturing process were obtained from five refineries to evaluate relationships between mutagenicity index (MI), PAC ring content and gas chromatographic distillation (GCD) curves. As expected, a positive linear relationship between MI and PAC ring content occurred, most specifically for 3-6 ring PAC (R 2 =0.68). A negative correlation was found between MI and temperature at 5% vaporization by GCD (R 2 =0.72), indicating that samples with greater amounts of lower boiling constituents were more likely to be carcinogenic. The inverse relationship between boiling range and carcinogenicity was further demonstrated by fractionation of select RAE samples (MI=0.50+0.07; PAC=1.70+0.51wt%; n=5) into low and high boiling fractions, where lower boiling fractions were both more carcinogenic than the higher boiling fractions (MI=2.36±0.55 and 0.17±0.11, respectively) and enriched in 3-6 ring PACs (5.20+0.70wt% and 0.97+0.35wt%, respectively). The criteria defining carcinogenicity was established as 479°C for the 5% vaporization points by GCD, with an approximate 95% probability of a future sample having an MI below the recommended limit of 0.4 for RAEs. Overall, these results provide a cost-efficient and real-time tool by which the carcinogenic potential of RAEs can be assessed at the refinery level, ultimately providing a means to readily monitor and minimize the carcinogenic potential of RAEs. Copyright © 2016. Published by Elsevier Ireland Ltd.

A two-dimensional contaminant fate and transport model for the lower Athabasca River

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brownlee, B.G.; Booty, W.G.; MacInnis, G.A.

1995-12-31

The lower Athabasca River flows through the Athabasca Oil Sands deposits in northeastern Alberta. Two oil sands mining/extraction/upgrading plants operate near the river downstream from Fort McMurray. Process water is stored in large tailings ponds. One of the plants (Suncor) has a licensed discharge (mostly cooling water) to the river. This effluent contains low concentrations ({<=} 1 {micro}g/L) of various polycyclic aromatic compounds (PACs). Several tributary streams which cut through oil sands deposits are potential sources of hydrocarbons to the Athabasca. The authors have found that river suspended sediments give positive responses in a number of toxicity tests, using bothmore » direct and indirect (organic-solvent extract) methods. Several environmental impact assessments are required as a result of industry expansion. To provide an assessment tool for PACs, the authors are developing a two-dimensional contaminant fate and transport model for a 120-km portion of the Athabasca River downstream from Fort McMurray. Hydraulic calibration of the model was done using sodium and chloride from a major tributary as tracers. Two groups of compounds are being modelled: (1) PACs from the Suncor effluent, and (2) PACs from natural/background sources. PAC concentrations in the river were typically < 1 ng/L, requiring large volume extractions and highly sensitive analysis. Processes such as sediment-water partitioning and biodegradation are being estimated from field experiments using river water and suspended sediment. Photodegradation is likely unimportant in this turbid river due to low penetration of 280--350 nm light. Initially, volatilization will be modelled using estimated or literature values for Henry`s constants, but may require more refined estimates from laboratory experiments.« less

On-road traffic emissions of polycyclic aromatic hydrocarbons and their oxy- and nitro- derivative compounds measured in road tunnel environments.

PubMed

Keyte, Ian J; Albinet, Alexandre; Harrison, Roy M

2016-10-01

Vehicular emissions are a key source of polycyclic aromatic compounds (PACs), including polycyclic aromatic hydrocarbons (PAHs) and their oxygenated (OPAH) and nitrated (NPAH) derivatives, in the urban environment. Road tunnels are a useful environment for the characterisation of on-road vehicular emissions, providing a realistic traffic fleet and a lack of direct sunlight, chemical reactivity and non-traffic sources. In the present investigation the concentrations of selected PAHs, OPAHs and NPAHs have been measured in the Parc des Princes Tunnel in Paris (PdPT, France), and at the Queensway Road Tunnel and an urban background site in Birmingham (QT, U.K). A higher proportion of semi-volatile (3-4 ring) PAH, OPAH and NPAH compounds are associated with the particulate phase compared with samples from the ambient environment. A large (~85%) decline in total PAH concentrations is observed between 1992 and 2012 measurements in QT. This is attributed primarily to the introduction of catalytic converters in the U.K as well as increasingly stringent EU vehicle emissions legislation. In contrast, NPAH concentrations measured in 2012 are similar to those measured in 1996. This observation, in addition to an increased proportion of (Phe+Flt+Pyr) in the observed PAH burden in the tunnel, is attributed to the increased number of diesel passenger vehicles in the U.K during this period. Except for OPAHs, comparable PAH and NPAH concentrations are observed in both investigated tunnels (QT and PdP). Significant differences are shown for specific substances between PAC chemical profiles in relation with the national traffic fleet differences (33% diesel passenger cars in U.K. vs 69% in France and up to 80% taking into account all vehicle categories). The dominating and sole contribution of 1-Nitropyrene observed in the PdPT NPAH profile strengthens the promising use of this compound as a diesel exhaust marker for PM source apportionment studies. Copyright © 2016 British Geological Survey, NERC. Published by Elsevier B.V. All rights reserved.

Adsorption of selected endocrine disrupting compounds and pharmaceuticals on activated biochars.

PubMed

Jung, Chanil; Park, Junyeong; Lim, Kwang Hun; Park, Sunkyu; Heo, Jiyong; Her, Namguk; Oh, Jeill; Yun, Soyoung; Yoon, Yeomin

2013-12-15

Chemically activated biochar produced under oxygenated (O-biochar) and oxygen-free (N-biochar) conditions were characterized and the adsorption of endocrine disrupting compounds (EDCs): bisphenol A (BPA), atrazine (ATR), 17 α-ethinylestradiol (EE2), and pharmaceutical active compounds (PhACs); sulfamethoxazole (SMX), carbamazepine (CBM), diclofenac (DCF), ibuprofen (IBP) on both biochars and commercialized powdered activated carbon (PAC) were investigated. Characteristic analysis of adsorbents by solid-state nuclear magnetic resonance (NMR) was conducted to determine better understanding about the EDCs/PhACs adsorption. N-biochar consisted of higher polarity moieties with more alkyl (0-45 ppm), methoxyl (45-63 ppm), O-alkyl (63-108 ppm), and carboxyl carbon (165-187 ppm) content than other adsorbents, while aromaticity of O-biochar was higher than that of N-biochar. O-biochar was composed mostly of aromatic moieties, with low H/C and O/C ratios compared to the highly polarized N-biochar that contained diverse polar functional groups. The higher surface area and pore volume of N-biochar resulted in higher adsorption capacity toward EDCs/PhACs along with atomic-level molecular structural property than O-biochar and PAC. N-biochar had a highest adsorption capacity of all chemicals, suggesting that N-biochar derived from loblolly pine chip is a promising sorbent for agricultural and environmental applications. The adsorption of pH-sensitive dissociable SMX, DCF, IBP, and BPA varied and the order of adsorption capacity was correlated with the hydrophobicity (Kow) of adsorbates throughout the all adsorbents, whereas adsorption of non-ionizable CBM, ATR, and EE2 in varied pH allowed adsorbents to interact with hydrophobic property of adsorbates steadily throughout the study. Copyright © 2013 Elsevier B.V. All rights reserved.

Concentrations, loads, and yields of particle-associated contaminants in urban creeks, Austin, Texas, 1999-2004

USGS Publications Warehouse

Mahler, B.J.; Van Metre, P.C.; Wilson, J.T.; Guilfoyle, A.L.; Sunvison, M.W.

2006-01-01

Concentrations, loads, and yields of particle-associated (hydrophobic) contaminants (PACs) in urban runoff in creeks in Austin, Texas, were characterized using an innovative approach: large-volume suspended-sediment sampling. This approach isolates suspended sediment from the water column in quantities sufficient for direct chemical analysis of PACs. During 1999-2004, samples were collected after selected rain events from each of five stream sites and Barton Springs for a study by the U.S. Geological Survey, in cooperation with the City of Austin. Sediment isolated from composited samples was analyzed for major elements, metals, organochlorine compounds, and polycyclic aromatic hydrocarbons (PAHs). In addition, at the Shoal Creek and Boggy Creek sites, individual samples for some events were analyzed to investigate within-event variation in sediment chemistry. Organochlorine compounds detected in suspended sediment included chlordane, dieldrin, DDD, DDE, DDT, and polychlorinated biphenyls (PCBs). Concentrations of PACs varied widely both within and between sites, with higher concentrations at the more urban sites and multiple nondetections at the least-urban sites. Within-site variation for metals and PAHs was smaller than between-site variation, and concentrations and yields of these and the organochlorine compounds correlated positively to the percentage of urban land use in the watershed. Loads of most PACs tested correlated significantly with suspended-sediment loads. Concentrations of most PACs correlated strongly with three measures of urban land use. Variation in suspended-sediment chemistry during runoff events was investigated at the Shoal and Boggy Creek sites. Five of the eight metals analyzed, dieldrin, chlordane, PCBs, and PAHs were detected at the highest concentrations in the first sample collected at the Shoal Creek site, a first-flush effect, but not at the Boggy Creek site. Temporal patterns in concentrations of DDT and its breakdown products varied from one event to the next. In spite of the first-flush effect in concentrations at the Shoal Creek site, most of the contaminant load was transported at peak discharge, when suspended-sediment concentration and load are maximum.

Effect of oxidation and extent of oxidation on biologically active PACs in asphalt products.

PubMed

Trumbore, David; Osborn, Linda; Blackburn, Gary; Niebo, Ron; Kriech, Anthony; Maxim, L Daniel

2011-10-01

Recent studies have reported divergent results in rodent cancer assays using fume condensates from a variety of asphalt products. This paper presents results of a study investigating the role of oxidation, or extent of oxidation, on these findings. Five straight run asphalts, made from widely used crude oils, were used as inputs to both production scale and laboratory oxidation units and processed to a range of softening points used in common roofing products. For each of the five asphalts studied, the oxidation reaction significantly decreased measures of polycyclic aromatic compounds (PACs) that have been linked, previously and in analyses included in this study, to tumor induction in rodent bioassays. Mutagenicity index determined by the modified Ames assay was reduced between 41% and 50% from the input asphalt to the final oxidized product. A fluorescence method tuned to a subset of PAC compounds that have been associated with carcinogenic behavior in mouse bioassays was reduced between 39% and 71%. The decrease was largest in the first quarter of the oxidation reaction. These findings indicate that oxidation, by itself, was not a likely factor in the tumor induction seen in the previous studies. Rather, other factors such as the conditions of fume generation and crude source (coupled with possible differences in distillation endpoints) were more likely to have determined the outcomes. Analyses of previously published data, presented in this paper, suggest that the modified Ames and fluorescence assays are valuable screening tools for use in future health-related asphalt research.

Impact of clay mineral on air oxidation of PAH-contaminated soils.

PubMed

Biache, Coralie; Kouadio, Olivier; Lorgeoux, Catherine; Faure, Pierre

2014-09-01

This work investigated the impact of a clay mineral (bentonite) on the air oxidation of the solvent extractable organic matters (EOMs) and the PAHs from contaminated soils. EOMs were isolated from two coking plant soils and mixed with silica sand or bentonite. These samples, as well as raw soils and bentonite/soil mixtures, were oxidized in air at 60 and 100 °C for 160 days. Mineralization was followed by measuring the CO2 produced over the experiments. EOM, polycyclic aromatic compound (PAC), including PAH, contents were also determined. Oxidation led to a decrease in EOM contents and PAH concentrations, these diminutions were enhanced by the presence of bentonite. Transfer of carbon from EOM to insoluble organic matter pointed out a condensation phenomenon leading to a stabilization of the contamination. Higher mineralization rates, observed during the oxidation of the soil/bentonite mixtures, seem to indicate that this clay mineral had a positive influence on the transformation of PAC into CO2.

Chemometric assessment of enhanced bioremediation of oil contaminated soils.

PubMed

Soleimani, Mohsen; Farhoudi, Majid; Christensen, Jan H

2013-06-15

Bioremediation is a promising technique for reclamation of oil polluted soils. In this study, six methods for enhancing bioremediation were tested on oil contaminated soils from three refinery areas in Iran (Isfahan, Arak, and Tehran). The methods included bacterial enrichment, planting, and addition of nitrogen and phosphorous, molasses, hydrogen peroxide, and a surfactant (Tween 80). Total petroleum hydrocarbon (TPH) concentrations and CHEMometric analysis of Selected Ion Chromatograms (SIC) termed CHEMSIC method of petroleum biomarkers including terpanes, regular, diaromatic and triaromatic steranes were used for determining the level and type of hydrocarbon contamination. The same methods were used to study oil weathering of 2 to 6 ring polycyclic aromatic compounds (PACs). Results demonstrated that bacterial enrichment and addition of nutrients were most efficient with 50% to 62% removal of TPH. Furthermore, the CHEMSIC results demonstrated that the bacterial enrichment was more efficient in degradation of n-alkanes and low molecular weight PACs as well as alkylated PACs (e.g. C₃-C₄ naphthalenes, C₂ phenanthrenes and C₂-C₃ dibenzothiophenes), while nutrient addition led to a larger relative removal of isoprenoids (e.g. norpristane, pristane and phytane). It is concluded that the CHEMSIC method is a valuable tool for assessing bioremediation efficiency. Copyright © 2013 Elsevier B.V. All rights reserved.

Reconstruction of atmospheric soot history in inland regions from lake sediments over the past 150 years

PubMed Central

Han, Y. M.; Wei, C.; Huang, R.-J.; Bandowe, B. A. M.; Ho, S. S. H.; Cao, J. J.; Jin, Z. D.; Xu, B. Q.; Gao, S. P.; Tie, X. X.; An, Z. S.; Wilcke, W.

2016-01-01

Historical reconstruction of atmospheric black carbon (BC, in the form of char and soot) is still constrained for inland areas. Here we determined and compared the past 150-yr records of BC and polycyclic aromatic compounds (PACs) in sediments from two representative lakes, Huguangyan (HGY) and Chaohu (CH), in eastern China. HGY only receives atmospheric deposition while CH is influenced by riverine input. BC, char, and soot have similar vertical concentration profiles as PACs in both lakes. Abrupt increases in concentrations and mass accumulation rates (MARs) of soot have mainly occurred since ~1950, the establishment of the People’s Republic of China, when energy usage changed to more fossil fuel contributions reflected by the variations in the concentration ratios of char/soot and individual PACs. In HGY, soot MARs increased by ~7.7 times in the period 1980–2012 relative to the period 1850–1950. Similar increases (~6.7 times) were observed in CH. The increase in soot MARs is also in line with the emission inventory records in the literature and the fact that the submicrometer-sized soot particles can be dispersed regionally. The study provides an alternative method to reconstruct the atmospheric soot history in populated inland areas. PMID:26750586

PAH and soot emissions from burning components of medical waste: examination/surgical gloves and cotton pads.

PubMed

Levendis, Y A; Atal, A; Carlson, J B; Quintana, M D

2001-01-01

This is a laboratory investigation on the emissions from batch combustion of representative infectious ("red bag") medical waste components, such as medical examination latex gloves and sterile cotton pads. Plastics and cloth account for the majority of the red bag wastes by mass and, certainly, by volume. An electrically heated, horizontal muffle furnace was used for batch combustion of small quantities of shredded fuels (0.5-1.5 g) at a gas temperature of approximately 1000 degrees C. The residence time of the post-combustion gases in the furnace was approximately 1 s. At the exit of the furnace, the following emissions were measured: CO, CO2, NOx, particulates and polynuclear aromatic compounds (PACs). The first three gaseous emissions were measured with continuous gas analyzers. Soot and PAC emissions were simultaneously measured by passing the furnace effluent through a filter (to collect condensed-phase PACs) and a bed of XAD-4 adsorbent (to capture gaseous-phase PACs). Analysis involved soxhlet extraction, followed by gas chromatography-mass spectrometry (GC-MS). Results were contrasted with previously measured emissions from batch combustion of pulverized coal and tire-derived fuel (TDF) under similar conditions. Results showed that the particulate soot) and cumulative PAC emissions from batch combustion of latex gloves were more than an order of magnitude higher than those from cotton pads. The following values are indicative of the relative trends (but not necessarily absolute values) in emission yields: 26% of the mass of the latex was converted to soot, 11% of which was condensed PAC. Only 2% of the mass of cotton pads was converted to soot, and only 3% of the weight of that soot was condensed PAC. The PAC yields from latex were comparable to those from TDF. The PAC yields from cotton were higher than those from coal. A notable exception to this trend was that the three-ring gas-phase PAC yields from cotton were more significant than those from latex. Emission yields of CO and CO2 from batch combustion of cotton were, respectively, comparable and higher than those from latex, despite the fact that the carbon content of cotton was half that of latex. This is indicative of the more effective combustion of cotton. Nearly all of the mass of carbon of cotton gasified to CO and CO2 while only small fractions of the carbon in latex were converted to CO2 and CO (20% and 10%, respectively). Yields of NOx from batch combustions of latex and cotton accounted for 15% and 12%, respectively, of the mass of fuel nitrogen indicating that more fuel nitrogen was converted to NOx in the former case, possibly due to higher flame temperatures. No SO2 emissions were detected, indicating that during the fuel-rich combustion of latex, its sulfur content was converted to other compounds (such as H2S) or remained in the soot.

Leukoproliferative response of splenocytes from English sole (Pleuronectes vetulus) exposed to chemical contaminants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arkoosh, M.R.; Clemons, E.; Huffman, P.

The leukoproliferative (LP) response of splenic leukocytes from the marine benthic fish English sole (Pleuronectes vetulus) stimulated with the mitogens lipopolysaccharide (LPS), convanavalin A (Con A), and pokeweed mitogen (PWM) was examined as a biomarker of immunotoxic effects. English sole were exposed to contaminants, either by injection of an organic-solvent extract of a sediment containing polycyclic aromatic compounds (PACs) or placed for up to 5 weeks on a reference sediment containing 0.15 to 1.5% (v/v) of the PAC-contaminated sediment. English sole either injected with the contaminated extract or held on PAC-contaminated sediment had an augmented response to Con A. Themore » LP response to LPS showed no relationship to PAC exposure in laboratory-exposed fish, while PWM showed no consistent relationship to exposure to PACs. In a field study, English sole captured from an urban area in Puget Sound, Washington, USA, contaminated with PACs and other chemical contaminants had a significantly augmented LP response to Con A and PWM in comparison to the LP response in fish from a nonurban reference site. Fish from another nonurban site also had an augmented LP response to Con A, indicating that the elevation of the Con A LP response can also result from factors other than chemical contaminant exposure. In addition, English sole from this site also had an augmented LP response to LPS, whereas fish from urban sites did not exhibit an augmented LP response to LPS. Overall, the results demonstrated that although the LP response in splenic leukocytes of English sole to Con A was linked to contaminant exposure, the LP response to Con A did not exhibit high specificity as an indicator of chemical contaminant exposure. However, the concerted use of Con A, LPS, and PWM allowed for identification of apparent chemical contaminant-induced alterations of the LP response in English sole from an urban area of Puget Sound.« less

The mammalian toxicological hazards of petroleum-derived substances: an overview of the petroleum industry response to the high production volume challenge program.

PubMed

McKee, Richard H; White, Russell

2014-01-01

Petroleum-derived substances are complex and composed of aliphatic (normal-, iso-, and cycloparaffins), olefinic, and/or aromatic constituents. Approximately 400 of these complex substances were evaluated as part of the US Environmental Protection Agency voluntary High Production Volume (HPV) Challenge program. The substances were separated into 13 groups (categories), and all available data were assessed. Toxicology testing was conducted as necessary to fully address the end points encompassed by the HPV initiative. In a broad sense, volatile hydrocarbons may cause acute central nervous system effects, and those that are liquids at room temperature pose aspiration hazards if taken into the lungs as liquids and may also cause skin irritation. Higher boiling substances may contain polycyclic aromatic constituents (PACs) that can be mutagenic and carcinogenic and may also cause developmental effects. Substances containing PACs can also cause target organ and developmental effects. The effects of aliphatic constituents include liver enlargement and/or renal effects in male rats via an α-2u-globulin-mediated process and, in some cases, small but statistically significant reductions in hematological parameters. Crude oils may contain other constituents, particularly sulfur- and nitrogen-containing compounds, which are removed during refining. Aside from these more generic considerations, some specific petroleum substances may contain unusually toxic constituents including benzene, 1,3-butadiene, and/or n-hexane, which should also be taken into account if present at toxicologically relevant levels.

Acute, subchronic, and developmental toxicological properties of lubricating oil base stocks.

PubMed

Dalbey, Walden E; McKee, Richard H; Goyak, Katy Olsavsky; Biles, Robert W; Murray, Jay; White, Russell

2014-01-01

Lubricating oil base stocks (LOBs) are substances used in the manufacture of finished lubricants and greases. They are produced from residue remaining after atmospheric distillation of crude oil that is subsequently fractionated by vacuum distillation and additional refining steps. Initial LOB streams that have been produced by vacuum distillation but not further refined may contain polycyclic aromatic compounds (PACs) and may present carcinogenic hazards. In modern refineries, LOBs are further refined by multistep processes including solvent extraction and/or hydrogen treatment to reduce the levels of PACs and other undesirable constituents. Thus, mildly (insufficiently) refined LOBs are potentially more hazardous than more severely (sufficiently) refined LOBs. This article discusses the evaluation of LOBs using statistical models based on content of PACs; these models indicate that insufficiently refined LOBs (potentially carcinogenic LOBs) can also produce systemic and developmental effects with repeated dermal exposure. Experimental data were also obtained in ten 13-week dermal studies in rats, eight 4-week dermal studies in rabbits, and seven dermal developmental toxicity studies with sufficiently refined LOBs (noncarcinogenic and commonly marketed) in which no observed adverse effect levels for systemic toxicity and developmental toxicity were 1000 to 2000 mg/kg/d with dermal exposures, typically the highest dose tested. Results in both oral and inhalation developmental toxicity studies were similar. This absence of toxicologically relevant findings was consistent with lower PAC content of sufficiently refined LOBs. Based on data on reproductive organs with repeated dosing and parameters in developmental toxicity studies, sufficiently refined LOBs are likely to have little, if any, effect on reproductive parameters.

Poly[(arylene ethynylene)-alt-(arylene vinylene)]s Based on Anthanthrone and Its Derivatives: Synthesis and Photophysical, Electrochemical, Electroluminescent, and Photovoltaic Properties

PubMed Central

2017-01-01

Anthanthrone and its derivatives are large polycyclic aromatic compounds (PACs) that pose a number of challenges for incorporation into the structure of soluble conjugated polymers. For the first time, this group of PACs was employed as the building blocks for the synthesis of copolymers (P1–P5) based on poly[(arylene ethynylene)-alt-(arylene vinylene)]s backbone (−Ph–C≡C–Anth–C≡C–Ph–CH=CH–Ph–CH=CH−)n. During the synthesis of P1–P5, different alkyloxy side chains were incorporated in order to tune the properties of the polymers. Of the copolymer series only P1 (containing anthanthrone and branched 2-ethylhexyloxy side chains on phenylenes), P2 and P3 (for which the anthanthrones containing carbonyl groups were converted to anthanthrene containing alkyloxy substituents) were soluble. The photophysical, electrochemical, electroluminescent and photovoltaic properties of P1–P3 are reported, compared and discussed with respect to the effects of side chains. PMID:29151617

Organic emissions from coal pyrolysis: mutagenic effects.

PubMed Central

Braun, A G; Wornat, M J; Mitra, A; Sarofim, A F

1987-01-01

Four different types of coal have been pyrolyzed in a laminar flow, drop tube furnace in order to establish a relationship between polycyclic aromatic compound (PAC) evolution and mutagenicity. Temperatures of 900K to 1700K and particle residence times up to 0.3 sec were chosen to best simulate conditions of rapid rate pyrolysis in pulverized (44-53 microns) coal combustion. The specific mutagenic activity (i.e., the activity per unit sample weight) of extracts from particulates and volatiles captured on XAD-2 resin varied with coal type according to the order: subbituminous greater than high volatile bituminous greater than lignite greater than anthracite. Total mutagenic activity (the activity per gram of coal pyrolyzed), however, varied with coal type according to the order: high volatile bituminous much greater than subbituminous = lignite much greater than anthracite, due primarily to high organic yield during high volatile bituminous coal pyrolysis. Specific mutagenic activity peaked in a temperature range of 1300K to 1500K and generally appeared at higher temperatures and longer residence times than peak PAC production. PMID:3311724

Dermal exposure and urinary 1-hydroxypyrene among asphalt roofing workers

DOE Office of Scientific and Technical Information (OSTI.GOV)

McClean, M.D.; Rinehart, R.D.; Sapkota, A.

2007-07-01

The primary objective of this study was to identify significant determinants of dermal exposure to polycyclic aromatic compounds (PACs) among asphalt roofing workers and use urinary 1-hydroxyprene (1-OHP) measurements to evaluate the effect of dermal exposure on total absorbed dose. The study population included 26 asphalt roofing workers who performed three primary tasks: tearing off old roofs, putting down new roofs, and operating the kettle at ground level. During multiple consecutive work shifts, dermal patch samples were collected from the underside of each worker's wrists and were analyzed for PACs, pyrene, and benzo(a)pyrene (BAP). During the same work week, urinemore » samples were collected at pre-shift, post-shift, and bedtime each day and were analyzed for 1-OHP (205 urine samples). Linear mixed effects models were used to evaluate the dermal measurements for the purpose of identifying important determinants of exposure, and to evaluate urinary 1-OHP measurements for the purpose of identifying important determinants of total absorbed dose. Dermal exposures to PAC, pyrene, and BAP were found to vary significantly by roofing task and by the presence of an old coal tar pitch roof. For each of the three analytes, the adjusted mean dermal exposures associated with tear-off were approximately four times higher than exposures associated with operating the kettle. Exposure to coal tar pitch was associated with a 6-fold increase in PAC exposure, an 8-fold increase in pyrene exposure and a 35-fold increase in BAP exposure. The presence of coal tar pitch was the primary determinant of dermal exposure, particularly for exposure to BAP. However, the task-based differences that were observed while controlling for pitch suggest that exposure to asphalt also contributes to dermal exposures.« less

Procaspase-activating compound 1 induces a caspase-3-dependent cell death in cerebellar granule neurons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aziz, Gulzeb; Akselsen, Oyvind W.; Hansen, Trond V.

2010-09-15

Procaspase-activating compound 1, PAC-1, has been introduced as a direct activator of procaspase-3 and has been suggested as a therapeutic agent against cancer. Its activation of procaspase-3 is dependent on the chelation of zinc. We have tested PAC-1 and an analogue of PAC-1 as zinc chelators in vitro as well as their ability to activate caspase-3 and induce cell death in chicken cerebellar granule neuron cultures. These neurons are non-dividing, primary cells with normal caspase-3. The results reported herein show that PAC-1 chelates zinc, activates procaspase-3, and leads to caspase-3-dependent cell death in neurons, as the specific caspase-3-inhibitor Ac-DEVD-cmk inhibitedmore » both the caspase-3 activity and cell death. Thus, chicken cerebellar granule neurons is a suitable model to study mechanisms of interference with apoptosis of PAC-1 and similar compounds. Furthermore, the present study also raises concern about potential neurotoxicity of PAC-1 if used in cancer therapy.« less

Source identification of petroleum hydrocarbons in soil and sediments from Iguaçu River Watershed, Paraná, Brazil using the CHEMSIC method (CHEMometric analysis of Selected Ion Chromatograms).

PubMed

Gallotta, Fabiana D C; Christensen, Jan H

2012-04-27

A chemometric method based on principal component analysis (PCA) of pre-processed and combined sections of selected ion chromatograms (SICs) is used to characterise the hydrocarbon profiles in soil and sediment from Araucária, Guajuvira, General Lúcio and Balsa Nova Municipalities (Iguaçu River Watershed, Paraná, Brazil) and to indicate the main sources of hydrocarbon pollution. The study includes 38 SICs of polycyclic aromatic compounds (PACs) and four of petroleum biomarkers in two separate analyses. The most contaminated samples are inside the Presidente Getúlio Vargas Refinery area. These samples represent a petrogenic pattern and different weathering degrees. Samples from outside the refinery area are either less or not contaminated, or contain mixtures of diagenetic, pyrogenic and petrogenic inputs where different proportions predominate. The locations farthest away from industrial activity (Balsa Nova) contains the lowest levels of PAC contamination. There are no evidences to conclude positive matches between the samples from outside the refinery area and the Cusiana spilled oil. Copyright © 2012 Elsevier B.V. All rights reserved.

Particle-associated contaminants in street dust, parking lot dust, soil, lake-bottom sediment, and suspended and streambed sediment, Lake Como and Fosdic Lake watersheds, Fort Worth, Texas, 2004

USGS Publications Warehouse

Wilson, Jennifer T.; Van Metre, Peter C.; Werth, Charles J.; Yang, Yanning

2006-01-01

A previous study by the U.S. Geological Survey of impaired water bodies in Fort Worth, Texas, reported elevated but variable concentrations of particle-associated contaminants (PACs) comprising chlorinated hydrocarbons, polycyclic aromatic hydrocarbons, and trace elements in suspended and bed sediment of lakes and streams affected by urban land use. The U.S. Geological Survey, in cooperation with the City of Fort Worth, collected additional samples during October 2004 to investigate sources of PACs in the watersheds of two impaired lakes: Lake Como and Fosdic Lake. Source materials and aquatic sediment were sampled and analyzed for PACs. Source materials sampled consisted of street dust and soil from areas with residential and commercial land use and parking lot dust from sealed and unsealed parking lots. Aquatic sediment sampled consisted of bottom-sediment cores from the two lakes and suspended and streambed sediment from the influent stream of each lake. Samples were analyzed for chlorinated hydrocarbons (organochlorine pesticides and polychlorinated biphenyls), polycyclic aromatic hydrocarbons, major and trace elements, organic carbon, grain size, and radionuclides.

Vertical Stratification of Peat Pore Water Dissolved Organic Matter Composition in a Peat Bog in Northern Minnesota: Pore Water DOM composition in a peat bog

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tfaily, Malak M.; Wilson, Rachel M.; Cooper, William T.

We characterized dissolved organic matter (DOM) composition throughout the peat column at the Marcell S1 forested bog in northern Minnesota and tested the hypothesis that redox oscillations associated with cycles of wetting and drying at the surface of the fluctuating water table correlate with increased carbon, sulfur and nitrogen turn over. We found significant vertical stratification of DOM molecular composition and EEM-PARAFAC components within the peat column. In particular the intermediate depth zone (~ 50 cm) was identified as a zone where maximum decomposition and turnover is taking place. Surface DOM was dominated by inputs from surface vegetation. The intermediate-depthmore » zone was an area of high organic matter reactivity and increased microbial activity with diagenetic formation of many unique compounds, among them polycyclic aromatic compounds (PAC) that contain both nitrogen and sulfur heteroatoms. These compounds have been previously observed in coal-derived compounds and were assumed to be responsible for coal's biological activity. Biological processes triggered by redox oscillations taking place at the intermediate depth zone of the peat profile at the S1 bog are assumed to be responsible for the formation of these heteroatomic PACs in this system. Alternatively these compounds could stem from black carbon and nitrogen derived from fires that have occurred at the site in the past. Surface and deep DOM exhibited more similar characteristics, compared to the intermediate-depth zone, with the deep layer exhibiting greater input of microbially degraded organic matter than the surface suggesting that the entire peat profile consists of similar parent material at different degrees of decomposition and that lateral and vertical advection of pore water from the surface to the deeper horizons is responsible for such similarities. Our findings suggest that molecular composition of DOM in peatland pore water is dynamic and is a function of ecosystem activity, water table and redox oscillation and porewater advection.« less

Predictors of dermal exposures to polycyclic aromatic compounds among hot-mix asphalt paving workers.

PubMed

Cavallari, Jennifer M; Osborn, Linda V; Snawder, John E; Kriech, Anthony J; Olsen, Larry D; Herrick, Robert F; McClean, Michael D

2012-03-01

The primary objective of this study was to identify the source and work practices that affect dermal exposure to polycyclic aromatic compounds (PACs) among hot-mix asphalt (HMA) paving workers. Four workers were recruited from each of three asphalt paving crews (12 workers) and were monitored for three consecutive days over 4 weeks for a total of 12 sampling days per worker (144 worker days). Two sampling weeks were conducted under standard conditions for dermal exposures. The third week included the substitution of biodiesel for diesel oil used to clean tools and equipment and the fourth week included dermal protection through the use of gloves, hat and neck cloth, clean pants, and long-sleeved shirts. Dermal exposure to PACs was quantified using two methods: a passive organic dermal (POD) sampler specifically developed for this study and a sunflower oil hand wash technique. Linear mixed-effects models were used to evaluate predictors of PAC exposures. Dermal exposures measured under all conditions via POD and hand wash were low with most samples for each analyte being below the limit of the detection with the exception of phenanthrene and pyrene. The geometric mean (GM) concentrations of phenanthrene were 0.69 ng cm(-2) on the polypropylene layer of the POD sampler and 1.37 ng cm(-2) in the hand wash sample. The GM concentrations of pyrene were 0.30 ng cm(-2) on the polypropylene layer of the POD sampler and 0.29 ng cm(-2) in the hand wash sample. Both the biodiesel substitution and dermal protection scenarios were effective in reducing dermal exposures. Based on the results of multivariate linear mixed-effects models, increasing frequency of glove use was associated with significant (P < 0.0001) reductions for hand wash and POD phenanthrene and pyrene concentrations; percent reductions ranged from 40 to 90%. Similar reductions in hand wash concentrations of phenanthrene (P = 0.01) and pyrene (P = 0.003) were observed when biodiesel was substituted for diesel oil as a cleaning agent, although reductions were not significant for the POD sampler data. Although task was not a predictor of dermal exposure, job site characteristics such as HMA application temperature, asphalt grade, and asphalt application rate (tons per hour) were found to significantly affect exposure. Predictive models suggest that the combined effect of substituting biodiesel for diesel oil as a cleaning agent, frequent glove use, and reducing the HMA application temperature from 149°C (300°F) to 127°C (260°F) may reduce dermal exposures by 76-86%, varying by analyte and assessment method. Promising strategies for reducing dermal exposure to PACs among asphalt paving workers include requiring the use of dermal coverage (e.g. wearing gloves and/or long sleeves), substituting biodiesel for diesel oil as a cleaning agent, and decreasing the HMA application temperature.

Evaluation of the dermal carcinogenicity of lubricant base oils by the mouse skin painting bioassay and other proposed methods.

PubMed

Chasey, K L; McKee, R H

1993-01-01

Lubricant base oils are petroleum products that are predominantly derived from the vacuum distillation of crude oil. Various types of refinement can be employed during the manufacturing process, and evidence suggests that certain of the associated process streams produce skin cancer. Polycyclic aromatic compounds (PACs), some of which are considered as the causative agents, are removed, concentrated or chemically converted during the refinement process. In order to understand the effects of various types of refinement processes on carcinogenic potential, 94 oils were evaluated in the mouse epidermal cancer bioassay. This Exxon database is unique, because of the wide range of crude oils and processing histories represented. Seven processing history classifications are described, and conclusions concerning the impacts of each refinement process on dermal carcinogenicity are discussed. This research also included an evaluation of selected biological and chemical test methods for predicting carcinogenic potential. These included a modified version of the Ames test for mutagenicity, as well as analytical characterizations of the polycyclic aromatic structures in the oils. For classification purposes, a sample was considered to be carcinogenic if it resulted in the production of two or more tumor-bearing animals (in test groups of either 40 or 50 animals). The modified Ames test was considered to be positive if the mutagenicity index was > or = 2.0, and PAC analyses were similarly designated as positive or negative according to proposed guidelines. All of the alternative test methods showed similar agreement with dermal carcinogenicity bioassay data; concordance values were > or = 80%. However, each test was incorrect in ca. 10%-20% of the cases evaluated.(ABSTRACT TRUNCATED AT 250 WORDS)

Atmospheric deposition of polycyclic aromatic compounds and associated sources in an urban and a rural area of Chongqing, China.

PubMed

Tian, Mi; Yang, FuMo; Chen, SheJun; Wang, HuanBo; Chen, Yang; Zhang, LiuYi; Zhang, LeiMing; Xiang, Li; Qiao, BaoQing

2017-11-01

Monthly bulk (dry + wet) deposition samples were collected at an urban and a rural site in Chongqing, southwestern China during May 2014 to April 2015 for analyzing the contents of parent polycyclic aromatic hydrocarbons (PPAHs) and three types of substituted PAHs (SPAHs) including oxygenated PAHs (OPAHs), nitrated PAHs (NPAHs) and methyl PAHs (MPAHs). Annual average (±standard deviation) deposition fluxes of ΣPPAHs, ΣOPAHs, and ΣMPAHs were 536 ± 216; 221 ± 118, and 131 ± 41.9 ng/m 2 /d, respectively, in the urban area, and 347 ± 185, 160 ± 112, and 85.2 ± 32.0 ng/m 2 /d, respectively in the rural area. Deposition of ΣNPAHs (6.01 ± 3.93 and 3.91 ± 4.84 ng/m 2 /d) were about two orders of magnitude lower than those of ΣPPAHs. In the urban area, temporal variations of PPAHs and MPAHs fluxes were positively correlated with particle deposition, while the trends of OPAHs and NPAHs were probably controlled by secondary formation. In the rural area, SPAHs and PPAHs deposition fluxes had similar temporal trends but differed from particle deposition. High relative humidity in Chongqing likely played an important role in facilitating the partitioning of OPAHs to atmospheric aerosols and resulting in the relatively high OPAHs level in winter. Principle component analysis identified secondary formation (21.7%) and combustion emission (52.7%) as two important contributors to polycyclic aromatic compounds (PACs) deposition fluxes in urban area. Copyright © 2017 Elsevier Ltd. All rights reserved.

Unexpectedly high mortality in Pacific herring embryos exposed to the 2007 Cosco Busan oil spill in San Francisco Bay.

PubMed

Incardona, John P; Vines, Carol A; Anulacion, Bernadita F; Baldwin, David H; Day, Heather L; French, Barbara L; Labenia, Jana S; Linbo, Tiffany L; Myers, Mark S; Olson, O Paul; Sloan, Catherine A; Sol, Sean; Griffin, Frederick J; Menard, Karl; Morgan, Steven G; West, James E; Collier, Tracy K; Ylitalo, Gina M; Cherr, Gary N; Scholz, Nathaniel L

2012-01-10

In November 2007, the container ship Cosco Busan released 54,000 gallons of bunker fuel oil into San Francisco Bay. The accident oiled shoreline near spawning habitats for the largest population of Pacific herring on the west coast of the continental United States. We assessed the health and viability of herring embryos from oiled and unoiled locations that were either deposited by natural spawning or incubated in subtidal cages. Three months after the spill, caged embryos at oiled sites showed sublethal cardiac toxicity, as expected from exposure to oil-derived polycyclic aromatic compounds (PACs). By contrast, embryos from the adjacent and shallower intertidal zone showed unexpectedly high rates of tissue necrosis and lethality unrelated to cardiotoxicity. No toxicity was observed in embryos from unoiled sites. Patterns of PACs at oiled sites were consistent with oil exposure against a background of urban sources, although tissue concentrations were lower than expected to cause lethality. Embryos sampled 2 y later from oiled sites showed modest sublethal cardiotoxicity but no elevated necrosis or mortality. Bunker oil contains the chemically uncharacterized remains of crude oil refinement, and one or more of these unidentified chemicals likely interacted with natural sunlight in the intertidal zone to kill herring embryos. This reveals an important discrepancy between the resolving power of current forensic analytical chemistry and biological responses of keystone ecological species in oiled habitats. Nevertheless, we successfully delineated the biological impacts of an oil spill in an urbanized coastal estuary with an overlapping backdrop of atmospheric, vessel, and land-based sources of PAC pollution.

Mutagenic effect of extracts from particulate matter collected with sediment traps in the archipelago of Stockholm and the open northern Baltic

DOE Office of Scientific and Technical Information (OSTI.GOV)

Broman, D.; Naef, C.; Rannug, U.

The load of various hydrophobic organic compounds (HOCs) on the Baltic Sea aquatic environment is considerable. This investigation samples the water area around Stockholm, of special concern since it is one of the most densely populated urban areas in the Baltic region. Stockholm also houses several power plants, municipal waste incinerators, waste water treatment plants, ports and oil terminals. The runoff from a large lake also passes through the estuarine-like archipelago of Stockholm. Due to the high particulate-water partition coefficients (K[sub p]) of most ecotoxicologically relevant HOCs, particulate matter (PM) becomes very important for occurrence and distribution in the aquaticmore » environment. This PM is the basic food source for important organisms in the benthic, pelagic and littoral parts of the aquatic ecosystem. The load of various HOCs such as petrogenic hydrocarbons (PHCs), various polynuclear aromatic compounds (PACs), and chlorinated hydrocarbons such as polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in association with PM in the aquatic environment of the Stockholm area is well documented. However, the ecotoxicological relevance of organic extracts of PM, including the above identified compounds and various unidentified HOCs, is not fully evaluated. To evaluate the genotoxic potential of extracts of PM, collected with sediment traps in the Stockholm water area and in the open northern Baltic, we used the Ames test on Salmonella typhimurium strain TA100, with and without a metabolizing system. After extraction and before the mutagenicity tests all PM samples were fractionated on an HPLC-system into three fractions containing aliphatic/monoaromatic-, diaromatic, (containing, e.g., PCDD/Fs and PCBs) and polyaromatic compounds (containing various PACs). The relative mutagenic potential of these fractions at the different sediment trap sampling stations are discussed and evaluated. 13 refs., 1 tab.« less

A comprehensive evaluation of the carcinogenic potential of middle distillate fuels.

PubMed

Nessel, C S

1999-02-01

Middle distillate fuels (MDFs), which include jet fuel, kerosene, and diesel fuel, are a class of hydrocarbons distilled from crude oil at approximately 350-700 degrees F (176-371 degrees C). Although MDFs generally do not contain appreciable levels of potentially carcinogenic polycyclic aromatic compounds (PACs), they have produced weak tumorigenic responses in mouse skin characterized by low tumor yield and long latency. Recent studies demonstrated that the tumorigenic effects of these MDFs were dependent upon chronic dermal irritation. In the absence of skin irritation, tumors did not develop. Mechanistic studies suggest that straight-run MDFs containing low levels of PACs cause skin tumors through a nongenotoxic mechanism. MDFs cause chronic skin irritation and injury with repeated application to the skin. They have been found to have little or no activity in the modified Ames mutagenicity assay, lack tumor initiating activity, and are active skin tumor promoters. It has been hypothesized that the tumorigenic response to MDFs results from the promotion of preexisting, spontaneously initiated cells. Two recent studies, a one-year tumor promotion study and a two-year skin painting study, evaluated the role of skin irritation on the tumorigenic activity of MDFs in mice. MDFs were applied in pure and diluted forms to assess the effect of equal weekly doses of irritating and nonirritating test materials. The tumorigenicity of straight-run MDFs correlated to the level of skin irritation. No significant increase in tumor incidence occurred under conditions that resulted in minimal skin irritation and injury. These studies indicate that the tumorigenic activity of MDFs containing low levels of PACs is secondary to chronic skin irritation. These materials should not present a carcinogenic hazard in the absence of prolonged skin irritation.

Impact of roasting on the flavan-3-ol composition, sensory-related chemistry, and in vitro pancreatic lipase inhibitory activity of cocoa beans.

PubMed

Stanley, Todd H; Van Buiten, Charlene B; Baker, Scott A; Elias, Ryan J; Anantheswaran, Ramaswamy C; Lambert, Joshua D

2018-07-30

Roasting is an important cocoa processing step, but has been reported to reduce the polyphenol content in the beans. We investigated the impact of whole-bean roasting on the polyphenol content, aroma-related chemistry, and in vitro pancreatic lipase (PL) inhibitory activity of cocoa under a range of roasting conditions. Total phenolics, (-)-epicatechin, and proanthocyanidin (PAC) dimer - pentamer content was reduced by roasting. By contrast, roasting at 150 °C or greater increased the levels of catechin and PAC hexamers and heptamers. These compounds have greater PL inhibitory potency. Consistent with these changes in PAC composition and this previous data, we found that roasting at 170 °C time-dependently increased PL inhibitory activity. Cocoa aroma-related compounds increased with roasting above 100 °C, whereas deleterious sensory-related compounds formed at more severe temperatures. Our results indicate that cocoa roasting can be optimized to increase the content of larger PACs and anti-PL activity, while maintaining a favorable aroma profile. Copyright © 2018 Elsevier Ltd. All rights reserved.

40 CFR 721.775 - Brominated aromatic com-pound (generic name).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Brominated aromatic com-pound (generic... Specific Chemical Substances § 721.775 Brominated aromatic com-pound (generic name). (a) Chemical... as a brominated aromatic compound (PMN P-84-824) is subject to reporting under this section for the...

Does powder and granular activated carbon perform equally in immobilizing chlorobenzenes in soil?

PubMed

Song, Yang; Wang, Fang; Kengara, Fredrick Orori; Bian, Yongrong; Yang, Xinglun; Gu, Chenggang; Ye, Mao; Jiang, Xin

2015-01-01

The objective of this study is to compare the efficacies of powder activated carbon (PAC) and granular activated carbon (GAC) as amendments for the immobilization of volatile compounds in soil. Soil artificially-spiked with chlorobenzenes (CBs) was amended with either PAC or GAC to obtain an application rate of 1%. The results showed that the dissipation and volatilization of CBs from the amended soil significantly decreased compared to the unamended soil. The bioavailabilities of CBs, which is expressed as butanol extraction and earthworm accumulation, were significantly reduced in PAC and GAC amended soils. The lower chlorinated and hence more volatile CBs experienced higher reductions in both dissipation and bioavailability in the amended soils. The GAC and PAC equally immobilized more volatile CBs in soil. Therefore, it could be concluded that along with environmental implication, applying GAC was the more promising approach for the effective immobilization of volatile compounds in soil.

Tumor prevalence and biomarkers of genotoxicity in brown bullhead (Ameiurus nebulosus) in Chesapeake Bay tributaries

USGS Publications Warehouse

Pinkney, Alfred E.; Harshbarger, John C.; Karouna-Renier, Natalie K.; Jenko, Kathryn; Balk, Lennart; Skarphéðinsdóttir, Halldora; Liewenborg, Birgitta; Rutter, Michael A.

2011-01-01

We surveyed four Chesapeake Bay tributaries for skin and liver tumors in brown bullhead (Ameiurus nebulosus). We focused on the South River, where the highest skin tumor prevalence (53%) in the Bay watershed had been reported. The objectives were to 1) compare tumor prevalence with nearby rivers (Severn and Rhode) and a more remote river (Choptank); 2) investigate associations between tumor prevalence and polynuclear aromatic hydrocarbons (PAHs) and alkylating agents; and 3) statistically analyze Chesapeake Bay bullhead tumor data from 1992 through 2008. All four South River collections exhibited high skin tumor prevalence (19% to 58%), whereas skin tumor prevalence was 2%, 10%, and 52% in the three Severn collections; 0% and 2% in the Choptank collections; and 5.6% in the Rhode collection. Liver tumor prevalence was 0% to 6% in all but one South River collection (20%) and 0% to 6% in the three other rivers. In a subset of samples, PAH-like biliary metabolites and 32P-DNA adducts were used as biomarkers of exposure and response to polycyclic aromatic compounds (PACs). Adducts from alkylating agents were detected as O6-methyl-2'-deoxyguanosine (O6Me-dG) and O6-ethyl-2'-deoxyguanosine (O6Et-dG) modified DNA. Bullheads from the contaminated Anacostia River were used as a positive control for DNA adducts. 32P-DNA adduct concentrations were significantly higher in Anacostia bullhead livers compared with the other rivers. We identified alkyl DNA adducts in bullhead livers from the South and Anacostia, but not the Choptank. Neither the PAH-like bile metabolite data, sediment PAH data, nor the DNA adduct data suggest an association between liver or skin tumor prevalence and exposure to PACs or alkylating agents in the South, Choptank, Severn, or Rhode rivers. Logistic regression analysis of the Chesapeake Bay database revealed that sex and length were significant covariates for liver tumors and length was a significant covariate for skin tumors.

Method of upgrading oils containing hydroxyaromatic hydrocarbon compounds to highly aromatic gasoline

DOEpatents

Baker, E.G.; Elliott, D.C.

1993-01-19

The present invention is a multi-stepped method of converting an oil which is produced by various biomass and coal conversion processes and contains primarily single and multiple ring hydroxyaromatic hydrocarbon compounds to highly aromatic gasoline. The single and multiple ring hydroxyaromatic hydrocarbon compounds in a raw oil material are first deoxygenated to produce a deoxygenated oil material containing single and multiple ring aromatic compounds. Then, water is removed from the deoxygenated oil material. The next step is distillation to remove the single ring aromatic compounds as gasoline. In the third step, the multiple ring aromatics remaining in the deoxygenated oil material are cracked in the presence of hydrogen to produce a cracked oil material containing single ring aromatic compounds. Finally, the cracked oil material is then distilled to remove the single ring aromatics as gasoline.

Personal Breathing Zone Exposures among Hot-Mix Asphalt Paving Workers; Preliminary Analysis for Trends and Analysis of Work Practices That Resulted in the Highest Exposure Concentrations

PubMed Central

Osborn, Linda V.; Snawder, John E.; Kriech, Anthony J.; Cavallari, Jennifer M.; McClean, Michael D.; Herrick, Robert F.; Blackburn, Gary R.; Olsen, Larry D.

2015-01-01

An exposure assessment of hot-mix asphalt (HMA) paving workers was conducted to determine which of four exposure scenarios impacted worker exposure and dose. Goals of this report are to present the personal-breathing zone (PBZ) data, discuss the impact of substituting the releasing/cleaning agent, and discuss work practices that resulted in the highest exposure concentration for each analyte. One-hundred-seven PBZ samples were collected from HMA paving workers on days when diesel oil was used as a releasing/cleaning agent. An additional 36 PBZ samples were collected on days when B-100 (100% biodiesel, containing no petroleum-derived products) was used as a substitute releasing/cleaning agent. Twenty-four PBZ samples were collected from a reference group of concrete workers, who also worked in outdoor construction but had no exposure to asphalt emissions. Background and field blank samples were also collected daily. Total particulates and the benzene soluble fraction were determined gravimetrically. Total organic matter was determined using gas chromatography (GC) with flame ionization detection and provided qualitative information about other exposure sources contributing to worker exposure besides asphalt emissions. Thirty-three individual polycyclic aromatic compounds (PACs) were determined using GC with time-offlight mass spectrometry; results were presented as either the concentration of an individual PAC or a summation of the individual PACs containing either 2- to 3-rings or 4- to 6-rings. Samples were also screened for PACs containing 4- to 6-rings using fluorescence spectroscopy. Arithmetic means, medians, and box plots of the PBZ data were used to evaluate trends in the data. Box plots illustrating the diesel oil results were more variable than the B-100. Also, the highest diesel oil results were much higher in concentration than the highest B-100 results. An analysis of the highest exposure results and field notes revealed a probable association between these exposures and the use of diesel oil, use of a diesel-powered screed, elevated HMA paving application temperatures, lubricating and working on broken-down equipment, and operation of a broom machine. PMID:24195533

Personal breathing zone exposures among hot-mix asphalt paving workers; preliminary analysis for trends and analysis of work practices that resulted in the highest exposure concentrations.

PubMed

Osborn, Linda V; Snawder, John E; Kriech, Anthony J; Cavallari, Jennifer M; McClean, Michael D; Herrick, Robert F; Blackburn, Gary R; Olsen, Larry D

2013-01-01

An exposure assessment of hot-mix asphalt (HMA) paving workers was conducted to determine which of four exposure scenarios impacted worker exposure and dose. Goals of this report are to present the personal-breathing zone (PBZ) data, discuss the impact of substituting the releasing/cleaning agent, and discuss work practices that resulted in the highest exposure concentration for each analyte. One-hundred-seven PBZ samples were collected from HMA paving workers on days when diesel oil was used as a releasing/cleaning agent. An additional 36 PBZ samples were collected on days when B-100 (100% biodiesel, containing no petroleum-derived products) was used as a substitute releasing/cleaning agent. Twenty-four PBZ samples were collected from a reference group of concrete workers, who also worked in outdoor construction but had no exposure to asphalt emissions. Background and field blank samples were also collected daily. Total particulates and the benzene soluble fraction were determined gravimetrically. Total organic matter was determined using gas chromatography (GC) with flame ionization detection and provided qualitative information about other exposure sources contributing to worker exposure besides asphalt emissions. Thirty-three individual polycyclic aromatic compounds (PACs) were determined using GC with time-of-flight mass spectrometry; results were presented as either the concentration of an individual PAC or a summation of the individual PACs containing either 2- to 3-rings or 4- to 6-rings. Samples were also screened for PACs containing 4- to 6-rings using fluorescence spectroscopy. Arithmetic means, medians, and box plots of the PBZ data were used to evaluate trends in the data. Box plots illustrating the diesel oil results were more variable than the B-100. Also, the highest diesel oil results were much higher in concentration than the highest B-100 results. An analysis of the highest exposure results and field notes revealed a probable association between these exposures and the use of diesel oil, use of a diesel-powered screed, elevated HMA paving application temperatures, lubricating and working on broken-down equipment, and operation of a broom machine.

Method of upgrading oils containing hydroxyaromatic hydrocarbon compounds to highly aromatic gasoline

DOEpatents

Baker, Eddie G.; Elliott, Douglas C.

1993-01-01

The present invention is a multi-stepped method of converting an oil which is produced by various biomass and coal conversion processes and contains primarily single and multiple ring hydroxyaromatic hydrocarbon compounds to highly aromatic gasoline. The single and multiple ring hydroxyaromatic hydrocarbon compounds in a raw oil material are first deoxygenated to produce a deoxygenated oil material containing single and multiple ring aromatic compounds. Then, water is removed from the deoxygenated oil material. The next step is distillation to remove the single ring aromatic compouns as gasoline. In the third step, the multiple ring aromatics remaining in the deoxygenated oil material are cracked in the presence of hydrogen to produce a cracked oil material containing single ring aromatic compounds. Finally, the cracked oil material is then distilled to remove the single ring aromatics as gasoline.

High-Molecular-Weight Proanthocyanidins in Foods: Overcoming Analytical Challenges in Pursuit of Novel Dietary Bioactive Components.

PubMed

Neilson, Andrew P; O'Keefe, Sean F; Bolling, Bradley W

2016-01-01

Proanthocyanidins (PACs) are an abundant but complex class of polyphenols found in foods and botanicals. PACs are polymeric flavanols with a variety of linkages and subunits. Connectivity and degree of polymerization (DP) determine PAC bioavailability and bioactivity. Current quantitative and qualitative methods may ignore a large percentage of dietary PACs. Subsequent correlations between intake and activity are hindered by a lack of understanding of the true PAC complexity in many foods. Additionally, estimates of dietary intakes are likely inaccurate, as nutrient databank values are largely based on standards from cocoa (monomers to decamers) and blueberries (mean DP of 36). Improved analytical methodologies are needed to increase our understanding of the biological roles of these complex compounds.

Anaerobic Catabolism of Aromatic Compounds: a Genetic and Genomic View

PubMed Central

Carmona, Manuel; Zamarro, María Teresa; Blázquez, Blas; Durante-Rodríguez, Gonzalo; Juárez, Javier F.; Valderrama, J. Andrés; Barragán, María J. L.; García, José Luis; Díaz, Eduardo

2009-01-01

Summary: Aromatic compounds belong to one of the most widely distributed classes of organic compounds in nature, and a significant number of xenobiotics belong to this family of compounds. Since many habitats containing large amounts of aromatic compounds are often anoxic, the anaerobic catabolism of aromatic compounds by microorganisms becomes crucial in biogeochemical cycles and in the sustainable development of the biosphere. The mineralization of aromatic compounds by facultative or obligate anaerobic bacteria can be coupled to anaerobic respiration with a variety of electron acceptors as well as to fermentation and anoxygenic photosynthesis. Since the redox potential of the electron-accepting system dictates the degradative strategy, there is wide biochemical diversity among anaerobic aromatic degraders. However, the genetic determinants of all these processes and the mechanisms involved in their regulation are much less studied. This review focuses on the recent findings that standard molecular biology approaches together with new high-throughput technologies (e.g., genome sequencing, transcriptomics, proteomics, and metagenomics) have provided regarding the genetics, regulation, ecophysiology, and evolution of anaerobic aromatic degradation pathways. These studies revealed that the anaerobic catabolism of aromatic compounds is more diverse and widespread than previously thought, and the complex metabolic and stress programs associated with the use of aromatic compounds under anaerobic conditions are starting to be unraveled. Anaerobic biotransformation processes based on unprecedented enzymes and pathways with novel metabolic capabilities, as well as the design of novel regulatory circuits and catabolic networks of great biotechnological potential in synthetic biology, are now feasible to approach. PMID:19258534

Biotechnological production of aromatic compounds of the extended shikimate pathway from renewable biomass.

PubMed

Lee, Jin-Ho; Wendisch, Volker F

2017-09-10

Aromatic chemicals that contain an unsaturated ring with alternating double and single bonds find numerous applications in a wide range of industries, e.g. paper and dye manufacture, as fuel additives, electrical insulation, resins, pharmaceuticals, agrochemicals, in food, feed and cosmetics. Their chemical production is based on petroleum (BTX; benzene, toluene, and xylene), but they can also be obtained from plants by extraction. Due to petroleum depletion, health compliance, or environmental issues such as global warming, the biotechnological production of aromatics from renewable biomass came more and more into focus. Lignin, a complex polymeric aromatic molecule itself, is a natural source of aromatic compounds. Many microorganisms are able to catabolize a plethora of aromatic compounds and interception of these pathways may lead to the biotechnological production of value-added aromatic compounds which will be discussed for Corynebacterium glutamicum. Biosynthesis of aromatic amino acids not only gives rise to l-tryptophan, L-tyrosine and l-phenylalanine, but also to aromatic intermediates such as dehydroshikimate or chorismate from which value-added aromatic compounds can be derived. In this review, we will summarize recent strategies for the biotechnological production of aromatic and related compounds from renewable biomass by Escherichia coli, Pseudomonas putida, C. glutamicum and Saccharomyces cerevisiae. In particular, we will focus on metabolic engineering of the extended shikimate pathway. Copyright © 2016 Elsevier B.V. All rights reserved.

PERFLUORINATED AROMATIC COMPOUND

DTIC Science & Technology

octafluorobiphenyl, and perfluoroaliphatic aldehydes. Synthetic routes to perfluoro cyclohexyls via reactions of phenyl and pentafluorphenyl lithium with...other perfluorinated aromatic compounds were employed in the synthesis of perfluorinated aromatic model compounds and polymers. The hydrogenic analogues...hydrazides, and imides. Synthetic routes to perfluoro aralkyl compounds are being investigated. Starting materials are tetrafluorobenzene

Effects of ozonation, powdered activated carbon adsorption, and coagulation on the removal of disinfection by-product precursors in reservoir water.

PubMed

Wang, Feng; Gao, Baoyu; Yue, Qinyan; Bu, Fan; Shen, Xue

2017-07-01

Effects of ozonation and powdered activated carbon on removal of dissolved organic matter (DOM) and disinfection by-product (DBP) in reservoir water were intensively investigated in this study. Both the formation of carbonaceous DBP (C-DBP) and nitrogenous DBP (N-DBP) as well as their speciation were analyzed. Results exhibited that the addition of powdered activated carbon (PAC) greatly improved the removal of aromatic protein. Trihalomethanes (THMs) and haloacetonitriles (HANs) were the dominant species in C-DBP and N-DBP. The integrated coagulation and PAC processes could remove more than 70% of THMs and 93% of HANs precursors, while only 10.5 and 45% of capture were achieved by the single coagulation. The added ozone lowered the yields of HANs but synchronously increased the more toxic bromine-containing THMs from 78.5 to 128.1 μg/L. Kinetics parameters for THM formation indicated that the precursor creating the THMs fast could be easily removed by both the coagulation and PAC adsorption.

Development of a sampling method for the simultaneous monitoring of straight-chain alkanes, straight-chain saturated carbonyl compounds and monoterpenes in remote areas.

PubMed

Detournay, Anaïs; Sauvage, Stéphane; Locoge, Nadine; Gaudion, Vincent; Leonardis, Thierry; Fronval, Isabelle; Kaluzny, Pascal; Galloo, Jean-Claude

2011-04-01

Studies have shown that biogenic compounds, long chain secondary compounds and long lifetime anthropogenic compounds are involved in the formation of organic aerosols in both polluted areas and remote places. This work aims at developing an active sampling method to monitor these compounds (i.e. 6 straight-chain saturated aldehydes from C6 to C11; 8 straight-chain alkanes from C9 to C16; 6 monoterpenes: α-pinene, β-pinene, camphene, limonene, α-terpinene, & γ-terpinene; and 5 aromatic compounds: toluene, ethylbenzene, meta-, para- and ortho-xylenes) in remote areas. Samples are collected onto multi-bed sorbent cartridges at 200 mL min(-1) flow rate, using the automatic sampler SyPAC (TERA-Environnement, Crolles, France). No breakthrough was observed for sampling volumes up to 120 L (standard mixture at ambient temperature, with a relative humidity of 75%). As ozone has been shown to alter the samples (losses of 90% of aldehydes and up to 95% of terpenes were observed), the addition of a conditioned manganese dioxide (MnO(2)) scrubber to the system has been validated (full recovery of the affected compounds for a standard mixture at 50% relative humidity--RH). Samples are first thermodesorbed and then analysed by GC/FID/MS. This method allows suitable detection limits (from 2 ppt for camphene to 13 ppt for octanal--36 L sampled), and reproducibility (from 1% for toluene to 22% for heptanal). It has been successfully used to determine the diurnal variation of the target compounds (six 3 h samples a day) during winter and summer measurement campaigns at a remote site in the south of France.

Development of genetically engineered bacteria for production of selected aromatic compounds

DOEpatents

Ward, Thomas E.; Watkins, Carolyn S.; Bulmer, Deborah K.; Johnson, Bruce F.; Amaratunga, Mohan

2001-01-01

The cloning and expression of genes in the common aromatic pathway of E. coli are described. A compound for which chorismate, the final product of the common aromatic pathway, is an anabolic intermediate can be produced by cloning and expressing selected genes of the common aromatic pathway and the genes coding for enzymes necessary to convert chorismate to the selected compound. Plasmids carrying selected genes of the common aromatic pathway are also described.

Effects of halogenated aromatics/aliphatics and nitrogen(N)-heterocyclic aromatics on estimating the persistence of future pharmaceutical compounds using a modified QSAR model.

PubMed

Lim, Seung Joo; Fox, Peter

2014-02-01

The effects of halogenated aromatics/aliphatics and nitrogen(N)-heterocyclic aromatics on estimating the persistence of future pharmaceutical compounds were investigated using a modified half life equation. The potential future pharmaceutical compounds investigated were approximately 2000 pharmaceutical drugs currently undergoing the United States Food and Drug Administration (US FDA) testing. EPI Suite (BIOWIN) model estimates the fates of compounds based on the biodegradability under aerobic conditions. While BIOWIN considered the biodegradability of a compound only, the half life equation used in this study was modified by biodegradability, sorption and cometabolic oxidation. It was possible that the potential future pharmaceutical compounds were more accurately estimated using the modified half life equation. The modified half life equation considered sorption and cometabolic oxidation of halogenated aromatic/aliphatics and nitrogen(N)-heterocyclic aromatics in the sub-surface, while EPI Suite (BIOWIN) did not. Halogenated aliphatics in chemicals were more persistent than halogenated aromatics in the sub-surface. In addition, in the sub-surface environment, the fates of organic chemicals were much more affected by halogenation in chemicals than by nitrogen(N)-heterocyclic aromatics. © 2013.

Insight into unresolved complex mixtures of aromatic hydrocarbons in heavy oil via two-dimensional gas chromatography coupled with time-of-flight mass spectrometry analysis.

PubMed

Weng, Na; Wan, Shan; Wang, Huitong; Zhang, Shuichang; Zhu, Guangyou; Liu, Jingfu; Cai, Di; Yang, Yunxu

2015-06-12

The aromatic hydrocarbon fractions of five crude oils representing a natural sequence of increasing degree of biodegradation from the Liaohe Basin, NE, China, were analyzed using conventional gas chromatography-mass spectrometry (GC-MS) and comprehensive two-dimensional gas chromatography (GC×GC). Because of the limited peak capability and low resolution, compounds in the aromatic fraction of a heavily biodegraded crude oil that were analyzed by GC-MS appeared as unresolved complex mixtures (UCMs) or GC "humps". They could be separated based on their polarity by GC×GC. UCMs are composed mainly of aromatic biomarkers and aromatic hydrocarbons with branched alkanes or cycloalkanes substituents. The quantitative results achieved by GC×GC-FID were shown that monoaromatic hydrocarbons account for the largest number and mass of UCMs in the aromatic hydrocarbon fraction of heavily biodegraded crude oil, at 45% by mass. The number and mass of diaromatic hydrocarbons ranks second at 33% by mass, followed by the aromatic biomarker compounds, triaromatic, tetraaromatic, and pentaaromatic hydrocarbons, that account for 10%, 6%, 1.5%, and 0.01% of all aromatic compounds by mass, respectively. In the heavily biodegraded oil, compounds with monocyclic cycloalkane substituents account for the largest proportion of mono- and diaromatic hydrocarbons, respectively. The C4-substituted compounds account for the largest proportion of naphthalenes and the C3-substituted compounds account for the largest proportion of phenanthrenes, which is very different from non-biodegraded, slightly biodegraded, and moderately biodegraded crude oil. It is inferred that compounds of monoaromatic, diaromatic and triaromatic hydrocarbons are affected by biodegradation, that compounds with C1-, C2-substituents are affected by the increase in degree of biodegradation, and that their relative content decreased, whereas compounds with C3-substituents or more were affected slightly or unaffected, and their relative content also increased. The varying regularity of relative content of substituted compounds may be used to reflect the degree of degradation of heavy oil. Moreover, biomarkers for the aromatic hydrocarbons of heavily biodegraded crude oil are mainly aromatic steranes, aromatic secohopanes, aromatic pentacyclotriterpanes, and benzohopanes. According to resultant data, aromatic secohopanes could be used as a specific marker because of their relatively high concentration. This aromatic compound analysis of a series of biodegraded crude oil is useful for future research on the quantitative characterization of the degree of biodegradation of heavy oil, unconventional oil maturity evaluation, oil source correlation, depositional environment, and any other geochemical problems. Copyright © 2015 Elsevier B.V. All rights reserved.

Biodegradation of Aromatic Compounds by Escherichia coli

PubMed Central

Díaz, Eduardo; Ferrández, Abel; Prieto, María A.; García, José L.

2001-01-01

Although Escherichia coli has long been recognized as the best-understood living organism, little was known about its abilities to use aromatic compounds as sole carbon and energy sources. This review gives an extensive overview of the current knowledge of the catabolism of aromatic compounds by E. coli. After giving a general overview of the aromatic compounds that E. coli strains encounter and mineralize in the different habitats that they colonize, we provide an up-to-date status report on the genes and proteins involved in the catabolism of such compounds, namely, several aromatic acids (phenylacetic acid, 3- and 4-hydroxyphenylacetic acid, phenylpropionic acid, 3-hydroxyphenylpropionic acid, and 3-hydroxycinnamic acid) and amines (phenylethylamine, tyramine, and dopamine). Other enzymatic activities acting on aromatic compounds in E. coli are also reviewed and evaluated. The review also reflects the present impact of genomic research and how the analysis of the whole E. coli genome reveals novel aromatic catabolic functions. Moreover, evolutionary considerations derived from sequence comparisons between the aromatic catabolic clusters of E. coli and homologous clusters from an increasing number of bacteria are also discussed. The recent progress in the understanding of the fundamentals that govern the degradation of aromatic compounds in E. coli makes this bacterium a very useful model system to decipher biochemical, genetic, evolutionary, and ecological aspects of the catabolism of such compounds. In the last part of the review, we discuss strategies and concepts to metabolically engineer E. coli to suit specific needs for biodegradation and biotransformation of aromatics and we provide several examples based on selected studies. Finally, conclusions derived from this review may serve as a lead for future research and applications. PMID:11729263

Determination of chiral pharmaceuticals and illicit drugs in wastewater and sludge using microwave assisted extraction, solid-phase extraction and chiral liquid chromatography coupled with tandem mass spectrometry.

PubMed

Evans, Sian E; Davies, Paul; Lubben, Anneke; Kasprzyk-Hordern, Barbara

2015-07-02

This is the first study presenting a multi-residue method allowing for comprehensive analysis of several chiral pharmacologically active compounds (cPACs) including beta-blockers, antidepressants and amphetamines in wastewater and digested sludge at the enantiomeric level. Analysis of both the liquid and solid matrices within wastewater treatment is crucial to being able to carry out mass balance within these systems. The method developed comprises filtration, microwave assisted extraction and solid phase extraction followed by chiral liquid chromatography coupled with tandem mass spectrometry to analyse the enantiomers of 18 compounds within all three matrices. The method was successfully validated for 10 compounds within all three matrices (amphetamine, methamphetamine, MDMA, MDA, venlafaxine, desmethylvenlafaxine, citalopram, metoprolol, propranolol and sotalol), 7 compounds validated for the liquid matrices only (mirtazapine, salbutamol, fluoxetine, desmethylcitalopram, atenolol, ephedrine and pseudoephedrine) and 1 compound (alprenolol) passing the criteria for solid samples only. The method was then applied to wastewater samples; cPACs were found at concentration ranges in liquid matrices of: 1.7 ng L(-1) (metoprolol) - 1321 ng L(-1) (tramadol) in influent,

Using normal ranges for interpreting results of monitoring and tiering to guide future work: A case study of increasing polycyclic aromatic compounds in lake sediments from the Cold Lake oil sands (Alberta, Canada) described in Korosi et al. (2016).

PubMed

Munkittrick, Kelly R; Arciszewski, Tim J

2017-12-01

Since the publishing of the Kelly et al. papers (2009, 2010) describing elevated contaminants in snow near the Alberta oil sands, there has been a significant expansion of monitoring efforts, enhanced by $50M a year contributed by industry to a regional Joint Oil Sands Monitoring (JOSM) program. In parallel to the intensification of research and monitoring efforts, including expansion of measured indicators, techniques for chemical analysis have also become more sensitive. Both factors contribute to the increased sensitivity and power, and improve our capacity to detect any change. The increase in capability requires a counterbalance to account for trivial change. This can be done using an interpretative approach that requires contextualization of differences to meaningfully inform environmental monitoring programs and provide focus for action. Experience obtained through 25 years of involvement with Canada's Environmental Effects Monitoring (EEM) program has shown that a tiered program informed by triggers can provide the context to make decisions about monitoring priorities. Here we provide a potential interpretation framework using a case study around the Korosi et al. (2016) study which found recent increases in alkylated polycyclic aromatic compounds (aPACs) in the Cold Lake in situ oil sands area. Public contaminant profiles from the JOSM studies in the oil sands region are used to evaluate the changes using an interpretation framework based on estimated normal ranges using existing data for site-specific, local and regional (distant) levels that was modelled after the tiered Canadian EEM design. Copyright © 2017 Elsevier Ltd. All rights reserved.

Procaspase-activating compound-1 induces apoptosis in Trypanosoma cruzi.

PubMed

de Castro, Emanuella; Reus, Thamile Luciane; de Aguiar, Alessandra Melo; Ávila, Andrea Rodrigues; de Arruda Campos Brasil de Souza, Tatiana

2017-12-01

Some therapeutics for parasitic, cardiac and neurological diseases activate apoptosis. Therefore, the study of apoptotic proteins in pathogenic organisms is relevant. However, the molecular mechanism of apoptosis in unicellular organisms remain elusive, despite morphological evidence of its occurrence. In Trypanosoma cruzi, the causative agent of Chagas disease, metacaspase 3 (TcMCA3), seems to have a key role in parasite apoptosis. Accordingly, this work provides data concerning TcMCA3 regulation through its interaction with procaspase-activating compound 1 (PAC-1), a procaspase 3 activator. Indeed, PAC-1 reduced T. cruzi epimastigote viability with an IC 50 of 14.12 µM and induced loss of mitochondrial potential and exposure of phosphatidylserine, features of the apoptotic process. Notwithstanding, those PAC-1-inducible effects were not conserved in metacyclic trypomastigotes. Moreover, PAC-1 reduced the viability of mammalian cells with a greater IC 50 (25.70 µM) compared to T. cruzi epimastigotes, indicating distinct modes of binding between caspases and metacaspases. To shed light on the selectivity of metacaspases and caspases, we determined the structural features related to the PAC-1 binding sites in both types of proteins. These data are important for improving the understanding of the apoptosis pathway in T. cruzi so that TcMCA3 could be better targeted with future pharmaceuticals.

Data on performance of air stripping tower- PAC integrated system for removing of odor, taste, dye and organic materials from drinking water-A case study in Saqqez, Iran.

PubMed

Pirsaheb, Meghdad; Mohammadi, Jalil; Khosravi, Touba; Sharafi, Hooshmnd; Moradi, Masoud

2018-06-01

Unpleasant taste or smell are more importantly constituents of drinking-water, lead to complaints from consumers. Dye and organic matter as well change in disinfection practice may generate taste and an odorous compound in treated water. According to low efficiency of conventional methods to remove taste and odor compounds, present study was aimed to evaluate the performance of air stripping tower- Poly Aluminum Chloride (PAC) integrated system to remove odor and taste, dye and organic materials from drinking water. Different air to water ratio and PAC doses were used to remove considered parameters in certain condition. The results of this study indicated that the maximum removal efficiency of 86.2, 76.47, 58.46 and 41.27% of taste and odor, dye, COD and TOC were achieved by the air stripping tower- PAC integrated system, respectively. However, the physico-chemical characteristics of water and adsorbent effect on the of substances removal efficiency considerably. It can be stated that the air striping tower - PAC integrated system is able to reduce the odor and taste-causing substances and organic matter to a level which is recommended by the Institute of Standards and Industrial Research of Iran.

Enhanced superoxide anion production in activated peritoneal macrophages from English sole (Pleuronectes vetulus) exposed to PACs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clemons, E.; Arkoosh, M.; Casillas, E.

In fish, as in mammals, macrophages play a vital role in the destruction of infective organisms. The purpose of this study was to determine if peritoneal macrophages (M{O}s) from English sole (Pleuronectes vetulus), a marine benthic fish, have an altered ability to produce cytotoxic reactive oxygen intermediates (ROIs) after exposure to polycyclic aromatic compounds (PACs). ROIs are the principle product of M{O}s used to destroy engulfed organisms. Assay conditions, including the concentration of M{O}s, type of in vitro stimulant, tissue culture media, and incubation time were optimized to measure the production of superoxide anion (O{sub 2}{minus}), the progenitor ROI, inmore » English sole M{O}s. English sole were injected with an organic solvent extract of a PAH-contaminated sediment, equivalent to 20g sediment/kg fish, via their dorsal lymphatic sinus, and peritoneal M{O}s were harvested on days 1, 3, 5, 7, and 14 post injection. Activated peritoneal M{O}s from English sole injected with the sediment extract produced significantly more superoxide radicals after stimulation in vitro with either opsonized zymosan (OZ) or phorbol myristate acetate (PMA) than the vehicle injected or control fish. Specifically, activated peritoneal M{O}s stimulated with PMA in vitro produced greater amounts (compared to controls) of O{sub 2}{minus} on days 7 and 14 after exposure, whereas the same cells stimulated with OZ showed heightened production only on day 7 after exposure. No differences in the basal amounts of O{sub 2}{minus} production from activated peritoneal M{O}s between the treatment groups were observed. This study shows that exposure of English sole to PACs altered production of O{sub 2}{minus} by macrophages, however, the consequence to the immunocompetence of exposed fish remains to be elucidated.« less

Essential oil composition of stems and fruits of Caralluma europaea N.E.Br. (Apocynaceae).

PubMed

Zito, Pietro; Sajeva, Maurizio; Bruno, Maurizio; Maggio, Antonella; Rosselli, Sergio; Formisano, Carmen; Senatore, Felice

2010-01-27

The essential oil of the stems and fruits of Caralluma europaea (Guss.) N.E.Br. (Apocynaceae) from Lampedusa Island has been obtained by hydrodistillation and its composition analyzed. The analyses allowed the identification and quantification of 74 volatile compounds, of which 16 were aromatic and 58 non-aromatic. Stems and fruits contained 1.4% and 2.7% of aromatic compounds respectively, while non-aromatic were 88.3% and 88.8%. Non-aromatic hydrocarbons were the most abundant compounds in both organs, followed by fatty acids. Data showed differences in the profiles between stems and fruits which shared only eighteen compounds; stems accounted for 38 compounds while fruits for 53. Fruits showed a higher diversity especially in aromatic compounds with twelve versus four in stems. Among the volatiles identified in stems and fruits of C. europaea 26 are present in other taxa of Apocynaceae, 52 are semiochemicals for many insects, and 21 have antimicrobial activity. The possible ecological role of the volatiles found is briefly discussed.

Performance enhancement with powdered activated carbon (PAC) addition in a membrane bioreactor (MBR) treating distillery effluent.

PubMed

Satyawali, Yamini; Balakrishnan, Malini

2009-10-15

This work investigated the effect of powdered activated carbon (PAC) addition on the operation of a membrane bioreactor (MBR) treating sugarcane molasses based distillery wastewater (spentwash). The 8L reactor was equipped with a submerged 30 microm nylon mesh filter with 0.05 m(2) filtration area. Detailed characterization of the commercial wood charcoal based PAC was performed before using it in the MBR. The MBR was operated over 200 days at organic loading rates (OLRs) varying from 4.2 to 6.9 kg m(-3)d(-1). PAC addition controlled the reactor foaming during start up and enhanced the critical flux by around 23%; it also prolonged the duration between filter cleaning. Operation at higher loading rates was possible and for a given OLR, the chemical oxygen demand (COD) removal was higher with PAC addition. However, biodegradation in the reactor was limited and the high molecular weight compounds were not affected by PAC supplementation. The functional groups on PAC appear to interact with the polysaccharide portion of the sludge, which may reduce its propensity to interact with the nylon mesh.

Process for removing halogenated aliphatic and aromatic compounds from petroleum products

DOEpatents

Googin, J.M.; Napier, J.M.; Travaglini, M.A.

1983-09-20

A process is described for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contacting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible compound, such as, water or a polyhydroxy compound, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of water or polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the water or polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds and the low polar or nonpolar solvent are separated by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered from recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced. 1 fig.

Process for removing halogenated aliphatic and aromatic compounds from petroleum products

DOEpatents

Googin, John M.; Napier, John M.; Travaglini, Michael A.

1983-01-01

A process for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contacting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible compound, such as, water or a polyhydroxy compound, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of water or polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the water or polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds and the low polar or nonpolar solvent are separated by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered from recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced.

Molecular evidence of Zn chelation of the procaspase activating compound B-PAC-1 in B cell lymphoma.

PubMed

Sarkar, Aloke; Balakrishnan, Kumudha; Chen, Jefferson; Patel, Viralkumar; Neelapu, Sattva S; McMurray, John S; Gandhi, Varsha

2016-01-19

The resistance of apoptosis in cancer cells is pivotal for their survival and is typically ruled by mutations or dysregulation of core apoptotic cascade. Mantle cell lymphoma (MCL) is a non-Hodgkin's B-cell malignancy expressing higher anti-apoptotic proteins providing survival advantage. B-PAC-1, a procaspase activating compound, induces apoptosis by sequestering Zn bound to procaspase-3, but the amino acids holding Zn in Caspase-3 is not known. Here we show that reintroduction of WT caspase-3 or 7 in Caspase3-7 double knock-out (DKO) mouse embryonic fibroblasts (MEF) promoted B-PAC-1 to induce apoptosis (27-43%), but not in DKO MEFs or MEFs expressing respective Casp3-7 catalytic mutants (12-13%). Using caspase-6 and -9 exosite analysis, we identified and mutated predicted Zn-ligands in caspase-3 (H108A, C148S and E272A) and overexpressed into DKO MEFs. Mutants carrying E272A abrogated Zn-reversal of apoptosis induced by B-PAC-1 via higher XIAP and smac expressions but not in H108A or C148S mutants. Co-immunoprecipitation analysis revealed stronger XIAP-caspase-3 interaction suggesting a novel mechanism of impulsive apoptosis resistance by disrupting predicted Zn-ligands in caspase-3. B-PAC-1 sponsored apoptosis in MCL cell lines (30-73%) via caspase-3 and PARP cleavages accompanied by loss of Mcl-1 and IAPs including XIAP while Zn substantially abrogated B-PAC-1-driven apoptosis (18-36%). In contrary, Zn is dispensable to inhibit staurosporin, bendamustine, ABT199 or MK206-induced apoptosis. Consistent to cell lines, B-PAC-1 stimulated cell death in primary B-lymphoma cells via caspase-3 cleavage with decline in both Mcl-1 and XIAP. This study underscores the first genetic evidence that B-PAC-1 driven apoptosis is mediated via Zn chelation.

Diurnal variability of polycyclic aromatic compound (PAC) concentrations: Relationship with meteorological conditions and inferred sources

NASA Astrophysics Data System (ADS)

Alam, Mohammed S.; Keyte, Ian J.; Yin, Jianxin; Stark, Christopher; Jones, Alan M.; Harrison, Roy M.

2015-12-01

Polycyclic aromatic hydrocarbons (PAH) and their nitro and oxy derivatives have been sampled every three hours over one week in winter at two sites in Birmingham UK. One site is heavily influenced by road traffic and is close to residential dwellings, while the other site is a background urban location at some distance from both sources of emission. The time series of concentrations has been examined along with the ratio of concentrations between the two sampling sites. A comparison of averaged diurnal profiles has shown different patterns of behaviour which has been investigated through calculating ratios of concentration at 18:00-21:00 h relative to that at 06:00-09:00 h. This allows identification of those compounds with a strong contribution to a traffic-related maximum at 06:00-09:00 h which are predominantly the low molecular weight PAHs, together with a substantial group of quinones and nitro-PAHs. Changes in partitioning between vapour and particulate forms are unlikely to influence the ratio as the mean temperature at both times was almost identical. Most compounds show an appreciable increase in concentrations in the evening which is attributed to residential heating emissions. Compounds dominated by this source show high ratios of 18:00-21:00 concentrations relative to 06:00-09:00 concentrations and include higher molecular weight PAH and a substantial group of both quinones and nitro-PAH. The behaviour of retene, normally taken as an indicator of biomass burning, is suggestive of wood smoke only being one contributor to the evening peak in PAH and their derivatives, with coal combustion presumably being the other main contributor. Variations of PAH concentrations with wind speed show a dilution behaviour consistent with other primary pollutants, and high concentrations of a range of air pollutants were observed in an episode of low temperatures and low wind speeds towards the end of the overall sampling period consistent with poor local dispersion processes. Results from a short summer campaign give indications of the formation of some nitro-PAH by atmospheric chemical reactions.

Oxidation of aromatic contaminants coupled to microbial iron reduction

USGS Publications Warehouse

Lovley, D.R.; Baedecker, M.J.; Lonergan, D.J.; Cozzarelli, I.M.; Phillips, E.J.P.; Siegel, D.I.

1989-01-01

THE contamination of sub-surface water supplies with aromatic compounds is a significant environmental concern1,2. As these contaminated sub-surface environments are generally anaerobic, the microbial oxidation of aromatic compounds coupled to nitrate reduction, sulphate reduction and methane production has been studied intensively1-7. In addition, geochemical evidence suggests that Fe(III) can be an important electron acceptor for the oxidation of aromatic compounds in anaerobic groundwater. Until now, only abiological mechanisms for the oxidation of aromatic compounds with Fe(III) have been reported8-12. Here we show that in aquatic sediments, microbial activity is necessary for the oxidation of model aromatic compounds coupled to Fe(III) reduction. Furthermore, a pure culture of the Fe(III)-reducing bacterium GS-15 can obtain energy for growth by oxidizing benzoate, toluene, phenol or p-cresol with Fe(III) as the sole electron acceptor. These results extend the known physiological capabilities of Fe(III)-reducing organisms and provide the first example of an organism of any type which can oxidize an aromatic hydrocarbon anaerobically. ?? 1989 Nature Publishing Group.

Process for removing halogenated aliphatic and aromatic compounds from petroleum products. [Polychlorinated biphenyls; methylene chloride; perchloroethylene; trichlorofluoroethane; trichloroethylene; chlorobenzene

DOEpatents

Googin, J.M.; Napier, J.M.; Travaglini, M.A.

1982-03-31

A process for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contracting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible polyhydroxy compound, such as, water, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds in the low polar or nonpolar solvent by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered for recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced. 2 tables.

40 CFR 721.775 - Brominated aromatic com-pound (generic name).

Code of Federal Regulations, 2013 CFR

2013-07-01

.... Requirements as specified in § 721.80 (j) (use as an additive flame retardant for plastics) and (q). (iv... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Brominated aromatic com-pound (generic... Specific Chemical Substances § 721.775 Brominated aromatic com-pound (generic name). (a) Chemical...

40 CFR 721.775 - Brominated aromatic com-pound (generic name).

Code of Federal Regulations, 2014 CFR

2014-07-01

.... Requirements as specified in § 721.80 (j) (use as an additive flame retardant for plastics) and (q). (iv... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Brominated aromatic com-pound (generic... Specific Chemical Substances § 721.775 Brominated aromatic com-pound (generic name). (a) Chemical...

40 CFR 721.775 - Brominated aromatic com-pound (generic name).

Code of Federal Regulations, 2012 CFR

2012-07-01

.... Requirements as specified in § 721.80 (j) (use as an additive flame retardant for plastics) and (q). (iv... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Brominated aromatic com-pound (generic... Specific Chemical Substances § 721.775 Brominated aromatic com-pound (generic name). (a) Chemical...

Device for aqueous detection of nitro-aromatic compounds

DOEpatents

Reagen, W.K.; Schulz, A.L.; Ingram, J.C.; Lancaster, G.D.; Grey, A.E.

1994-04-26

This invention relates to a compact and portable detection apparatus for nitro-aromatic based chemical compounds, such as nitrotoluenes, dinitrotoluenes, and trinitrotoluene (TNT). The apparatus is based upon the use of fiber optics using filtered light. The preferred process of the invention relies upon a reflective chemical sensor and optical and electronic components to monitor a decrease in fluorescence when the nitro-aromatic molecules in aqueous solution combine and react with a fluorescent polycyclic aromatic compound. 4 figures.

Device for aqueous detection of nitro-aromatic compounds

DOEpatents

Reagen, William K.; Schulz, Amber L.; Ingram, Jani C.; Lancaster, Gregory D.; Grey, Alan E.

1994-01-01

This invention relates to a compact and portable detection apparatus for ro-aromatic based chemical compounds, such as nitrotoluenes, dinitrotoluenes, and trinitrotoluene (TNT). The apparatus is based upon the use of fiber optics using filtered light. The preferred process of the invention relies upon a reflective chemical sensor and optical and electronic components to monitor a decrease in fluorescence when the nitro-aromatic molecules in aqueous solution combine and react with a fluorescent polycyclic aromatic compound.

The cranberry flavonoids PAC DP-9 and quercetin aglycone induce cytotoxicity and cell cycle arrest and increase cisplatin sensitivity in ovarian cancer cells

PubMed Central

WANG, YIFEI; HAN, ALEX; CHEN, EVA; SINGH, RAKESH K.; CHICHESTER, CLINTON O.; MOORE, RICHARD G.; SINGH, AJAY P.; VORSA, NICHOLI

2015-01-01

Cranberry flavonoids (flavonols and flavan-3-ols), in addition to their antioxidant properties, have been shown to possess potential in vitro activity against several cancers. However, the difficulty of isolating cranberry compounds has largely limited anticancer research to crude fractions without well-defined compound composition. In this study, individual cranberry flavonoids were isolated to the highest purity achieved so far using gravity and high performance column chromatography and LC-MS characterization. MTS assay indicated differential cell viability reduction of SKOV-3 and OVCAR-8 ovarian cancer cells treated with individual cranberry flavonoids. Treatment with quercetin aglycone and PAC DP-9, which exhibited the strongest activity, induced apoptosis, led to caspase-3 activation and PARP deactivation, and increased sensitivity to cisplatin. Furthermore, immunofluorescence microscopy and western blot study revealed reduced expression and activation of epidermal growth factor receptor (EGFR) in PAC DP-9 treated SKOV-3 cells. In addition, quercetin aglycone and PAC DP-9 deactivated MAPK-ERK pathway, induced downregulation of cyclin D1, DNA-PK, phosphohistone H3 and upregulation of p21, and arrested cell cycle progression. Overall, this study demonstrates promising in vitro cytotoxic and anti-proliferative properties of two newly characterized cranberry flavonoids, quercetin aglycone and PAC DP-9, against ovarian cancer cells. PMID:25776829

Compounds having aromatic rings and side-chain amide-functionality and a method for transporting monovalent anions across biological membranes using the same

DOEpatents

Davis, Jeffery T [College Park, MD; Sidorov, Vladimir [Richmond, VA; Kotch, Frank W [New Phila., PA

2008-04-08

A compound containing at least two aromatic rings covalently bonded together, with each aromatic ring containing at least one oxyacetamide-based side chain, the compound being capable of forming a chloride ion channel across a lipid bilayer, and transporting chloride ion across the lipid bilayer.

Aromatic metabolism of filamentous fungi in relation to the presence of aromatic compounds in plant biomass.

PubMed

Mäkelä, Miia R; Marinović, Mila; Nousiainen, Paula; Liwanag, April J M; Benoit, Isabelle; Sipilä, Jussi; Hatakka, Annele; de Vries, Ronald P; Hildén, Kristiina S

2015-01-01

The biological conversion of plant lignocellulose plays an essential role not only in carbon cycling in terrestrial ecosystems but also is an important part of the production of second generation biofuels and biochemicals. The presence of the recalcitrant aromatic polymer lignin is one of the major obstacles in the biofuel/biochemical production process and therefore microbial degradation of lignin is receiving a great deal of attention. Fungi are the main degraders of plant biomass, and in particular the basidiomycete white rot fungi are of major importance in converting plant aromatics due to their ability to degrade lignin. However, the aromatic monomers that are released from lignin and other aromatic compounds of plant biomass are toxic for most fungi already at low levels, and therefore conversion of these compounds to less toxic metabolites is essential for fungi. Although the release of aromatic compounds from plant biomass by fungi has been studied extensively, relatively little attention has been given to the metabolic pathways that convert the resulting aromatic monomers. In this review we provide an overview of the aromatic components of plant biomass, and their release and conversion by fungi. Finally, we will summarize the applications of fungal systems related to plant aromatics. Copyright © 2015 Elsevier Inc. All rights reserved.

Retardation effect of nitrogen compounds and condensed aromatics on shale oil catalytic cracking processing and their characterization.

PubMed

Li, Nan; Chen, Chen; Wang, Bin; Li, Shaojie; Yang, Chaohe; Chen, Xiaobo

Untreated shale oil, shale oil treated with HCl aqueous solution and shale oil treated with HCl and furfural were used to do comparative experiments in fixed bed reactors. Nitrogen compounds and condensed aromatics extracted by HCl and furfural were characterized by electrospray ionization Fourier transform cyclotron resonance mass spectrometry and gas chromatography and mass spectrometry, respectively. Compared with untreated shale oil, the conversion and yield of liquid products increased considerably after removing basic nitrogen compounds by HCl extraction. Furthermore, after removing nitrogen compounds and condensed aromatics by both HCl and furfural, the conversion and yield of liquid products further increased. In addition, N 1 class species are predominant in both basic and non-basic nitrogen compounds, and they are probably indole, carbazole, cycloalkyl-carbazole, pyridine and cycloalkyl-pyridine. As for the condensed aromatics, most of them possess aromatic rings with two to three rings and zero to four carbon atom.

PERFLUORINATED AROMATIC COMPOUNDS

DTIC Science & Technology

decafluorodiphenylamine, 3,3’,4,4’-tetra substituted- hexafluorobiphenyls, tetrafluororesorcinol, perfluoroaromatic thioethers, and dithiols. These...and other perfluorinated aromatic compounds are the intermediates employed in the synthesis of perfluorinated model compounds and polymers.

Bacterial Degradation of Aromatic Compounds

PubMed Central

Seo, Jong-Su; Keum, Young-Soo; Li, Qing X.

2009-01-01

Aromatic compounds are among the most prevalent and persistent pollutants in the environment. Petroleum-contaminated soil and sediment commonly contain a mixture of polycyclic aromatic hydrocarbons (PAHs) and heterocyclic aromatics. Aromatics derived from industrial activities often have functional groups such as alkyls, halogens and nitro groups. Biodegradation is a major mechanism of removal of organic pollutants from a contaminated site. This review focuses on bacterial degradation pathways of selected aromatic compounds. Catabolic pathways of naphthalene, fluorene, phenanthrene, fluoranthene, pyrene, and benzo[a]pyrene are described in detail. Bacterial catabolism of the heterocycles dibenzofuran, carbazole, dibenzothiophene, and dibenzodioxin is discussed. Bacterial catabolism of alkylated PAHs is summarized, followed by a brief discussion of proteomics and metabolomics as powerful tools for elucidation of biodegradation mechanisms. PMID:19440284

Bond cleavage of lignin model compounds into aromatic monomers using supported metal catalysts in supercritical water

PubMed Central

Yamaguchi, Aritomo; Mimura, Naoki; Shirai, Masayuki; Sato, Osamu

2017-01-01

More efficient use of lignin carbon is necessary for carbon-efficient utilization of lignocellulosic biomass. Conversion of lignin into valuable aromatic compounds requires the cleavage of C–O ether bonds and C–C bonds between lignin monomer units. The catalytic cleavage of C–O bonds is still challenging, and cleavage of C–C bonds is even more difficult. Here, we report cleavage of the aromatic C–O bonds in lignin model compounds using supported metal catalysts in supercritical water without adding hydrogen gas and without causing hydrogenation of the aromatic rings. The cleavage of the C–C bond in bibenzyl was also achieved with Rh/C as a catalyst. Use of this technique may greatly facilitate the conversion of lignin into valuable aromatic compounds. PMID:28387304

Three-dimensional aromatic networks.

PubMed

Toyota, Shinji; Iwanaga, Tetsuo

2014-01-01

Three-dimensional (3D) networks consisting of aromatic units and linkers are reviewed from various aspects. To understand principles for the construction of such compounds, we generalize the roles of building units, the synthetic approaches, and the classification of networks. As fundamental compounds, cyclophanes with large aromatic units and aromatic macrocycles with linear acetylene linkers are highlighted in terms of transannular interactions between aromatic units, conformational preference, and resolution of chiral derivatives. Polycyclic cage compounds are constructed from building units by linkages via covalent bonds, metal-coordination bonds, or hydrogen bonds. Large cage networks often include a wide range of guest species in their cavity to afford novel inclusion compounds. Topological isomers consisting of two or more macrocycles are formed by cyclization of preorganized species. Some complicated topological networks are constructed by self-assembly of simple building units.

A comparative study of coagulation, granular- and powdered-activated carbon for the removal of perfluorooctane sulfonate and perfluorooctanoate in drinking water treatment.

PubMed

Pramanik, Biplob Kumar; Pramanik, Sagor Kumar; Suja, Fatihah

2015-01-01

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) are persistent organic pollutants in the environment and their occurrence causes toxicological effects on humans. We examined different conventional coagulant treatments such as alum, ferric chloride and polyaluminium chloride in removing these compounds. These were then compared with a natural coagulant (Moringa oleifera). We also investigated the powdered-activated carbon (PAC) and granular-activated carbon (GAC) for removing these compounds. At an initial dose of 5 mg/L, polyaluminium chloride led to a higher reduction of PFOS/PFOA compared with alum which in turn was higher than ferric. The removal efficiency increased with the increase in coagulant dose and decrease in pH. M. oleifera was very effective in reducing PFOS and PFOA than conventional coagulants, with a reduction efficiencies of 65% and 72%, respectively, at a dose of 30 mg/L. Both PAC and GAC were very effective in reducing these compounds than coagulations. PAC led to a higher reduction in PFOS and PFOA than GAC due to its greater surface area and shorter internal diffusion distances. The addition of PAC (10 min contact time) with coagulation (at 5 mg/L dosage) significantly increased the removal efficiency, and the maximum removal efficiency was for M. oleifera with 98% and 94% for PFOS and PFOA, respectively. The reduction efficiency of PFOS/PFOA was reduced with the increase in dissolved organic concentration due to the adsorption competition between organic molecules and PFOS/PFOA.

Photocatalytic degradation of clofibric acid, carbamazepine and iomeprol using conglomerated TiO2 and activated carbon in aqueous suspension.

PubMed

Ziegmann, Markus; Frimmel, Fritz H

2010-01-01

The combination of powdered activated carbon (PAC) and TiO(2) has been tested for synergistic/antagonistic effects in the photocatalytic degradation of carbamazepine, clofibric acid and iomeprol. Synergistic effects are thought to be caused by rapid adsorption on the PAC surface followed by diffusion to the TiO(2) surface and photocatalytic degradation. The Freundlich constant K(F) was used for comparing the sorption properties of the three substances and it was found that K(F) for clofibric acid was 3 times lower than for carbamazepine and iomeprol, regardless of the kind of PAC used. A PAC with a distinct tendency to form conglomerates was selected so that a high percentage of the PAC surface was in direct proximity to the TiO(2) surface. The photocatalytic degradation of the pharmaceutically active compounds studied followed pseudo-first order kinetics. Synergistic effects only occurred for clofibric acid (factor 1.5) and an inverse relationship between adsorption affinity and synergistic effects was found. High affinity of the target substances to the PAC surface seemed to be counterproductive for the photocatalytic degradation.

Global simulation of aromatic volatile organic compounds in the atmosphere

NASA Astrophysics Data System (ADS)

Cabrera Perez, David; Taraborrelli, Domenico; Pozzer, Andrea

2015-04-01

Among the large number of chemical compounds in the atmosphere, the organic group plays a key role in the tropospheric chemistry. Specifically the subgroup called aromatics is of great interest. Aromatics are the predominant trace gases in urban areas due to high emissions, primarily by vehicle exhausts and fuel evaporation. They are also present in areas where biofuel is used (i.e residential wood burning). Emissions of aromatic compounds are a substantial fraction of the total emissions of the volatile organic compounds (VOC). Impact of aromatics on human health is very important, as they do not only contribute to the ozone formation in the urban environment, but they are also highly toxic themselves, especially in the case of benzene which is able to trigger a range of illness under long exposure, and of nitro-phenols which cause detrimental for humans and vegetation even at very low concentrations. The aim of this work is to assess the atmospheric impacts of aromatic compounds on the global scale. The main goals are: lifetime and budget estimation, mixing ratios distribution, net effect on ozone production and OH loss for the most emitted aromatic compounds (benzene, toluene, xylenes, ethylbenzene, styrene and trimethylbenzenes). For this purpose, we use the numerical chemistry and climate simulation ECHAM/MESSy Atmospheric Chemistry (EMAC) model to build the global atmospheric budget for the most emitted and predominant aromatic compounds in the atmosphere. A set of emissions was prepared in order to include biomass burning, vegetation and anthropogenic sources of aromatics into the model. A chemical mechanism based on the Master Chemical Mechanism (MCM) was developed to describe the chemical oxidation in the gas phase of these aromatic compounds. MCM have been reduced in terms of number of chemical equation and species in order to make it affordable in a 3D model. Additionally other features have been added, for instance the production of HONO via ortho-nitrophenols photolysis. The model results are compared with observations from different surface and aircraft campaigns in order to estimate the accuracy of the model.

Mass spectral analysis of long chain alkyl aromatic compounds synthesized from alpha-olefin alkylation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheng, M.T.; Hudson, J.D.

1994-12-31

Long chain alkyl aromatic compounds are important petrochemicals with many applications. They are generally synthesized by alkylating the corresponding aromatic nucleus. In this report, the authors will describe the mass spectral fragmentation of alkylphenols and alkylsalicylates.

Oxidative decomposition of aromatic hydrocarbons by electron beam irradiation

NASA Astrophysics Data System (ADS)

Han, Do-Hung; Stuchinskaya, Tatiana; Won, Yang-Soo; Park, Wan-Sik; Lim, Jae-Kyong

2003-05-01

Decomposition of aromatic volatile organic compounds (VOCs) under electron beam irradiation was studied in order to examine the kinetics of the process, to characterize the reaction product distribution and to develop a process of waste gas control technology. Toluene, ethylbenzene, o-, m-, p-xylenes and chlorobenzene were used as target materials. The experiments were carried out at doses ranging from 0.5 to 10 kGy, using a flow reactor utilized under electron beam irradiation. Maximum degrees of decomposition carried out at 10 kGy in air environment were 55-65% for “non-chlorinated” aromatic VOC and 85% for chlorobenzene. It was found that a combination of aromatic pollutants with chlorobenzene would considerably increase the degradation value up to nearly 50% compared to the same compounds in the absence of chlorine groups. Based on our experimental observation, the degradation mechanism of the aromatic compounds combined with chloro-compound suggests that a chlorine radical, formed from EB irradiation, induces a chain reaction, resulting in an accelerating oxidative destruction of aromatic VOCs.

Aromatic Amino Acid-Derived Compounds Induce Morphological Changes and Modulate the Cell Growth of Wine Yeast Species

PubMed Central

González, Beatriz; Vázquez, Jennifer; Cullen, Paul J.; Mas, Albert; Beltran, Gemma; Torija, María-Jesús

2018-01-01

Yeasts secrete a large diversity of compounds during alcoholic fermentation, which affect growth rates and developmental processes, like filamentous growth. Several compounds are produced during aromatic amino acid metabolism, including aromatic alcohols, serotonin, melatonin, and tryptamine. We evaluated the effects of these compounds on growth parameters in 16 different wine yeasts, including non-Saccharomyces wine strains, for which the effects of these compounds have not been well-defined. Serotonin, tryptamine, and tryptophol negatively influenced yeast growth, whereas phenylethanol and tyrosol specifically affected non-Saccharomyces strains. The effects of the aromatic alcohols were observed at concentrations commonly found in wines, suggesting a possible role in microbial interaction during wine fermentation. Additionally, we demonstrated that aromatic alcohols and ethanol are able to affect invasive and pseudohyphal growth in a manner dependent on nutrient availability. Some of these compounds showed strain-specific effects. These findings add to the understanding of the fermentation process and illustrate the diversity of metabolic communication that may occur among related species during metabolic processes. PMID:29696002

Enantiomeric Profiling of Chiral Pharmacologically Active Compounds in the Environment with the Usage of Chiral Liquid Chromatography 
Coupled with Tandem Mass Spectrometry

PubMed Central

Camacho-Muñoz, Dolores; Petrie, Bruce; Castrignanò, Erika; Kasprzyk-Hordern, Barbara

2016-01-01

The issue of drug chirality is attracting increasing attention among the scientific community. The phenomenon of chirality has been overlooked in environmental research (environmental occurrence, fate and toxicity) despite the great impact that chiral pharmacologically active compounds (cPACs) can provoke on ecosystems. The aim of this paper is to introduce the topic of chirality and its implications in environmental contamination. Special attention has been paid to the most recent advances in chiral analysis based on liquid chromatography coupled with mass spectrometry and the most popular protein based chiral stationary phases. Several groups of cPACs of environmental relevance, such as illicit drugs, human and veterinary medicines were discussed. The increase in the number of papers published in the area of chiral environmental analysis indicates that researchers are actively pursuing new opportunities to provide better understanding of environmental impacts resulting from the enantiomerism of cPACs. PMID:27713682

Controlling harmful algae blooms using aluminum-modified clay.

PubMed

Liu, Yang; Cao, Xihua; Yu, Zhiming; Song, Xiuxian; Qiu, Lixia

2016-02-15

The performances of aluminum chloride modified clay (AC-MC), aluminum sulfate modified clay (AS-MC) and polyaluminum chloride modified clay (PAC-MC) in the removal of Aureococcus anophagefferens were compared, and the potential mechanisms were analyzed according to the dispersion medium, suspension pH and clay surface charges. The results showed that AC-MC and AS-MC had better efficiencies in removing A.anophagefferens than PAC-MC. The removal mechanisms of the three modified clays varied. At optimal coagulation conditions, the hydrolysates of AC and AS were mainly monomers, and they transformed into Al(OH)3(am) upon their addition to algae culture, with the primary mechanism being sweep flocculation. The PAC mainly hydrolyzed to the polyaluminum compounds, which remained stable when added to the algae culture, and the flocculation mainly occurred through polyaluminum compounds. The suspension pH significantly influenced the aluminum hydrolysate and affected the flocculation between the modified clay and algae cells. Copyright © 2016 Elsevier Ltd. All rights reserved.

GLOBAL INVENTORY OF VOLATILE COMPOUND EMISSIONS FROM ANTHROPOGENIC SOURCES

EPA Science Inventory

The report describes a global inventory anthropogenic volatile organic compound (VOC) emissions that includes a separate inventory for each of seven pollutant groups--paraffins, olefins, aromatics, formaldehyde, other aldehydes, other aromatics, and marginally reactive compounds....

New Findings on Aromatic Compounds' Degradation and Their Metabolic Pathways, the Biosurfactant Production and Motility of the Halophilic Bacterium Halomonas sp. KHS3.

PubMed

Corti Monzón, Georgina; Nisenbaum, Melina; Herrera Seitz, M Karina; Murialdo, Silvia E

2018-04-24

The study of the aromatic compounds' degrading ability by halophilic bacteria became an interesting research topic, because of the increasing use of halophiles in bioremediation of saline habitats and effluents. In this work, we focused on the study of aromatic compounds' degradation potential of Halomonas sp. KHS3, a moderately halophilic bacterium isolated from hydrocarbon-contaminated seawater of the Mar del Plata harbour. We demonstrated that H. sp. KHS3 is able to grow using different monoaromatic (salicylic acid, benzoic acid, 4-hydroxybenzoic acid, phthalate) and polyaromatic (naphthalene, fluorene, and phenanthrene) substrates. The ability to degrade benzoic acid and 4-hydroxybenzoic acid was analytically corroborated, and Monod kinetic parameters and yield coefficients for degradation were estimated. Strategies that may enhance substrate bioavailability such as surfactant production and chemotactic responses toward aromatic compounds were confirmed. Genomic sequence analysis of this strain allowed us to identify several genes putatively related to the metabolism of aromatic compounds, being the catechol and protocatechuate branches of β-ketoadipate pathway completely represented. These features suggest that the broad-spectrum xenobiotic degrader H. sp. KHS3 could be employed as a useful biotechnological tool for the cleanup of aromatic compounds-polluted saline habitats or effluents.

Airborne Exposures to Polycyclic Aromatic Compounds Among Workers in Asphalt Roofing Manufacturing Facilities.

PubMed

Trumbore, David C; Osborn, Linda V; Johnson, Kathleen A; Fayerweather, William E

2015-01-01

We studied exposure of 151 workers to polycyclic aromatic compounds and asphalt emissions during the manufacturing of asphalt roofing products-including 64 workers from 10 asphalt plants producing oxidized, straight-run, cutback, and wax- or polymer-modified asphalts, and 87 workers from 11 roofing plants producing asphalt shingles and granulated roll roofing. The facilities were located throughout the United States and used asphalt from many refiners and crude oils. This article helps fill a gap in exposure data for asphalt roofing manufacturing workers by using a fluorescence technique that targets biologically active 4-6 ring polycyclic aromatic compounds and is strongly correlated with carcinogenic activity in animal studies. Worker exposures to polycyclic aromatic compounds were compared between manufacturing plants, at different temperatures and using different raw materials, and to important external benchmarks. High levels of fine limestone particulate in the plant air during roofing manufacturing increased polycyclic aromatic compound exposure, resulting in the hypothesis that the particulate brought adsorbed polycyclic aromatic compounds to the worker breathing zone. Elevated asphalt temperatures increased exposures during the pouring of asphalt. Co-exposures in these workplaces which act as confounders for both the measurement of total organic matter and fluorescence were detected and their influence discussed. Exposures to polycyclic aromatic compounds in asphalt roofing manufacturing facilities were lower than or similar to those reported in hot-mix paving application studies, and much below those reported in studies of hot application of built-up roofing asphalt. These relatively low exposures in manufacturing are primarily attributed to air emission controls in the facilities, and the relatively moderate temperatures, compared to built-up roofing, used in these facilities for oxidized asphalt. The exposure to polycyclic aromatic compounds was a very small part of the overall worker exposure to asphalt fume, on average less than 0.07% of the benzene-soluble fraction. Measurements of benzene-soluble fraction were uniformly below the American Conference of Governmental Industrial Hygienists' Threshold Limit Value for asphalt fume.

Amino Acids, Aromatic Compounds, and Carboxylic Acids: How Did They Get Their Common Names?

ERIC Educational Resources Information Center

Leung, Sam H.

2000-01-01

Surveys the roots of the common names of organic compounds most likely to be encountered by undergraduate organic chemistry students. Includes information for 19 amino acids, 17 aromatic compounds, and 21 carboxylic acids. (WRM)

Multi-Phase Equilibrium and Solubilities of Aromatic Compounds and Inorganic Compounds in Sub- and Supercritical Water: A Review.

PubMed

Liu, Qinli; Ding, Xin; Du, Bowen; Fang, Tao

2017-11-02

Supercritical water oxidation (SCWO), as a novel and efficient technology, has been applied to wastewater treatment processes. The use of phase equilibrium data to optimize process parameters can offer a theoretical guidance for designing SCWO processes and reducing the equipment and operating costs. In this work, high-pressure phase equilibrium data for aromatic compounds+water systems and inorganic compounds+water systems are given. Moreover, thermodynamic models, equations of state (EOS) and empirical and semi-empirical approaches are summarized and evaluated. This paper also lists the existing problems of multi-phase equilibria and solubility studies on aromatic compounds and inorganic compounds in sub- and supercritical water.

Construction and Optimization of a Heterologous Pathway for Protocatechuate Catabolism in Escherichia coli Enables Bioconversion of Model Aromatic Compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clarkson, Sonya M.; Giannone, Richard J.; Kridelbaugh, Donna M.

The production of biofuels from lignocellulose yields a substantial lignin by-product stream that currently has few applications. Biological conversion of lignin-derived compounds into chemicals and fuels has the potential to improve the economics of lignocellulose-derived biofuels, but few microbes are able both to catabolize lignin-derived aromatic compounds and to generate valuable products. WhileEscherichia colihas been engineered to produce a variety of fuels and chemicals, it is incapable of catabolizing most aromatic compounds. Therefore, we engineeredE. colito catabolize protocatechuate, a common intermediate in lignin degradation, as the sole source of carbon and energy via heterologous expression of a nine-gene pathway fromPseudomonasmore » putidaKT2440. Then, we used experimental evolution to select for mutations that increased growth with protocatechuate more than 2-fold. Increasing the strength of a single ribosome binding site in the heterologous pathway was sufficient to recapitulate the increased growth. After optimization of the core pathway, we extended the pathway to enable catabolism of a second model compound, 4-hydroxybenzoate. These engineered strains will be useful platforms to discover, characterize, and optimize pathways for conversions of lignin-derived aromatics. IMPORTANCELignin is a challenging substrate for microbial catabolism due to its polymeric and heterogeneous chemical structure. Therefore, engineering microbes for improved catabolism of lignin-derived aromatic compounds will require the assembly of an entire network of catabolic reactions, including pathways from genetically intractable strains. By constructing defined pathways for aromatic compound degradation in a model host would allow rapid identification, characterization, and optimization of novel pathways. Finally, we constructed and optimized one such pathway inE. colito enable catabolism of a model aromatic compound, protocatechuate, and then extended the pathway to a related compound, 4-hydroxybenzoate. This optimized strain can now be used as the basis for the characterization of novel pathways.« less

Construction and Optimization of a Heterologous Pathway for Protocatechuate Catabolism in Escherichia coli Enables Bioconversion of Model Aromatic Compounds.

PubMed

Clarkson, Sonya M; Giannone, Richard J; Kridelbaugh, Donna M; Elkins, James G; Guss, Adam M; Michener, Joshua K

2017-09-15

The production of biofuels from lignocellulose yields a substantial lignin by-product stream that currently has few applications. Biological conversion of lignin-derived compounds into chemicals and fuels has the potential to improve the economics of lignocellulose-derived biofuels, but few microbes are able both to catabolize lignin-derived aromatic compounds and to generate valuable products. While Escherichia coli has been engineered to produce a variety of fuels and chemicals, it is incapable of catabolizing most aromatic compounds. Therefore, we engineered E. coli to catabolize protocatechuate, a common intermediate in lignin degradation, as the sole source of carbon and energy via heterologous expression of a nine-gene pathway from Pseudomonas putida KT2440. We next used experimental evolution to select for mutations that increased growth with protocatechuate more than 2-fold. Increasing the strength of a single ribosome binding site in the heterologous pathway was sufficient to recapitulate the increased growth. After optimization of the core pathway, we extended the pathway to enable catabolism of a second model compound, 4-hydroxybenzoate. These engineered strains will be useful platforms to discover, characterize, and optimize pathways for conversions of lignin-derived aromatics. IMPORTANCE Lignin is a challenging substrate for microbial catabolism due to its polymeric and heterogeneous chemical structure. Therefore, engineering microbes for improved catabolism of lignin-derived aromatic compounds will require the assembly of an entire network of catabolic reactions, including pathways from genetically intractable strains. Constructing defined pathways for aromatic compound degradation in a model host would allow rapid identification, characterization, and optimization of novel pathways. We constructed and optimized one such pathway in E. coli to enable catabolism of a model aromatic compound, protocatechuate, and then extended the pathway to a related compound, 4-hydroxybenzoate. This optimized strain can now be used as the basis for the characterization of novel pathways. Copyright © 2017 American Society for Microbiology.

Detection of chlorinated aromatic compounds

DOEpatents

Ekechukwu, A.A.

1996-02-06

A method for making a composition for measuring the concentration of chlorinated aromatic compounds in aqueous fluids, and an optical probe for use with the method are disclosed. The composition comprises a hydrophobic polymer matrix, preferably polyamide, with a fluorescent indicator uniformly dispersed therein. The indicator fluoresces in the presence of the chlorinated aromatic compounds with an intensity dependent on the concentration of these compounds in the fluid of interest, such as 8-amino-2-naphthalene sulfonate. The probe includes a hollow cylindrical housing that contains the composition in its distal end. The probe admits an aqueous fluid to the probe interior for exposure to the composition. An optical fiber transmits excitation light from a remote source to the composition while the indicator reacts with chlorinated aromatic compounds present in the fluid. The resulting fluorescence light signal is reflected to a second optical fiber that transmits the light to a spectrophotometer for analysis. 5 figs.

Detection of chlorinated aromatic compounds

DOEpatents

Ekechukwu, Amy A.

1996-01-01

A method for making a composition for measuring the concentration of chloated aromatic compounds in aqueous fluids, and an optical probe for use with the method. The composition comprises a hydrophobic polymer matrix, preferably polyamide, with a fluorescent indicator uniformly dispersed therein. The indicator fluoresces in the presence of the chlorinated aromatic compounds with an intensity dependent on the concentration of these compounds in the fluid of interest, such as 8-amino-2-naphthalene sulfonate. The probe includes a hollow cylindrical housing that contains the composition in its distal end. The probe admits an aqueous fluid to the probe interior for exposure to the composition. An optical fiber transmits excitation light from a remote source to the composition while the indicator reacts with chlorinated aromatic compounds present in the fluid. The resulting fluorescence light signal is reflected to a second optical fiber that transmits the light to a spectrophotometer for analysis.

Conversion of 2-chloro-cis,cis-muconate and its metabolites 2-chloro- and 5-chloromuconolactone by chloromuconate cycloisomerases of pJP4 and pAC27.

PubMed Central

Vollmer, M D; Schlömann, M

1995-01-01

2-Chloro-cis,cis-muconate, the product of ortho-cleavage of 3-chlorocatechol, was converted by purified preparations of the pJP4- and pAC27-encoded chloromuconate cycloisomerases (EC 5.5.1.7) to trans-dienelactone (trans-4-carboxymethylenebut-2-en-4-olide). The same compound was also formed when (+)-2-chloro- and (+)-5-chloromuconolactone were substrates of these enzyme preparations. Thus, the pJP4- and pAC27-encoded chloromuconate cycloisomerases are able to catalyze chloride elimination from (+)-5-chloromuconolactone. The ability to convert (+)-2-chloromuconolactone differentiates these enzymes from other groups of cycloisomerases. PMID:7751312

Novel in vitro protein fragment complementation assay applicable to high-throughput screening in a 1536-well format.

PubMed

Hashimoto, Junko; Watanabe, Taku; Seki, Tatsuya; Karasawa, Satoshi; Izumikawa, Miho; Seki, Tomoe; Iemura, Shun-Ichiro; Natsume, Tohru; Nomura, Nobuo; Goshima, Naoki; Miyawaki, Atsushi; Takagi, Motoki; Shin-Ya, Kazuo

2009-09-01

Protein-protein interactions (PPIs) play key roles in all cellular processes and hence are useful as potential targets for new drug development. To facilitate the screening of PPI inhibitors as anticancer drugs, the authors have developed a high-throughput screening (HTS) system using an in vitro protein fragment complementation assay (PCA) with monomeric Kusabira-Green fluorescent protein (mKG). The in vitro PCA system was established by the topological formation of a functional complex between 2 split inactive mKG fragments fused to target proteins, which fluoresces when 2 target proteins interact to allow complementation of the mKG fragments. Using this assay system, the authors screened inhibitors for TCF7/beta-catenin, PAC1/PAC2, and PAC3 homodimer PPIs from 123,599 samples in their natural product library. Compound TB1 was identified as a specific inhibitor for PPI of PAC3 homodimer. TB1 strongly inhibited the PPI of PAC3 homodimer with an IC(50) value of 0.020 microM and did not inhibit PPI between TCF7/beta-catenin and PAC1/PAC2 even at a concentration of 250 microM. The authors thus demonstrated that this in vitro PCA system applicable to HTS in a 1536-well format is capable of screening for PPI inhibitors from a huge natural product library.

Pituitary adenylate cyclase-activating polypeptide type 1 (PAC1) receptor is expressed during embryonic development of the earthworm.

PubMed

Boros, Akos; Somogyi, Ildikó; Engelmann, Péter; Lubics, Andrea; Reglodi, Dóra; Pollák, Edit; Molnár, László

2010-03-01

Pituitary adenylate cyclase activating polypeptide (PACAP)-like molecules have been shown to be present in cocoon albumin and in Eisenia fetida embryos at an early developmental stage (E1) by immunocytochemistry and radioimmunoassay. Here, we focus on detecting the stage at which PAC1 receptor (PAC1R)-like immunoreactivity first appears in germinal layers and structures, e.g., various parts of the central nervous system (CNS), in developing earthworm embryos. PAC1R-like immunoreactivity was revealed by Western blot and Far Western blot as early as the E2 developmental stage, occurring in the ectoderm and later in specific neurons of the developing CNS. Labeled CNS neurons were first seen in the supraesophageal ganglion (brain) and subsequently in the subesophageal and ventral nerve cord ganglia. Ultrastructurally, PAC1Rs were located mainly on plasma membranes and intracellular membranes, especially on cisternae of the endoplasmic reticulum. Therefore, PACAP-like compounds probably influence the differentiation of germinal layers (at least the ectoderm) and of some neurons and might act as signaling molecules during earthworm embryonic development.

Partitioning studies of coal-tar constituents in a two-phase contaminated ground-water system

USGS Publications Warehouse

Rostad, C.E.; Pereira, W.E.; Hult, M.F.

1985-01-01

Organic compounds derived from coal-tar wastes in a contaminated aquifer in St. Louis Park, Minnesota, were identified, and their partition coefficients between the tar phase and aqueous phase were determined and compared with the corresponding n-octanol/water partition coefficients. Coal tar contains numerous polycyclic aromatic compounds, many of which are suspected carcinogens or mutagens. Groundwater contamination by these toxic compounds may pose an environmental health hazard in nearby public water-supply wells. Fluid samples from this aquifer developed two phases upon settling: an upper aqueous phase, and a lower oily-tar phase. After separating the phases, polycyclic aromatic compounds in each phase were isolated using complexation with N-methyl-2-pyrrolidone and identified by fused-silica capillary gas chromatography/mass spectrometry. Thirty-one of the polycyclic aromatic compounds were chosen for further study from four different classes: 12 polycyclic aromatic hydrocarbons, 10 nitrogen heterocycles, 5 sulfur heterocycles, and 4 oxygen heterocycles. Within each compound class, the tar/water partition coefficients of these compounds were reasonably comparable with the respective n-octanol/water partition coefficient.

Co-operative suppression of inflammatory responses in human dendritic cells by plant proanthocyanidins and products from the parasitic nematode Trichuris suis.

PubMed

Williams, Andrew R; Klaver, Elsenoor J; Laan, Lisa C; Ramsay, Aina; Fryganas, Christos; Difborg, Rolf; Kringel, Helene; Reed, Jess D; Mueller-Harvey, Irene; Skov, Søren; van Die, Irma; Thamsborg, Stig M

2017-03-01

Interactions between dendritic cells (DCs) and environmental, dietary and pathogen antigens play a key role in immune homeostasis and regulation of inflammation. Dietary polyphenols such as proanthocyanidins (PAC) may reduce inflammation, and we therefore hypothesized that PAC may suppress lipopolysaccharide (LPS) -induced responses in human DCs and subsequent T helper type 1 (Th1) -type responses in naive T cells. Moreover, we proposed that, because DCs are likely to be exposed to multiple stimuli, the activity of PAC may synergise with other bioactive molecules that have anti-inflammatory activity, e.g. soluble products from the helminth parasite Trichuris suis (TsSP). We show that PAC are endocytosed by monocyte-derived DCs and selectively induce CD86 expression. Subsequently, PAC suppress the LPS-induced secretion of interleukin-6 (IL-6) and IL-12p70, while enhancing secretion of IL-10. Incubation of DCs with PAC did not affect lymphocyte proliferation; however, subsequent interferon-γ production was markedly suppressed, while IL-4 production was unaffected. The activity of PAC was confined to oligomers (degree of polymerization ≥ 4). Co-pulsing DCs with TsSP and PAC synergistically reduced secretion of tumour necrosis factor-α, IL-6 and IL-12p70 while increasing IL-10 secretion. Moreover, both TsSP and PAC alone induced Th2-associated OX40L expression in DCs, and together synergized to up-regulate OX40L. These data suggest that PAC induce an anti-inflammatory phenotype in human DCs that selectively down-regulates Th1 response in naive T cells, and that they also act cooperatively with TsSP. Our results indicate a novel interaction between dietary compounds and parasite products to influence immune function, and may suggest that combinations of PAC and TsSP can have therapeutic potential for inflammatory disorders. © 2016 John Wiley & Sons Ltd.

Aromatic ring generation as a dust precursor in acetylene discharges

NASA Astrophysics Data System (ADS)

De Bleecker, Kathleen; Bogaerts, Annemie; Goedheer, Wim

2006-04-01

Production of aromatic hydrocarbon compounds as an intermediate step for particle formation in low-pressure acetylene discharges is investigated via a kinetic approach. The detailed chemical reaction mechanism contains 140 reactions among 55 species. The cyclic hydrocarbon chemistry is mainly based on studies of polycyclic aromatic hydrocarbon formation in cosmic environments. The model explicitly includes organic chain, cyclic molecules, radicals, and ions up to a size of 12 carbon atoms. The calculated density profiles show that the aromatic formation yields are quite significant, suggesting that aromatic compounds play a role in the underlying mechanisms of particle formation in hydrocarbon plasmas.

Low severity coal conversion by ionic hydrogenation: Quarterly report, October--December 1988

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maioriello, J.; Larsen, J.W.

1988-12-31

A newly developed reaction system consisting of H/sub 2/O:BF/sub 3//H/sub 2//(CH/sub 3/CN)/sub 2/PtCl/sub 2/ was applied to the ionic hydrogenation of aromatic and functionalized aromatic compounds. Hydrogenations were carried out in this aqueous system at 50/degree/C and 500 psi H/sub 2/. Aryl ethers were hydrogenated and cleaved, yielding deoxygenated, fully saturated compounds as the major products. Reactions of nitrogen-containing aromatic compounds resulted in partial saturation of aromatic rings without cleavage of the C-N bonds. Aromatic and PNA compounds can be fully or partially hydrogenated depending on their structures. Aromatic thiols, sulfides and thiophenes poison the catalyst; the oxidized sulfur formsmore » (sulfonic acids, sulfones) were not reduced and did not poison the catalyst. It was found that certain aromatic compounds were easier to hydrogenate than others. Ionic hydrogenation of Wyodak cola using a H/sub 2/O:BF/sub 3//H/sub 2//(MeCN)/sub 2/PtCl/sub 2/ resulted in no significant increase in THF extractability (5.8--9.6% THF-extractables, wt) over that of the parent coal (4.6--6.7% THF-extractables, wt). Ionic hydrogenation of a demineralized Wyodak coal (1 M aq. citric acid, reflux 1 day) resulted in a slight increase in THF extractability (10.4%) over the untreated parent coal (5.6--5.8%). 4 refs., 1 fig., 1 tab.« less

Toxicity of N-substituted aromatics to acetoclastic methanogenic activity in granular sludge

DOE Office of Scientific and Technical Information (OSTI.GOV)

Donlon, B.A.; Razo-Flores, E.; Field, J.A.

1995-11-01

N-substituted aromatics are important priority pollutants entering the environment primarily through anthropogenic activities associated associated with the industrial production of dyes, explosives, pestides, and pharmaceuticals. Anaerobic treatment of wastewaters discharged by these industries could potentially be problematical as a result of the high toxicity of N-substituted aromatics. The objective of this study was to examine the structure-toxicity relationship of N-substituted aromatic compounds to acetoclastic methanogenic bacteria. The toxicity was assayed to serum flasks by measuring methane production in granular sludge. Unacclimated cultures were used to minimize the biotransformation of the toxic organic chemicals during the test. The nature and themore » degree of the aromatic substitution were observed to have a profound effect on the toxicity of the test compound. Nitroaromatic compounds were, on the average, over 500-fold more toxic than their corresponding aromatic amines. Considering the facile reduction of nitro groups by anerobic microorganisms, a dramatic detoxification of nitroaromatics towards methanogens can be expected to occur during anaerobic wastewater treatment. While the toxicity exerted by the N-substituted aromatic compounds was closely correlated with compound apolarity (log P), it was observed that at any given log P, N-substituted phenols had a toxicity that was 2 orders of magnitude higher than that of chlorophenols and alkylphenols. This indicates that toxicity due to the chemical reactivity of nitroaromatics is much more important than partitioning effects in bacterial membranes. 41 refs., 3 figs., 1 tab.« less

Structural and functional characterization of solute binding proteins for aromatic compounds derived from lignin: p-coumaric acid and related aromatic acids.

PubMed

Tan, Kemin; Chang, Changsoo; Cuff, Marianne; Osipiuk, Jerzy; Landorf, Elizabeth; Mack, Jamey C; Zerbs, Sarah; Joachimiak, Andrzej; Collart, Frank R

2013-10-01

Lignin comprises 15-25% of plant biomass and represents a major environmental carbon source for utilization by soil microorganisms. Access to this energy resource requires the action of fungal and bacterial enzymes to break down the lignin polymer into a complex assortment of aromatic compounds that can be transported into the cells. To improve our understanding of the utilization of lignin by microorganisms, we characterized the molecular properties of solute binding proteins of ATP-binding cassette transporter proteins that interact with these compounds. A combination of functional screens and structural studies characterized the binding specificity of the solute binding proteins for aromatic compounds derived from lignin such as p-coumarate, 3-phenylpropionic acid and compounds with more complex ring substitutions. A ligand screen based on thermal stabilization identified several binding protein clusters that exhibit preferences based on the size or number of aromatic ring substituents. Multiple X-ray crystal structures of protein-ligand complexes for these clusters identified the molecular basis of the binding specificity for the lignin-derived aromatic compounds. The screens and structural data provide new functional assignments for these solute-binding proteins which can be used to infer their transport specificity. This knowledge of the functional roles and molecular binding specificity of these proteins will support the identification of the specific enzymes and regulatory proteins of peripheral pathways that funnel these compounds to central metabolic pathways and will improve the predictive power of sequence-based functional annotation methods for this family of proteins. Copyright © 2013 Wiley Periodicals, Inc.

Structural and functional characterization of solute binding proteins for aromatic compounds derived from lignin: p-coumaric acid and related aromatic acids

PubMed Central

Tan, Kemin; Chang, Changsoo; Cuff, Marianne; Osipiuk, Jerzy; Landorf, Elizabeth; Mack, Jamey C.; Zerbs, Sarah; Joachimiak, Andrzej; Collart, Frank R.

2013-01-01

Lignin comprises 15.25% of plant biomass and represents a major environmental carbon source for utilization by soil microorganisms. Access to this energy resource requires the action of fungal and bacterial enzymes to break down the lignin polymer into a complex assortment of aromatic compounds that can be transported into the cells. To improve our understanding of the utilization of lignin by microorganisms, we characterized the molecular properties of solute binding proteins of ATP.binding cassette transporter proteins that interact with these compounds. A combination of functional screens and structural studies characterized the binding specificity of the solute binding proteins for aromatic compounds derived from lignin such as p-coumarate, 3-phenylpropionic acid and compounds with more complex ring substitutions. A ligand screen based on thermal stabilization identified several binding protein clusters that exhibit preferences based on the size or number of aromatic ring substituents. Multiple X-ray crystal structures of protein-ligand complexes for these clusters identified the molecular basis of the binding specificity for the lignin-derived aromatic compounds. The screens and structural data provide new functional assignments for these solute.binding proteins which can be used to infer their transport specificity. This knowledge of the functional roles and molecular binding specificity of these proteins will support the identification of the specific enzymes and regulatory proteins of peripheral pathways that funnel these compounds to central metabolic pathways and will improve the predictive power of sequence-based functional annotation methods for this family of proteins. PMID:23606130

SOLVENT-FREE REDUCTION OF AROMATIC NITRO COMPOUNDS WITH ALUMINA-SUPPORTED HYDRAZINE UNDER MICROWAVE IRRADIATION

EPA Science Inventory

In a solvent-free microwave-expedited process, aromatic nitro compounds are readily reduced to the corresponding amino compounds in good yield with hydrazine hydrate supported on alumina in presence of FeCl3, 6H2), Fe(III) oxide hydroxide or Fe(III) oxides.

POWDERED ACTIVATED CARBON FROM NORTH DAKOTA LIGNITE: AN OPTION FOR DISINFECTION BY-PRODUCT CONTROL IN WATER TREATMENT PLANTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Daniel J. Stepan; Thomas A. Moe; Melanie D. Hetland

New federal drinking water regulations have been promulgated to restrict the levels of disinfection by-products (DBPs) in finished public water supplies. DBPs are suspected carcinogens and are formed when organic material is partially oxidized by disinfectants commonly used in the water treatment industry. Additional federal mandates are expected in the near future that will further affect public water suppliers with respect to DBPs. Powdered activated carbon (PAC) has traditionally been used by the water treatment industry for the removal of compounds contributing to taste and odor problems. PAC also has the potential to remove naturally occurring organic matter (NOM) frommore » raw waters prior to disinfection, thus controlling the formation of regulated DBPs. Many small water systems are currently using PAC for taste and odor control and have the potential to use PAC for controlling DBPs. This project, a cooperative effort between the Energy & Environmental Research Center (EERC), the Grand Forks Water Treatment Plant, and the University of North Dakota Department of Civil Engineering, consists of several interrelated tasks. The objective of the research was to evaluate a cost-effective PAC produced from North Dakota lignite for removing NOM from water and reducing trihalomethane formation potential. The research approach was to develop a statistically valid testing protocol that can be used to compare dose-response relationships between North Dakota lignite-derived PAC and commercially available PAC products. A statistical analysis was performed to determine whether significant correlations exist between operating conditions, water properties, PAC properties, and dose-response behavior. Pertinent physical and chemical properties were also measured for each of the waters and each of the PACs.« less

Biodegradation of aromatic compounds by white rot and ectomycorrhizal fungal species and the accumulation of chlorinated benzoic acid in ectomycorrhizal pine seedlings.

PubMed

Dittmann, Jens; Heyser, Wolfgang; Bücking, Heike

2002-10-01

The capability of different white rot (WR, Heterobasidion annosum, Phanerochaete chrysosporium, Trametes versicolor) and ectomycorrhizal (ECM, Paxillus involutus, Suillus bovinus) fungal species to degrade different aromatic compounds and the absorption of 3-chlorobenzoic acid (3-CBA) by ECM pine seedlings was examined. The effect of aromatic compounds on the fungal biomass development varied considerably and depended on (a) the compound, (b) the external concentration, and (c) the fungal species. The highest effect on the fungal biomass development was observed for 3-CBA. Generally the tolerance of WR fungi against aromatic compounds was higher than that of the biotrophic fungal species. The capability of different fungi to degrade aromatic substances varied between the species but not generally between biotrophic and saprotrophic fungi. The highest degradation capability for aromatic compounds was detected for T. versicolor and H. annosum, whereas for Phanerochaete chrysosporium and the ECM fungi lower degradation rates were found. However, Paxillus involutus and S. bovinus showed comparable degradation rates at low concentrations of benzoic acid and 4-hydroxybenzoic acid. In contrast to liquid cultures, where no biodegradation of 3-CBA by S. bovinus was observed, mycorrhizal pines inoculated with S. bovinus showed a low capability to remove 3-CBA from soil substrates. Additional X-ray microanalytical investigations showed, that 3-CBA supplied to mycorrhizal plants was accumulated in the root cell cytoplasm and is translocated across the endodermis to the shoot of mycorrhizal pine seedlings.

[Recent advances in Sphingobium sp. SYK-6 for lignin aromatic compounds degradation--a review].

PubMed

Zhang, Xiaoyan; Peng, Xue; Masai, Eiji

2014-08-04

Lignin is complex heteropolymer produced from hydroxycinnamyl alcohols through radical coupling. In nature, white-rot fungi are assumed initially to attack native lignin and release lignin-derived-low-molecular-weight compounds, and soil bacteria play an importent role for completely degradation of these compounds. Study on the soil bacteria degrading lignin-derived-low-molecular-weight compounds will give way to understand how aromatic compounds recycle in nature, and to utilize lignin compounds as the renewable materials for valuable materials production. Sphingobium sp. SYK-6 that grows on lignin biphenyl (5,5'-dehydrodivanillate) had been isolated from pulp effluent in 1987. We have researched this bacterium more than 25 years, a serious aromatic metabolic pathway has been determined, and related genes have been isolated. As the complete genome sequence of SYK-6 has been opened to the public in 2012, the entire aromatic compounds degradation mechanisms become more clear. Main contents in our review cover: (1) genome information; (2) aryl metabolism; (3) biphenyl metabolism; (4) ferulate metabolism; (5) tetrahydrofolate-dependent O-demethylation system for lignin compound degrdation; (6) protocatechuate 4,5-cleavage pathway; (7) multiple pathways for 3-O-methylgallate metabolism.

Effect of interlayer cations of montmorillonite on the biodegradation and adsorption of crude oil polycyclic aromatic compounds.

PubMed

Ugochukwu, Uzochukwu C; Manning, David A C; Fialips, Claire I

2014-09-01

Cation exchange capacity, surface acidity and specific surface area are surface properties of clay minerals that make them act as catalysts or supports in most biogeochemical processes hence making them play important roles in environmental control. However, the role of homoionic clay minerals during the biodegradation of polycyclic aromatic compounds is not well reported. In this study, the effect of interlayer cations of montmorillonites in the removal of some crude oil polycyclic aromatic compounds during biodegradation was investigated in aqueous clay/oil microcosm experiments with a hydrocarbon degrading microorganism community. The homoionic montmorillonites were prepared via cation exchange reactions by treating the unmodified montmorillonite with the relevant metallic chloride. The study indicated that potassium-montmorillonite and zinc-montmorillonite did not enhance the biodegradation of the polycyclic aromatic hydrocarbons whereas calcium-montmorillonite, and ferric-montmorillonite enhanced their biodegradation significantly. Adsorption of polycyclic aromatic hydrocarbons was significant during biodegradation with potassium- and zinc-montmorillonite where there was about 45% removal of the polycyclic aromatic compounds by adsorption in the experimental microcosm containing 5:1 ratio (w/w) of clay to oil. Copyright © 2014 Elsevier Ltd. All rights reserved.

Pt- and Pd-decorated MWCNTs for vapour and gas detection at room temperature

PubMed Central

Baccar, Hamdi; Clément, Pierrick; Abdelghani, Adnane

2015-01-01

Summary Here we report on the gas sensing properties of multiwalled carbon nanotubes decorated with sputtered Pt or Pd nanoparticles. Sputtering allows for an oxygen plasma treatment that removes amorphous carbon from the surface of the carbon nanotubes and creates oxygenated surface defects in which metal nanoparticles nucleate within a few minutes. The decoration with the 2 nm Pt or the 3 nm Pd nanoparticles is very homogeneous. This procedure is performed at the device level (i.e., for carbon nanotubes deposited onto sensor substrates) for many devices in one batch, which illustrates the scalability for the mass production of affordable nanosensors. The response to selected aromatic and non-aromatic volatile organic compounds, as well as pollutant gases has been studied. Pt- and Pd-decorated multiwalled carbon nanotubes show a fully reversible response to the non-aromatic volatile organic compounds tested when operated at room temperature. In contrast, these nanomaterials were not responsive to the aromatic compounds studied (measured at concentrations up to 50 ppm). Therefore, these sensors could be useful in a small, battery-operated alarm detector, for example, which is able to discriminate aromatic from non-aromatic volatile organic compounds in ambient. PMID:25977863

Prevention of urinary tract infections with vaccinium products.

PubMed

Davidson, Elyad; Zimmermann, Benno F; Jungfer, Elvira; Chrubasik-Hausmann, Sigrun

2014-03-01

Cranberries exert a dose-dependent inhibition of the adherence of E. coli fimbriae to uroepithelial cells. This was demonstrated in vitro but also ex vivo in vitro with urine from cranberry consumers. The active principle has not been identified in detail but type-A proanthocyanidins (PAC) play an important role in the mechanism of action. Since the three species, American cranberry (Vaccinium macrocarpon), European cranberry (Vaccinium oxycoccus) and/or lingonberry (Vaccinium vitis-idaea), have different patterns of type-A PACs, results from one species cannot be transferred to the others. It seems likely that most of the studies with monopreparations from V. macrocarpon were underdosed. Whereas photometric PAC quantification may overestimate the true content on co-active compounds, reversed phase high-performance liquid chromatograpy may underestimate them. Recent studies with PAC doses in the upper range (DMAC method) or declared type-A PAC content in the daily dose reveal a dose-dependent trend of clinical effectiveness, however, with a possible ceiling effect. In order to clarify this, future three-arm studies should investigate Vaccinium preparations with higher type-A PAC doses than previously used. We analysed two popular European vitis-idaea products, a mother juice and a proprietary extract. Both preparations may be appropriate to confirm the Vaccinium urinary tract infection-preventive effect beyond doubt. Copyright © 2013 John Wiley & Sons, Ltd.

The enhanced removal of carbonaceous and nitrogenous disinfection by-product precursors using integrated permanganate oxidation and powdered activated carbon adsorption pretreatment.

PubMed

Chu, Wenhai; Yao, Dechang; Gao, Naiyun; Bond, Tom; Templeton, Michael R

2015-12-01

Pilot-scale tests were performed to reduce the formation of a range of carbonaceous and nitrogenous disinfection by-products (C-, N-DBPs), by removing or transforming their precursors, with an integrated permanganate oxidation and powdered activated carbon adsorption (PM-PAC) treatment process before conventional water treatment processes (coagulation-sedimentation-filtration, abbreviated as CPs). Compared with the CPs, PM-PAC significantly enhanced the removal of DOC, DON, NH3(+)-N, and algae from 52.9%, 31.6%, 71.3%, and 83.6% to 69.5%, 61.3%, 92.5%, and 97.5%, respectively. PM pre-oxidation alone and PAC pre-adsorption alone did not substantially reduce the formation of dichloroacetonitrile, trichloroacetonitrile, N-nitrosodimethylamine and dichloroacetamide. However, the PM-PAC integrated process significantly reduced the formation of both C-DBPs and N-DBPs by 60-90% for six C-DBPs and 64-93% for six N-DBPs, because PM oxidation chemically altered the molecular structures of nitrogenous organic compounds and increased the adsorption capacity of the DBP precursors, thus highlighting a synergistic effect of PM and PAC. PM-PAC integrated process is a promising drinking water technology for the reduction of a broad spectrum of C-DBPs and N-DBPs. Copyright © 2015 Elsevier Ltd. All rights reserved.

Novel combination of photoactive species: photoresists formed from selectively esterified novolacs and polyfunctional photoactive compounds

NASA Astrophysics Data System (ADS)

Jeffries, Alfred T., III; Brzozowy, David J.; Naiini, Ahmad A.; Gallagher-Wetmore, Paula M.

1997-07-01

The addition of selected PACs to resists comprised of selectively esterified DNQ novolacs improves their performance in terms of side wall angle and resolution compared to resists whose photoactive component is composed of entirely selectively esterified DNQ novolacs. The performance gain is particularly evident for the resists with two selectively esterified fractions. A conventional 60/40 m-cresol/p-cresol novolac was synthesized and fractionated into five nearly equal weight fractions using supercritical fluids (SCF) fractionation technique. Resists were made from either a single esterified fraction [fraction Two, esterification level (EL), 42%] or dual esterified fractions (fractions Two and Four, EL 21% each), a selection of PACs and the remaining unesterified fractions. They were compared to a control containing only the corresponding esterified fraction(s). The PACs A and B were effective at increasing the resist profile angle for 0.50 (mu) features in the singly esterified novalacs in comparison to the control material and exhibited flat tops. The resolution and profiles of dual esterified fraction resists improved significantly when low levels of PACs were added to dual esterified fraction control resist. The comparison was made from 0.40 (mu) features. The resist made using PAC C is the best candidate for photospeed although its profile angle is less in comparison to PACs A and B.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ijam, M.J.; Al-Qatami, S.Y.; Arif, S.F.

For several decades removal of aromatics from crude oil fractions has been practiced in oil refining to produce fuels and lubricants of lower aromatic content and hence of improved quality. These aromatics are suitable raw materials for the manufacture of aromatic solvents, aromatic process oils, high octane gasoline, and as basic materials for making detergents, perfumes and dyes. A study for the UV and IR spectra of the aromatic hydrocarbons showed them to consist mainly of bi-, tri-, tetra-, and penta-substituted benzene, bicyclic and tricyclic compounds. Detailed studies have been reported of molecular structure and substituent effects have been reportedmore » on the retention characteristics of aromatic hydrocarbons on alumina, silica and various chemically bonded silicas containing {minus}C{sub 18}, {minus}NH{sub 2}, {minus}R(NH){sub 2}, {minus}CN, RCN, and phenyl-mercuric acetate for compound class (ring-numbered) high performance liquid chromatography separation. With the aid of a Finnegan type 9612-4000 GC/MS apparatus, the mixture of neutral + basic aromatic hydrocarbons was qualitatively identified and revealed the presence of more than 112 peaks. The neutral + basic aromatic hydrocarbons consist mainly of: 3.68% monoaromatics (C{sub 3} - C{sub 6} alkyl benzenes), 52.81% bicycloaromatics (C{sub 0} - C{sub 4} alkylnaphthalenes), 6.20% tricycloaromatics (C{sub 0} - C{sub 4} alkyl phenanthrenes), and 37.32% nonhydrocarbons aromatic compounds. The components in major HPLC peaks corresponding to bicycloaromatics were further separated into small groups (3-4 components in each) by HPLC using an ODS-reverse phase-C{sub 18} column. To separate a single component from the mixture is a difficult problem. The individual compounds in the separated fractions were identified by GC/MS (Hewlett Packard 5993 system).« less

Effectiveness of Liquid-Liquid Extraction, Solid Phase Extraction, and Headspace Technique for Determination of Some Volatile Water-Soluble Compounds of Rose Aromatic Water

PubMed Central

2017-01-01

Steam distillation is used to isolate scent of rose flowers. Rose aromatic water is commonly used in European cuisine and aromatherapy besides its use in cosmetic industry for its lovely scent. In this study, three different sampling techniques, liquid-liquid extraction (LLE), headspace technique (HS), and solid phase extraction (SPE), were compared for the analysis of volatile water-soluble compounds in commercial rose aromatic water. Some volatile water-soluble compounds of rose aromatic water were also analyzed by gas chromatography mass spectrometry (GCMS). In any case, it was concluded that one of the solid phase extraction methods led to higher recoveries for 2-phenylethyl alcohol (PEA) in the rose aromatic water than the liquid-liquid extraction and headspace technique. Liquid-liquid extraction method provided higher recovery ratios for citronellol, nerol, and geraniol than others. Ideal linear correlation coefficient values were observed by GCMS for quantitative analysis of volatile compounds (r2 ≥ 0.999). Optimized methods showed acceptable repeatability (RSDs < 5%) and excellent recovery (>95%). For compounds such as α-pinene, linalool, β-caryophyllene, α-humulene, methyl eugenol, and eugenol, the best recovery values were obtained with LLE and SPE. PMID:28791049

Effect of Activated Carbon Amendment on Bacterial Community Structure and Functions in a PAH Impacted Urban Soil

PubMed Central

2012-01-01

We collected urban soil samples impacted by polycyclic aromatic hydrocarbons (PAHs) from a sorbent-based remediation field trial to address concerns about unwanted side-effects of 2% powdered (PAC) or granular (GAC) activated carbon amendment on soil microbiology and pollutant biodegradation. After three years, total microbial cell counts and respiration rates were highest in the GAC amended soil. The predominant bacterial community structure derived from denaturing gradient gel electrophoresis (DGGE) shifted more strongly with time than in response to AC amendment. DGGE band sequencing revealed the presence of taxa with closest affiliations either to known PAH degraders, e.g. Rhodococcus jostii RHA-1, or taxa known to harbor PAH degraders, e.g. Rhodococcus erythropolis, in all soils. Quantification by real-time polymerase chain reaction yielded similar dioxygenases gene copy numbers in unamended, PAC-, or GAC-amended soil. PAH availability assessments in batch tests showed the greatest difference of 75% with and without biocide addition for unamended soil, while the lowest PAH availability overall was measured in PAC-amended, live soil. We conclude that AC had no detrimental effects on soil microbiology, AC-amended soils retained the potential to biodegrade PAHs, but the removal of available pollutants by biodegradation was most notable in unamended soil. PMID:22455603

Effect of activated carbon amendment on bacterial community structure and functions in a PAH impacted urban soil.

PubMed

Meynet, Paola; Hale, Sarah E; Davenport, Russell J; Cornelissen, Gerard; Breedveld, Gijs D; Werner, David

2012-05-01

We collected urban soil samples impacted by polycyclic aromatic hydrocarbons (PAHs) from a sorbent-based remediation field trial to address concerns about unwanted side-effects of 2% powdered (PAC) or granular (GAC) activated carbon amendment on soil microbiology and pollutant biodegradation. After three years, total microbial cell counts and respiration rates were highest in the GAC amended soil. The predominant bacterial community structure derived from denaturing gradient gel electrophoresis (DGGE) shifted more strongly with time than in response to AC amendment. DGGE band sequencing revealed the presence of taxa with closest affiliations either to known PAH degraders, e.g. Rhodococcus jostii RHA-1, or taxa known to harbor PAH degraders, e.g. Rhodococcus erythropolis, in all soils. Quantification by real-time polymerase chain reaction yielded similar dioxygenases gene copy numbers in unamended, PAC-, or GAC-amended soil. PAH availability assessments in batch tests showed the greatest difference of 75% with and without biocide addition for unamended soil, while the lowest PAH availability overall was measured in PAC-amended, live soil. We conclude that AC had no detrimental effects on soil microbiology, AC-amended soils retained the potential to biodegrade PAHs, but the removal of available pollutants by biodegradation was most notable in unamended soil. © 2012 American Chemical Society

[Cranberry (Vaccinium macrocarpon) and urinary tract infections: study model and review of literature].

PubMed

Lavigne, J-P; Bourg, G; Botto, H; Sotto, A

2007-11-01

Cranberries (Vaccinium macrocarpon) have long been the focus of interest for their beneficial effects in preventing urinary tract infections. Among cranberry compounds, a group of proanthocyanidins (PACs) with A-type linkages were isolated which exhibit bacterial anti-adhesion activity against uropathogenic Escherichia coli strains. These PAC inhibit P-fimbriae synthesis and induce a bacterial deformation. This activity was demonstrated on both antibiotic susceptible and resistant bacteria. This review focused on the last discoveries in the knowledge of cranberry effects.

Can Baird's and Clar's Rules Combined Explain Triplet State Energies of Polycyclic Conjugated Hydrocarbons with Fused 4nπ- and (4n + 2)π-Rings?

PubMed

Ayub, Rabia; Bakouri, Ouissam El; Jorner, Kjell; Solà, Miquel; Ottosson, Henrik

2017-06-16

Compounds that can be labeled as "aromatic chameleons" are π-conjugated compounds that are able to adjust their π-electron distributions so as to comply with the different rules of aromaticity in different electronic states. We used quantum chemical calculations to explore how the fusion of benzene rings onto aromatic chameleonic units represented by biphenylene, dibenzocyclooctatetraene, and dibenzo[a,e]pentalene modifies the first triplet excited states (T 1 ) of the compounds. Decreases in T 1 energies are observed when going from isomers with linear connectivity of the fused benzene rings to those with cis- or trans-bent connectivities. The T 1 energies decreased down to those of the parent (isolated) 4nπ-electron units. Simultaneously, we observe an increased influence of triplet state aromaticity of the central 4n ring as given by Baird's rule and evidenced by geometric, magnetic, and electron density based aromaticity indices (HOMA, NICS-XY, ACID, and FLU). Because of an influence of triplet state aromaticity in the central 4nπ-electron units, the most stabilized compounds retain the triplet excitation in Baird π-quartets or octets, enabling the outer benzene rings to adapt closed-shell singlet Clar π-sextet character. Interestingly, the T 1 energies go down as the total number of aromatic cycles within a molecule in the T 1 state increases.

MOLECULAR BASIS OF BIODEGRADATION OF CHLOROAROMATIC COMPOUNDS

EPA Science Inventory

Chlorinated aromatic hydrocarbons are widely used in industry and agriculture, and comprise the bulk of environmental pollutants. Although simple aromatic compounds are biodegradable by a variety of degradative pathways, their halogenated counterparts are more resistant to bacter...

Saccharomyces cerevisiae Mixed Culture of Blackberry (Rubus ulmifolius L.) Juice: Synergism in the Aroma Compounds Production

PubMed Central

Ragazzo-Sánchez, Juan Arturo; Ortiz-Basurto, Rosa Isela; Luna-Solano, Guadalupe; Calderón-Santoyo, Montserrat

2014-01-01

Blackberry (Rubus sp.) juice was fermented using four different strains of Saccharomyces cerevisiae (Vitilevure-CM4457, Enoferm-T306, ICV-K1, and Greroche Rhona-L3574) recognized because of their use in the wine industry. A medium alcoholic graduation spirit (<6°GL) with potential to be produced at an industrial scale was obtained. Alcoholic fermentations were performed at 28°C, 200 rpm, and noncontrolled pH. The synergistic effect on the aromatic compounds production during fermentation in mixed culture was compared with those obtained by monoculture and physic mixture of spirits produced in monoculture. The aromatic composition was determined by HS-SPME-GC. The differences in aromatic profile principally rely on the proportions in aromatic compounds and not on the number of those compounds. The multivariance analysis, principal component analysis (PCA), and factorial discriminant analysis (DFA) permit to demonstrate the synergism between the strains. PMID:25506606

The aromatic amino acids biosynthetic pathway: A core platform for products

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lievense, J.C.; Frost, J.W.

The aromatic amino acids biosynthetic pathway is viewed conventionally and primarily as the source of the amino acids L-tyrosine, L-phenylalanine. The authors have recognized the expanded role of the pathway as the major source of aromatic raw materials on earth. With the development of metabolic engineering approaches, it is now possible to biosynthesize a wide variety of aromatic compounds from inexpensive, clean, abundant, renewable sugars using fermentation methods. Examples of already and soon-to-be commercialized biosynthesis of such compounds are described. The long-term prospects are also assessed.

Biodegradation of organic pollutants in saline wastewater by halophilic microorganisms: a review.

PubMed

Castillo-Carvajal, Laura C; Sanz-Martín, José Luis; Barragán-Huerta, Blanca E

2014-01-01

Agro-food, petroleum, textile, and leather industries generate saline wastewater with a high content of organic pollutants such as aromatic hydrocarbons, phenols, nitroaromatics, and azo dyes. Halophilic microorganisms are of increasing interest in industrial waste treatment, due to their ability to degrade hazardous substances efficiently under high salt conditions. However, their full potential remains unexplored. The isolation and identification of halophilic and halotolerant microorganisms from geographically unrelated and geologically diverse hypersaline sites supports their application in bioremediation processes. Past investigations in this field have mainly focused on the elimination of polycyclic aromatic hydrocarbons and phenols, whereas few studies have investigated N-aromatic compounds, such as nitro-substituted compounds, amines, and azo dyes, in saline wastewater. Information regarding the growth conditions and degradation mechanisms of halophilic microorganisms is also limited. In this review, we discuss recent research on the removal of organic pollutants such as organic matter, in terms of chemical oxygen demand (COD), dyes, hydrocarbons, N-aliphatic and N-aromatic compounds, and phenols, in conditions of high salinity. In addition, some proposal pathways for the degradation of aromatic compounds are presented.

Natural Mediators in the Oxidation of Polycyclic Aromatic Hydrocarbons by Laccase Mediator Systems

PubMed Central

Johannes, Christian; Majcherczyk, Andrzej

2000-01-01

The oxidation of polycyclic aromatic compounds was studied in systems consisting of laccase from Trametes versicolor and so-called mediator compounds. The enzymatic oxidation of acenaphthene, acenaphthylene, anthracene, and fluorene was mediated by various laccase substrates (phenols and aromatic amines) or compounds produced and secreted by white rot fungi. The best natural mediators, such as phenol, aniline, 4-hydroxybenzoic acid, and 4-hydroxybenzyl alcohol were as efficient as the previously described synthetic compounds ABTS [2,2′-azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid)] and 1-hydroxybenzotriazole. The oxidation efficiency increased proportionally with the redox potentials of the phenolic mediators up to a maximum value of 0.9 V and decreased thereafter with redox potentials exceeding this value. Natural compounds such as methionine, cysteine, and reduced glutathione, containing sulfhydryl groups, were also active as mediator compounds. PMID:10653713

Bromination of aromatic compounds by residual bromide in sodium chloride matrix modifier salt during heated headspace GC/MS analysis.

PubMed

Fine, Dennis D; Ko, Saebom; Huling, Scott

2013-12-15

Analytical artifacts attributed to the bromination of toluene, xylenes, and trimethylbenzenes were found during the heated headspace gas chromatography/mass spectrometry (GC/MS) analysis of aqueous samples. The aqueous samples were produced from Fenton-like chemical oxidation reactions and contained aromatic compounds, hydrogen peroxide (H2O2), and ferric sulfate. Prior to GC/MS headspace analysis, the samples were acidified (pH<2), and sodium chloride was amended to the headspace vial as a matrix modifier. The brominated artifacts were generated during heated headspace analysis. Further, when samples were spiked with a mixture of volatile chlorinated and aromatic compounds (50 µg/L), poor spike recoveries of toluene and xylenes occurred, and in some cases complete loss of trimethylbenzenes and naphthalene resulted. Where poor recovery of aromatic spike compounds occurred, brominated aromatic compounds were found. The only significant source of bromine in the reaction scheme is the bromide typically present (<0.01% w/w) in the sodium chloride amended to the samples. Conversely, brominated artifacts were absent when a buffered salt mixture composed of sodium chloride and potassium phosphate dibasic/monobasic was used as a matrix modifier and raised the sample pH (pH~6). This indicated that the brominated artifacts resulted from the reaction of the aromatic compounds with BrCl, which was formed by the reaction of H2O2, chloride, and bromide under acidic conditions. An alternative matrix modifier salt is recommended that prevents the bromination reaction and avoids these deleterious effects on sample integrity during headspace analysis. Published by Elsevier B.V.

Comparison of the effectiveness of soil heating prior or during in situ chemical oxidation (ISCO) of aged PAH-contaminated soils.

PubMed

Ranc, Bérénice; Faure, Pierre; Croze, Véronique; Lorgeoux, Catherine; Simonnot, Marie-Odile

2017-04-01

Thermal treatments prior or during chemical oxidation of aged polycyclic aromatic hydrocarbon (PAH)-contaminated soils have already shown their ability to increase oxidation effectiveness. However, they were never compared on the same soil. Furthermore, oxygenated polycyclic aromatic hydrocarbons (O-PACs), by-products of PAH oxidation which may be more toxic and mobile than the parent PAHs, were very little monitored. In this study, two aged PAH-contaminated soils were heated prior (60 or 90 °C under Ar for 1 week) or during oxidation (60 °C for 1 week) with permanganate and persulfate, and 11 O-PACs were monitored in addition to the 16 US Environmental Protection Agency (US EPA) PAHs. Oxidant doses were based on the stoichiometric oxidant demand of the extractable organic fraction of soils by using organic solvents, which is more representative of the actual contamination than only the 16 US EPA PAHs. Higher temperatures actually resulted in more pollutant degradation. Two treatments were about three times more effective than the others: soil heating to 60 °C during persulfate oxidation and soil preheating to 90 °C followed by permanganate oxidation. The results of this study showed that persulfate effectiveness was largely due to its thermal activation, whereas permanganate was more sensitive to PAH availability than persulfate. The technical feasibility of these two treatments will soon be field-tested in the unsaturated zone of one of the studied aged PAH-contaminated soils.

Assessing Uncertainty of Interspecies Correlation Estimation Models for Aromatic Compounds

EPA Science Inventory

We developed Interspecies Correlation Estimation (ICE) models for aromatic compounds containing 1 to 4 benzene rings to assess uncertainty in toxicity extrapolation in two data compilation approaches. ICE models are mathematical relationships between surrogate and predicted test ...

Anaerobic Microbial Transformation of Aromatic Hydrocarbons and Mixtures of Aromatic Hydrocarbons and Halogenated Solvents

DTIC Science & Technology

1992-08-25

concentrations of these compounds may be toxic or Inhibitory to the microflora, especially if the microorganisms have not been exposed to these compounds before...Slow acclimation of the microflora to lower concentrations of these compounds , that occur at the outskirts of contamination plumes, gradually...sulfate may impair the capability of the microorganisms to degrade these compounds , although anaerobic respiration -- in theory -- is more favorable

The Effects of Molecular Properties on Ready Biodegradation of Aromatic Compounds in the OECD 301B CO2 Evolution Test.

PubMed

He, Mei; Mei, Cheng-Fang; Sun, Guo-Ping; Li, Hai-Bei; Liu, Lei; Xu, Mei-Ying

2016-07-01

Ready biodegradation is the primary biodegradability of a compound, which is used for discriminating whether a compound could be rapidly and readily biodegraded in the natural ecosystems in a short period and has been applied extensively in the environmental risk assessment of many chemicals. In this study, the effects of 24 molecular properties (including 2 physicochemical parameters, 10 geometrical parameters, 6 topological parameters, and 6 electronic parameters) on the ready biodegradation of 24 kinds of synthetic aromatic compounds were investigated using the OECD 301B CO2 Evolution test. The relationship between molecular properties and ready biodegradation of these aromatic compounds varied with molecular properties. A significant inverse correlation was found for the topological parameter TD, five geometrical parameters (Rad, CAA, CMA, CSEV, and N c), and the physicochemical parameter K ow, and a positive correlation for two topological parameters TC and TVC, whereas no significant correlation was observed for any of the electronic parameters. Based on the correlations between molecular properties and ready biodegradation of these aromatic compounds, the importance of molecular properties was demonstrated as follows: geometrical properties > topological properties > physicochemical properties > electronic properties. Our study first demonstrated the effects of molecular properties on ready biodegradation by a number of experiment data under the same experimental conditions, which should be taken into account to better guide the ready biodegradation tests and understand the mechanisms of the ready biodegradation of aromatic compounds.

Evidence for behavioral attractiveness of methoxylated aromatics in a dynastid scarab beetle-pollinated araceae.

PubMed

Dötterl, Stefan; David, Anja; Boland, Wilhelm; Silberbauer-Gottsberger, Ilse; Gottsberger, Gerhard

2012-12-01

Many plants attract their pollinators with floral scents, and these olfactory signals are especially important at night, when visual signals become inefficient. Dynastid scarab beetles are a speciose group of night-active pollinators, and several plants pollinated by these insects have methoxylated aromatic compounds in their scents. However, there is a large gap in our knowledge regarding the compounds responsible for beetle attraction. We used chemical analytical analyses to determine temporal patterns of scent emission and the composition of scent released from inflorescences of Philodendron selloum. The attractiveness of the main components in the scent to the dynastid scarab beetle Erioscelis emarginata, the exclusive pollinator of this plant, was assessed in field biotests. The amount of scent increased rapidly in the evening, and large amounts of scent were released during the activity time of the beetle pollinators. Inflorescences emitted a high number of compounds of different biosynthetic origin, among them both uncommon and also widespread flower scents. Methoxylated aromatic compounds dominated the scent, and 4-methoxystyrene, the most abundant compound, attracted E. emarginata beetles. Other compounds, such as (Z)-jasmone and possibly also the methoxylated aromatic compound 3,4-dimethoxystyrene increased the attractiveness of 4-methoxystyrene. Methoxylated aromatics, which are known from other dynastid pollinated plants as well, are important signals in many scarab beetles in a different context (e.g., pheromones), thus suggesting that these plants exploit pre-existing preferences of the beetles for attracting this group of insects as pollinators.

Performance of biological magnetic powdered activated carbon for drinking water purification.

PubMed

Lompe, Kim Maren; Menard, David; Barbeau, Benoit

2016-06-01

Combining the high adsorption capacity of powdered activated carbon (PAC) with magnetic properties of iron oxide nanoparticles (NPs) leads to a promising composite material, magnetic PAC or MPAC, which can be separated from water using magnetic separators. We propose MPAC as an alternative adsorbent in the biological hybrid membrane process and demonstrate that PAC covered with magnetic NPs is suitable as growth support for heterotrophic and nitrifying bacteria. MPAC with mass fractions of 0; 23; 38 and 54% maghemite was colonized in small bioreactors for over 90 days. Although the bacterial community composition (16s rRNA analysis) was different on MPAC compared to PAC, NPs neither inhibited dissolved organic carbon and ammonia biological removals nor contributed to significant adsorption of these compounds. The same amount of active heterotrophic biomass (48 μg C/cm(3)) developed on MPAC with a mass fraction of 54% NPs as on the non-magnetic PAC control. While X-ray diffraction confirmed that size and type of iron oxides did not change over the study period, a loss in magnetization between 10% and 34% was recorded. Copyright © 2016 Elsevier Ltd. All rights reserved.

Redox shuttles having an aromatic ring fused to a 1,1,4,4-tetrasubstituted cyclohexane ring

DOEpatents

Weng, Wei; Zhang, Zhengcheng; Amine, Khalil

2015-12-01

An electrolyte includes an alkali metal salt; an aprotic solvent; and a redox shuttle additive including an aromatic compound having at least one aromatic ring fused with at least one non-aromatic ring, the aromatic ring having two or more oxygen or phosphorus-containing substituents.

Incombustible resin composition

NASA Technical Reports Server (NTRS)

Akima, T.

1982-01-01

Incombustible resin compositions composed of aromatic compounds were obtained through (1) combustion polymer material and (2) bisphenol A or halogenated bisphenol A and bisphenol A diglycidl ether or halogenated bisphenol A diglycidyl ether. The aromatic compound is an adduct of bifunctional phenols and bifunctional epoxy resins.

Reactions of aromatic diazonium salts with unsaturated compounds in the presence of nucleophiles

NASA Astrophysics Data System (ADS)

Grishchuk, B. D.; Gorbovoi, P. M.; Ganushchak, N. I.; Dombrovskii, A. V.

1994-03-01

The review surveys the reactions of aromatic diazonium salts with diene and monounsaturated compounds in the presence of nucleophiles. Certain further reactions of the reaction products and their application are considered. The bibliography includes 63 references.

Dendrimer encapsulated Silver nanoparticles as novel catalysts for reduction of aromatic nitro compounds

NASA Astrophysics Data System (ADS)

Asharani, I. V.; Thirumalai, D.; Sivakumar, A.

2017-11-01

Polyethylene glycol (PEG) core dendrimer encapsulated silver nanoparticles (AgNPs) were synthesized through normal chemical reduction method, where dendrimer acts as reducing and stabilizing agent. The encapsulated AgNPs were well characterized using TEM, DLS and XPS techniques. The synthesized AgNPs showed excellent catalytic activity towards the reduction of aromatic nitro compounds with sodium borohydride as reducing agent and the results substantiate that dendrimer encapsulated AgNPs can be an effective catalyst for the substituted nitro aromatic reduction reactions. Also the kinetics of different nitro compounds reductions was studied and presented.

Superficial distribution of aromatic compounds and geomicrobiology of sediments from Suruí Mangrove, Guanabara Bay, RJ, Brazil.

PubMed

Fontana, Luiz F; da Silva, Frederico S; de Figueiredo, Natália G; Brum, Daniel M; Netto, Annibal D Pereira; de Gigueiredo Junior, Alberto G; Crapez, Mirian A C

2010-12-01

The distribution of selected aromatic compounds and microbiology were assessed in superficial sediments from Suruí Mangrove, Guanabara Bay. Samples were collected at 23 stations, and particle size, organic matter, aromatic compounds, microbiology activity, biopolymers, and topography were determined. The concentration of aromatic compounds was distributed in patches over the entire mangrove, and their highest total concentration was determinated in the mangrove's central area. Particle size differed from most mangroves in that Suruí Mangrove has chernies on the edges and in front of the mangrove, and sand across the whole surface, which hampers the relationship between particle size and hydrocarbons. An average @ 10% p/p of organic matter was obtained, and biopolymers presented high concentrations, especially in the central and back areas of the mangrove. The biopolymers were distributed in high concentrations. The presence of fine sediments is an important factor in hydrocarbon accumulation. With high concentration of organic matter and biopolymers, and the topography with chernies and roots protecting the mangrove, calmer areas are created with the deposition of material transported by wave action. Compared to global distributions, concentrations of aromatic compounds in Suruí Mangrove may be classified from moderate to high, showing that the studied area is highly impacted.

Small-Molecule Procaspase-3 Activation Sensitizes Cancer to Treatment with Diverse Chemotherapeutics

PubMed Central

2016-01-01

Conventional chemotherapeutics remain essential treatments for most cancers, but their combination with other anticancer drugs (including targeted therapeutics) is often complicated by unpredictable synergies and multiplicative toxicities. As cytotoxic anticancer chemotherapeutics generally function through induction of apoptosis, we hypothesized that a molecularly targeted small molecule capable of facilitating a central and defining step in the apoptotic cascade, the activation of procaspase-3 to caspase-3, would broadly and predictably enhance activity of cytotoxic drugs. Here we show that procaspase-activating compound 1 (PAC-1) enhances cancer cell death induced by 15 different FDA-approved chemotherapeutics, across many cancer types and chemotherapeutic targets. In particular, the promising combination of PAC-1 and doxorubicin induces a synergistic reduction in tumor burden and enhances survival in murine tumor models of osteosarcoma and lymphoma. This PAC-1/doxorubicin combination was evaluated in 10 pet dogs with naturally occurring metastatic osteosarcoma or lymphoma, eliciting a biologic response in 3 of 6 osteosarcoma patients and 4 of 4 lymphoma patients. Importantly, in both mice and dogs, coadministration of PAC-1 with doxorubicin resulted in no additional toxicity. On the basis of the mode of action of PAC-1 and the high expression of procaspase-3 in many cancers, these results suggest the combination of PAC-1 with cytotoxic anticancer drugs as a potent and general strategy to enhance therapeutic response. PMID:27610416

Java-based cryptosystem for PACS and tele-imaging

NASA Astrophysics Data System (ADS)

Tjandra, Donny; Wong, Stephen T. C.; Yu, Yuan-Pin

1998-07-01

Traditional PACS systems are based on two-tier client server architectures, and require the use of costly, high-end client workstations for image viewing. Consequently, PACS systems using the two-tier architecture do not scale well as data increases in size and complexity. Furthermore, use of dedicated viewing workstations incurs costs in deployment and maintenance. To address these issues, the use of digital library technologies, such as the World Wide Web, Java, and CORBA, is being explored to distribute PACS data to serve a broader range of healthcare providers in an economic and efficient manner. Integration of PACS systems with digital library technologies allows access to medical information through open networks such as the Internet. However, use of open networks to transmit medical data introduces problems with maintaining privacy and integrity of patient information. Cryptography and digital timestamping is used to protect sensitive information from unauthorized access or tampering. A major concern when using cryptography and digital timestamping is the performance degradation associated with the mathematical calculations needed to encrypt/decrypt an image dataset, or to calculate the hash value of an image. The performance issue is compounded by the extra layer associated with the CORBA middleware, and the use of programming languages interpreted at the client side, such as Java. This paper study the extent to which Java-based cryptography and digital timestamping affects performance in a PACS system integrated with digital library technologies.

Polyimidazoles via aromatic nucleophilic displacement

NASA Technical Reports Server (NTRS)

Connell, John W. (Inventor); Hergenrother, Paul M. (Inventor)

1992-01-01

Polyimidazoles (PI) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenyl) imidazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The reactions are carried out in polar aprotic solvents such as N,N-dimethyl acetamide, sulfolane, N-methylpyrrolidinone, dimethylsulfoxide, or diphenylsulfone using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. The di(hydroxyphenyl) imidazole monomers are prepared by reacting an aromatic aldehyde with a dimethoxybenzil or by reacting an aromatic dialdehyde with a methoxybenzil in the presence of ammonium acetate. The di(methoxyphenyl) imidazole is subsequently treated with aqueous hydrobromic acid to give the di(hydroxphenyl) imidazole monomer. This synthetic route has provided high molecular weight PI of new chemical structure, is economically and synthetically more favorable than other routes, and allows for facile chemical structure variation due to the availability of a large variety of activated aromatic dihalides and dinitro compounds.

Polyimidazoles via aromatic nucleophilic displacement

NASA Technical Reports Server (NTRS)

Hergenrother, Paul M. (Inventor); Connell, John W. (Inventor)

1991-01-01

Polyimidazoles (Pl) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenyl)imidazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The reactions are carried out in polar aprotic solvents such as N,N-dimethylacetamide, sulfolane, N-methylpyrroldinone, dimethylsulfoxide, or diphenylsulfone using alkali metal bases such as potassium carbonate at elevated temperature under nitrogen. The di(hydroxyphenyl)imidazole monomers are prepared by reacting an aromatic aldehyde with a dimethoxybenzil or by reacting an aromatic dialdehyde with a methoxybenzil in the presence of ammonium acetate. The di(methoxyphenyl)imidazole is subsequently treated with aqueous hydrobromic acid to give the di(hydroxyphenyl)imidazole monomer. This synthetic route has provided high molecular weight Pl of new chemical structure, is economically and synthetically more favorable than other routes, and allows for facile chemical structure variation due to the availability of a large variety of activated aromatic dihalides and dinitro compounds.

Anaerobic Microbial Transformation of Aromatic Hydrocarbons and Mixtures of Aromatic Hydrocarbons and Halogenated Solvents.

DTIC Science & Technology

1992-08-25

High initial concentrations of these compounds may be toxic or inhibitory to the microflora, especially if the microorganisms have not been exposed to...these compounds before. Slow acclimation of the microflora to lower concentrations of these compounds , that occur at the outskirts of contamination...acceptors such as nitrate or sulfate may impair the capability of the microorganisms to degrade these compounds , although anaerobic respiration -- in theory

Natural mediators in the oxidation of polycyclic aromatic hydrocarbons by laccase mediator systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johannes, C.; Majcherczyk, A.

2000-02-01

The oxidation of polycyclic aromatic compounds was studied in systems consisting of laccase from Trametes versicolor and so-called mediator compounds. The enzymatic oxidation of acenaphthene, acenaphthylene, anthracene, and fluorene was mediated by various laccase substrates (phenols and aromatic amines) or compounds produced and secreted by white rot fungi. The best natural mediators, such as phenol, aniline, 4-hydroxybenzoic acid, and 4-hydroxybenzyl alcohol were as efficient as the previously described synthetic compounds ABTS [2,2{prime}-azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid)] and 1-hydroxybenzotriazole. The oxidation efficiency increased proportionally with the redox potentials of the phenolic mediators up to a maximum value of 0.9 V and decreased thereafter withmore » redox potentials exceeding this value. Natural compounds such as methionine, cysteine, and reduced glutathione, containing sulfhydryl groups, were also active as mediator compounds.« less

Vertical Stratification of Peat Pore Water Dissolved Organic Matter Composition in a Peat Bog in Northern Minnesota

NASA Astrophysics Data System (ADS)

Tfaily, Malak M.; Wilson, Rachel M.; Cooper, William T.; Kostka, Joel E.; Hanson, Paul; Chanton, Jeffrey P.

2018-02-01

We characterized dissolved organic matter (DOM) composition throughout the peat column at the Marcell S1 forested bog in northern Minnesota and tested the hypothesis that redox oscillations associated with cycles of wetting and drying at the surface of the fluctuating water table correlate with increased carbon, sulfur, and nitrogen turn over. We found significant vertical stratification of DOM molecular composition and excitation-emission matrix parallel factor analysis components within the peat column. In particular, the intermediate depth zone ( 50 cm) was identified as a zone where maximum decomposition and turnover is taking place. Surface DOM was dominated by inputs from surface vegetation. The intermediate depth zone was an area of high organic matter reactivity and increased microbial activity with diagenetic formation of many unique compounds, among them polycyclic aromatic compounds that contain both nitrogen and sulfur heteroatoms. These compounds have been previously observed in coal-derived compounds and were assumed to be responsible for coal's biological activity. Biological processes triggered by redox oscillations taking place at the intermediate depth zone of the peat profile at the S1 bog are assumed to be responsible for the formation of these heteroatomic PACs in this system. Alternatively, these compounds could stem from black carbon and nitrogen derived from fires that have occurred at the site in the past. Surface and deep DOM exhibited more similar characteristics, compared to the intermediate depth zone, with the deep layer exhibiting greater input of microbially degraded organic matter than the surface suggesting that the entire peat profile consists of similar parent material at different degrees of decomposition and that lateral and vertical advection of pore water from the surface to the deeper horizons is responsible for such similarities. Our findings suggest that molecular composition of DOM in peatland pore water is dynamic and is a function of ecosystem activity, water table, redox oscillation, and pore water advection.

Leaching of styrene and other aromatic compounds in drinking water from PS bottles.

PubMed

Ahmad, Maqbool; Bajahlan, Ahmad S

2007-01-01

Bottled water may not be safer, or healthier, than tap water. The present studies have proved that styrene and some other aromatic compounds leach continuously from polystyrene (PS) bottles used locally for packaging. Water sapmles in contact with PS were extracted by a preconcentration technique called as "purge and trap" and analysed by gas chromatograph-mass spectrometer (GC/MS). Eleven aromatic compounds were identified in these studies. Maximum concentration of styrene in PS bottles was 29.5 microg/L. Apart from styrene, ethyl benzene, toluene and benzene were also quantified but their concentrations were much less than WHO guide line values. All other compounds were in traces. Quality of plastic and storage time were the major factor in leaching of styrene. Concentration of styrene was increased to 69.53 microg/L after one-year storage. In Styrofoam and PS cups studies, hot water was found to be contaminated with styrene and other aromatic compounds. It was observed that temperature played a major role in the leaching of styrene monomer from Styrofoam cups. Paper cups were found to be safe for hot drinks.

Investigation on modes of toxic action to rats based on aliphatic and aromatic compounds and comparison with fish toxicity based on exposure routes.

PubMed

He, Jia; Li, Jin J; Wen, Yang; Tai, Hong W; Yu, Yang; Qin, Wei C; Su, Li M; Zhao, Yuan H

2015-06-01

The modes of toxic action (MOAs) play an important role in the assessment of the ecotoxicity of organic pollutants. However, few studies have been reported on the MOAs in rat toxicity. In this paper, the toxic contributions of functional groups in 1255 aromatic compounds were calculated from regression and were then compared with the toxic contributions in aliphatic compounds. The results show that some functional groups have same toxic contributions both in aromatic and aliphatic compounds, but some have not. To investigate the MOAs in rat toxicity, the distribution of toxic ratio (TR) was examined for well-known baseline and less inert compounds and thresholds of log TR=0.3 and 0.5 were used to classify baseline, less inert and reactive compounds. The results showed that some compounds identified as baseline compounds in fish toxicity were also classified as baseline compounds in rat toxicity. Except for phenols and anilines which were identified as less inert compounds in fish toxicity, aromatic compounds with functional groups such as ether, nitrile, nitrophenol, isocyanatoe and chloro were identified as less inert chemicals in rat toxicity. Reactive compounds identified in fish toxicity exhibit greater toxicity to rats. These compounds can undergo nucleophilic substitution, acylation and Schiff base formation with biological macromolecules. The critical body residues (CBRs) calculated from absorption and bioconcentration show that log 1/CBRs in rat toxicity are not equal to that in fish for some compounds. It suggests that the exposure route can affect the identification of MOAs between these two species for these compounds. Copyright © 2015 Elsevier Ltd. All rights reserved.

Removals of pesticides and pesticide transformation products during drinking water treatment processes and their impact on mutagen formation potential after chlorination.

PubMed

Matsushita, Taku; Morimoto, Ayako; Kuriyama, Taisuke; Matsumoto, Eisuke; Matsui, Yoshihiko; Shirasaki, Nobutaka; Kondo, Takashi; Takanashi, Hirokazu; Kameya, Takashi

2018-07-01

Removal efficiencies of 28 pesticide transformation products (TPs) and 15 parent pesticides during steps in drinking water treatment (coagulation-sedimentation, activated carbon adsorption, and ozonation) were estimated via laboratory-scale batch experiments, and the mechanisms underlying the removal at each step were elucidated via regression analyses. The removal via powdered activated carbon (PAC) treatment was correlated positively with the log K ow at pH 7. The adjusted coefficient of determination (r 2 ) increased when the energy level of the highest occupied molecular orbital (HOMO) was added as an explanatory variable, the suggestion being that adsorption onto PAC particles was largely governed by hydrophobic interactions. The residual error could be partly explained by π-π electron donor-acceptor interactions between the graphene surface of the PAC particles and the adsorbates. The removal via ozonation correlated positively with the energy level of the HOMO, probably because compounds with relatively high energy level HOMOs could more easily transfer an electron to the lowest unoccupied molecular orbital of ozone. Overall, the TPs tended to be more difficult to remove via PAC adsorption and ozonation than their parent pesticides. However, the TPs that were difficult to remove via PAC adsorption did not induce strong mutagenicity after chlorination, and the TPs that were associated with strong mutagenicity after chlorination could be removed via PAC adsorption. Therefore, PAC adsorption is hypothesized to be an effective method of treating drinking water to reduce the possibility of post-chlorination mutagenicity associated with both TPs and their parent pesticides. Copyright © 2018 Elsevier Ltd. All rights reserved.

On the Extraction of Aromatic Compounds from Hydrocarbons by Imidazolium Ionic Liquids

PubMed Central

Cassol, Cláudia C.; Umpierre, Alexandre P.; Ebeling, Günter; Ferrera, Bauer; Chiaro, Sandra S. X.; Dupont, Jairton

2007-01-01

The liquid-liquid equilibrium for the ternary system formed by n-octane and aromatic (alkylbenzenes) and heteroaromatic compounds (nitrogen and sulfur containing heterocyles) and 1-alkyl-3-methylimidazolium ionic liquids (ILs) associated with various anions has been investigated. The selectivity on the extraction of a specific aromatic compound is influenced by anion volume, hydrogen bond strength between the anion and the imidazolium cation and the length of the 1-methyl-3-alkylimidazolium alkyl side chain. The interaction of alkylbenzenes and sulfur heterocyles with the IL is preferentially through CH-π hydrogen bonds and the quantity of these aromatics in the IL phase decreases with the increase of the steric hindrance imposed by the substituents on the aromatic nucleus. In the case of nitrogen heterocycles the interaction occurs preferentially through N(heteroaromatic)-H(imidazolium) hydrogen bonds and the extraction process is largely controlled by the nitrogen heterocycle pKa. Competitive extraction experiments suggest that benzene, pyridine and dibenzothiophene do not compete for the same hydrogen bond sites of the IL.

Pseudomonads biodegradation of aromatic compounds in oil sands process-affected water.

PubMed

Zhang, Yanyan; McPhedran, Kerry N; Gamal El-Din, Mohamed

2015-07-15

Aromatic naphthenic acids (NAs) have been shown to be more toxic than the classical NAs found in oil sands process-affected water (OSPW). To reduce this toxicity, Pseudomonas fluorescens and Pseudomonas putida were used to determine their ability to biodegrade aromatic compounds including treatments considering the impacts of external carbon and iron addition. Results showed that with added carbon P. fluorescens and P. putida have the capability of biodegrading these aromatics. In the presence of external carbon, gene expression of a functional PAH-ring hydroxylating dioxygenase (PAH-RHDα) was determined through reverse transcription real-time PCR, suggesting active degradation of OSPW aromatic compounds. Although no significant classical NAs removal was observed during this process, toxicity was reduced by 49.3% under optimal conditions. OSPW toxicity was eliminated with the combination of ozonation at a dose of 80 mg/L followed by biodegradation, indicating that it is a promising combined OSPW treatment approach for the safe discharge to the aquatic environment. Copyright © 2015 Elsevier B.V. All rights reserved.

Irradiated Benzene Ice Provides Clues to Meteoritic Organic Chemistry

NASA Technical Reports Server (NTRS)

Callahan, Michael Patrick; Gerakines, Perry Alexander; Martin, Mildred G.; Hudson, Reggie L.; Peeters, Zan

2013-01-01

Aromatic hydrocarbons account for a significant portion of the organic matter in carbonaceous chondrite meteorites, as a component of both the low molecular weight, solvent-extractable compounds and the insoluble organic macromolecular material. Previous work has suggested that the aromatic compounds in carbonaceous chondrites may have originated in the radiation-processed icy mantles of interstellar dust grains. Here we report new studies of the organic residue made from benzene irradiated at 19 K by 0.8 MeV protons. Polyphenyls with up to four rings were unambiguously identified in the residue by gas chromatography-mass spectrometry. Atmospheric pressure photoionization Fourier transform mass spectrometry was used to determine molecular composition, and accurate mass measurements suggested the presence of polyphenyls, partially hydrogenated polyphenyls, and other complex aromatic compounds. The profile of low molecular weight compounds in the residue compared well with extracts from the Murchison and Orgueil meteorites. These results are consistent with the possibility that solid phase radiation chemistry of benzene produced some of the complex aromatics found in meteorites.

Biodegradation studies of selected hydrocarbons from diesel oil.

PubMed

Sepic, E; Trier, C; Leskovsek, H

1996-10-01

In-vitro biodegradation of aliphatic and aromatic hydrocarbons present in diesel oil by Pseudomonas fluorescens, Texaco was studied in an aqueous medium. Small aliquots of diesel oil and its aromatic fraction were incubated aerobically for periods of up to seven months and analysed by GC-MS. Biotic losses proved to be greater for aliphatic than aromatic compounds. Most biodegradation occurred within the first 20 d of incubation. The most rapid biodegradation, up to 65% in 8 d, was observed for n-alkanes (C14-C18). The same compounds were also shown to be less affected by abiotic losses. Biodegradation of n-alkanes from diesel oil and diesel oil itself showed first order kinetics for the initial incubation period. Aromatic compounds proved to be resistant to biodegradation and only phenanthrene had been degraded (30%) within 6 months.

In Vitro Enzymatic Depolymerization of Lignin with Release of Syringyl, Guaiacyl, and Tricin Units

PubMed Central

Gall, Daniel L.; Kontur, Wayne S.; Lan, Wu; Kim, Hoon; Li, Yanding; Ralph, John

2017-01-01

ABSTRACT New environmentally sound technologies are needed to derive valuable compounds from renewable resources. Lignin, an abundant polymer in terrestrial plants comprised predominantly of guaiacyl and syringyl monoaromatic phenylpropanoid units, is a potential natural source of aromatic compounds. In addition, the plant secondary metabolite tricin is a recently discovered and moderately abundant flavonoid in grasses. The most prevalent interunit linkage between guaiacyl, syringyl, and tricin units is the β-ether linkage. Previous studies have shown that bacterial β-etherase pathway enzymes catalyze glutathione-dependent cleavage of β-ether bonds in dimeric β-ether lignin model compounds. To date, however, it remains unclear whether the known β-etherase enzymes are active on lignin polymers. Here we report on enzymes that catalyze β-ether cleavage from bona fide lignin, under conditions that recycle the cosubstrates NAD+ and glutathione. Guaiacyl, syringyl, and tricin derivatives were identified as reaction products when different model compounds or lignin fractions were used as substrates. These results demonstrate an in vitro enzymatic system that can recycle cosubstrates while releasing aromatic monomers from model compounds as well as natural and engineered lignin oligomers. These findings can improve the ability to produce valuable aromatic compounds from a renewable resource like lignin. IMPORTANCE Many bacteria are predicted to contain enzymes that could convert renewable carbon sources into substitutes for compounds that are derived from petroleum. The β-etherase pathway present in sphingomonad bacteria could cleave the abundant β–O–4-aryl ether bonds in plant lignin, releasing a biobased source of aromatic compounds for the chemical industry. However, the activity of these enzymes on the complex aromatic oligomers found in plant lignin is unknown. Here we demonstrate biodegradation of lignin polymers using a minimal set of β-etherase pathway enzymes, the ability to recycle needed cofactors (glutathione and NAD+) in vitro, and the release of guaiacyl, syringyl, and tricin as depolymerized products from lignin. These observations provide critical evidence for the use and future optimization of these bacterial β-etherase pathway enzymes for industrial-level biotechnological applications designed to derive high-value monomeric aromatic compounds from lignin. PMID:29180366

Inhibition of hydroxyl radical reaction with aromatics by dissolved natural organic matter

USGS Publications Warehouse

Lindsey, M.E.; Tarr, M.A.

2000-01-01

Reaction of aromatic compounds with hydroxyl radical is inhibited by dissolved natural organic matter (NOM). The degree of inhibition is significantly greater than that expected based on a simple model in which aromatic compound molecules bound to NOM are considered to be unreactive. In this study, hydroxyl radical was produced at steady-state concentrations using Fenton chemistry (H2O2 + Fe2+ ??? Fe3+ + HO- + HO??). Suwannee River fulvic acid and humic acid were used as NOM. The most likely mechanism for the observed inhibition is that hydroxyl radical formation occurs in microenvironmental sites remote from the aromatic compounds. In addition to changes in kinetics, pyrene hydroxyl radical reaction also exhibited a mechanistic change in the presence of fulvic acid. The mechanism changed from a reaction that was apparently firstorder in pyrene to one that was apparently secondorder in pyrene, indicating that pyrene self-reaction may have become the dominant mechanism in the presence of fulvic acid. Dissolved NOM causes significant changes in the rate and mechanism of hydroxyl radical degradation of aromatic compounds. Consequently, literature rate constants measured in pure water will not be useful for predicting the degradation of pollutants in environmental systems. The kinetic and mechanistic information in this study will be useful for developing improved degradation methods involving Fenton chemistry.Reaction of aromatic compounds with hydroxyl radical is inhibited by dissolved natural organic matter (NOM). The degree of inhibition is significantly greater than that expected based on a simple model in which aromatic compounds molecules bounds to NOM are considered to be unreactive. In this study, hydroxyl radical was produced at steady-state concentrations using Fenton chemistry (H2O2 + Fe2+ ??? Fe3+ + HO- + HO??). Suwannee River fulvic acid and humic acid were used as NOM. The most likely mechanisms for the observed inhibition is that hydroxyl radical formation occurs in microenvironmental sites remote from the aromatic compounds. In addition to changes in kinetics, pyrene hydroxyl radical reaction also exhibited a mechanistic change in the presence of fulvic acid. The mechanism changed from a reaction that was apparently first-order in pyrene to one that was apparently second-order in pyrene, indicating that pyrene self-reaction may have become the dominant mechanism in the presence of fulvic acid. Dissolved NOM causes significant changes in the rate and mechanism of hydroxyl radical degradation of aromatic compounds. Consequently, literature rate constants measured in pure water will not be useful for predicting the degradation of pollutants in environmental systems. The kinetic and mechanistic information in this study will be useful for developing improved degradation methods involving Fenton chemistry.

EFFECT OF IRRADIANCE SPECTRA ON THE PHOTOINDUCED TOXICITY OF THREE POLYCYCLIC AROMATIC HYDROCARBONS

EPA Science Inventory

Photoinduced toxicity of polycyclic aromatic hydrocarbons (PAHs) is dependent on the concentration of compounds present and the dose of light received. Of the light present, only those wavelengths absorbed by the compound have the potential to initiate the photochemical events un...

THE EFFECT OF IRRADIANCE SPECTRA ON THE PHOTOACTIVATED TOXICITY OF THREE POLYCYCLIC AROMATIC HYDROCARBONS

EPA Science Inventory

Photoinduced toxicity of polycyclic aromatic hydrocarbons (PAHs) is dependent on the concentration of compounds present and the dose of light recieved. Of the light present, only those wavelengths absorbed by the compound have the potential to initiate the photochemical events un...

Polycyclic aromatic hydrocarbons and volatile organic compounds in biochar and biochar-amended soil: A review

USDA-ARS?s Scientific Manuscript database

Residual pollutants including polycyclic aromatic hydrocarbons (PAHs), volatile organic compounds (VOCs), and carbon(aceous) nanoparticles are inevitably generated during the pyrolysis of waste biomass, and remain on the solid co-product called biochar. Such pollutants could have adverse effects on ...

Ionization of EPA Contaminants in Direct and Dopant-Assisted Atmospheric Pressure Photoionization and Atmospheric Pressure Laser Ionization

NASA Astrophysics Data System (ADS)

Kauppila, Tiina J.; Kersten, Hendrik; Benter, Thorsten

2015-06-01

Seventy-seven EPA priority environmental pollutants were analyzed using gas chromatography-mass spectrometry (GC-MS) equipped with an optimized atmospheric pressure photoionization (APPI) and an atmospheric pressure laser ionization (APLI) interface with and without dopants. The analyzed compounds included e.g., polycyclic aromatic hydrocarbons (PAHs), nitro compounds, halogenated compounds, aromatic compounds with phenolic, acidic, alcohol, and amino groups, phthalate and adipatic esters, and aliphatic ethers. Toluene, anisole, chlorobenzene, and acetone were tested as dopants. The widest range of analytes was ionized using direct APPI (66/77 compounds). The introduction of dopants decreased the amount of compounds ionized in APPI (e.g., 54/77 with toluene), but in many cases the ionization efficiency increased. While in direct APPI the formation of molecular ions via photoionization was the main ionization reaction, dopant-assisted (DA) APPI promoted ionization reactions, such as charge exchange and proton transfer. Direct APLI ionized a much smaller amount of compounds than APPI (41/77 compounds), showing selectivity towards compounds with low ionization energies (IEs) and long-lived resonantly excited intermediate states. DA-APLI, however, was able to ionize a higher amount of compounds (e.g. 51/77 with toluene), as the ionization took place entirely through dopant-assisted ion/molecule reactions similar to those in DA-APPI. Best ionization efficiency in APPI and APLI (both direct and DA) was obtained for PAHs and aromatics with O- and N-functionalities, whereas nitro compounds and aliphatic ethers were the most difficult to ionize. Halogenated aromatics and esters were (mainly) ionized in APPI, but not in APLI.

Use of gas chromatography-mass spectrometry-olfactometry and a conventional flask test to identify off-flavor compounds generated from phenylalanine during chlorination of drinking water.

PubMed

Matsushita, Taku; Sakuma, Miki; Tazawa, Shiori; Hatase, Taiki; Shirasaki, Nobutaka; Matsui, Yoshihiko

2017-11-15

Off-flavor in drinking water can be caused by transformation products (TPs) generated from organic compounds, such as amino acids, present during chlorination. However, the contributions of many of these TPs to overall off-flavor have not been quantified, mainly because the lack of appropriate chemical standards prevents sensory evaluation by means of a conventional flask test. In the present study, we used gas chromatography-mass spectrometry-olfactometry (GC-MS-O) to identify compounds responsible for the off-flavor generated by chlorination of an aqueous solution of the amino acid phenylalanine, and we propose a sensory evaluation procedure for quantification of the contributions of the identified TPs to the overall off-flavor, regardless of the availability of chemical standards of the TPs. GC-MS-O revealed that two TPs, N-chlorophenylacetaldimine and 2-chloro-2-phenylacetaldehyde, for which chemical standards are not commercially available, were the main components responsible for the off-flavor of the chlorinated solution. By using a sensory evaluation procedure involving a combination of GC-MS-O and a conventional flask test, we quantified the contributions of TPs to the overall off-flavor of the chlorinated solution. Approximately 60% of the off-flavor was attributable to free chlorine (13%), 2-chloro-2-phenylacetaldehyde (13%), trichloramine (12%) phenylacetaldehyde (11%) phenylacetonitrile (8%), and N-chlorophenylacetaldimine (2%). Treatment with powdered activated carbon (PAC) removed the off-flavor. Experiments with chlorination of 15 N-labeled phenylalanine suggested that PAC reductively decomposed trichloramine into N 2 gas and adsorbed all of the other identified TPs. Superfine PAC (median diameter, 0.7 μm) removed the off-flavor more rapidly than normal-size PAC (median diameter, 8.0 μm). Copyright © 2017 Elsevier Ltd. All rights reserved.

Selective Sorbents For Purification Of Hydrocarbons

DOEpatents

Yang, Ralph T.; Yang, Frances H.; Takahashi, Akira; Hernandez-Maldonado, Arturo J.

2006-04-18

A method for removing thiophene and thiophene compounds from liquid fuel includes contacting the liquid fuel with an adsorbent which preferentially adsorbs the thiophene and thiophene compounds. The adsorption takes place at a selected temperature and pressure, thereby producing a non-adsorbed component and a thiophene/thiophene compound-rich adsorbed component. The adsorbent includes either a metal or a metal ion that is adapted to form p-complexation bonds with the thiophene and/or thiophene compounds, and the preferential adsorption occurs by p-complexation. A further method includes selective removal of aromatic compounds from a mixture of aromatic and aliphatic compounds.

Selective sorbents for purification of hydrocarbons

DOEpatents

Yang, Ralph T.; Hernandez-Maldonado, Arturo J.; Yang, Frances H.; Takahashi, Akira

2006-08-22

A method for removing thiophene and thiophene compounds from liquid fuel includes contacting the liquid fuel with an adsorbent which preferentially adsorbs the thiophene and thiophene compounds. The adsorption takes place at a selected temperature and pressure, thereby producing a non-adsorbed component and a thiophene/thiophene compound-rich adsorbed component. The adsorbent includes either a metal or a metal cation that is adapted to form .pi.-complexation bonds with the thiophene and/or thiophene compounds, and the preferential adsorption occurs by .pi.-complexation. A further method includes selective removal of aromatic compounds from a mixture of aromatic and aliphatic compounds.

Selective sorbents for purification of hydrocarbons

DOEpatents

Yang, Ralph T.; Yang, Frances H.; Takahashi, Akira; Hernandez-Maldonado, Arturo J.

2006-05-30

A method for removing thiophene and thiophene compounds from liquid fuel includes contacting the liquid fuel with an adsorbent which preferentially adsorbs the thiophene and thiophene compounds. The adsorption takes place at a selected temperature and pressure, thereby producing a non-adsorbed component and a thiophene/thiophene compound-rich adsorbed component. The adsorbent includes either a metal or a metal cation that is adapted to form .pi.-complexation bonds with the thiophene and/or thiophene compounds, and the preferential adsorption occurs by .pi.-complexation. A further method includes selective removal of aromatic compounds from a mixture of aromatic and aliphatic compounds.

Selective sorbents for purification of hydrocartons

DOEpatents

Yang, Ralph T.; Yang, Frances H.; Takahashi, Akira; Hermandez-Maldonado, Arturo J.

2006-12-12

A method for removing thiophene and thiophene compounds from liquid fuel includes contacting the liquid fuel with an adsorbent which preferentially adsorbs the thiophene and thiophene compounds. The adsorption takes place at a selected temperature and pressure, thereby producing a non-adsorbed component and a thiophene/thiophene compound-rich adsorbed component. The adsorbent includes either a metal or a metal ion that is adapted to form .pi.-complexation bonds with the thiophene and/or thiophene compounds, and the preferential adsorption occurs by .pi.-complexation. A further method includes selective removal of aromatic compounds from a mixture of aromatic and aliphatic compounds.

Micro-milling of spent granular activated carbon for its possible reuse as an adsorbent: Remaining capacity and characteristics.

PubMed

Pan, Long; Takagi, Yuichi; Matsui, Yoshihiko; Matsushita, Taku; Shirasaki, Nobutaka

2017-05-01

We milled granular activated carbons (GACs) that had been used for 0-9 years in water treatment plants and produced carbon particles with different sizes and ages: powdered activated carbons (PAC, median diameter 12-42 μm), superfine PAC (SPAC, 0.9-3.5 μm), and submicron-sized SPAC (SSPAC, 220-290 nm). The fact that SPAC produced from 1-year-old GAC and SSPAC from 2-year-old GAC removed 2-methylisoborneol (MIB) from water with an efficiency similar to that of virgin PAC after a carbon contact time of 30 min suggests that spent GAC could be reused for water treatment after being milled. This potential for reuse was created by increasing the equilibrium adsorption capacity via reduction of the carbon particle size and improving the adsorption kinetics. During long-term (>1 year) use in GAC beds, the volume of pores in the carbon, particularly pores with widths of 0.6-0.9 nm, was greatly reduced. The equilibrium adsorption capacities of the carbon for compounds with molecular sizes in this range could therefore decrease with increasing carbon age. Among these compounds, the decreases of capacities were prominent for hydrophobic compounds, including MIB. For hydrophobic compounds, however, the equilibrium adsorption capacities could be increased with decreasing carbon particle size. The iodine number, among other indices, was best correlated with the equilibrium adsorption capacity of the MIB and would be a good index to assess the remaining MIB adsorption capacity of spent carbon. Spent GAC can possibly be reused as SPAC or SSPAC if its iodine number is ≥ 600 mg/g. Copyright © 2017 Elsevier Ltd. All rights reserved.

Investigation of Source of Irritant Gas Produced by PATRIOT Missile System Air Conditioners

DTIC Science & Technology

1986-03-31

is the mass fragment CF3 . It is a common fragment of perfluorinated hydrocarbons, and is found to be present in most of the compounds detected by...used would allow detection of the target par3meters acrolein, aromatics, a broad range of organic compounds ,. formaldehyde, and hydrogen cyanide...organic compounds were observed. Thus, aromatic organic compounds were not produced by or from any of the four new units tested. 4 1CZ 3) With the

DNA tests for strawberry: mesifurane "sherry" aroma - FaOMT-SI/NO

USDA-ARS?s Scientific Manuscript database

The amazing flavor and texture in strawberries is caused by a complex balance of numerous sugars and aromatic compounds. One of the most important aromatic compounds contributing to the flavor we have come to love in strawberries is mesifurane. Mesifurane produces a sweet sherry-like aroma and incre...

Aqueous and Tissue Residue-Based Interspecies Correlation Estimation Models Provide Conservative Hazard Estimates for Aromatic Compounds

EPA Science Inventory

Interspecies correlation estimation (ICE) models were developed for 30 nonpolar aromatic compounds to allow comparison of prediction accuracy between 2 data compilation approaches. Type 1 models used data combined across studies, and type 2 models used data combined only within s...

Effective Reuse of Electroplating Rinse Wastewater by Combining PAC with H2O2/UV Process.

PubMed

Yen, Hsing Yuan; Kang, Shyh-Fang; Lin, Chen Pei

2015-04-01

This study evaluated the performance of treating electroplating rinse wastewater by powder activated carbon (PAC) adsorption, H2O2/UV oxidation, and their combination to remove organic compounds and heavy metals. The results showed that neither the process of PAC adsorption nor H2O2/UV oxidation could reduce COD to 100 mg/L, as enforced by the Taiwan Environmental Protection Agency. On the other hand, the water sample treated by the combined approach of using PAC (5 g/L) pre-adsorption and H2O2/UV post-oxidation (UV of 64 W, H2O2 of 100 mg/L, oxidation time of 90 min), COD and DOC were reduced to 8.2 mg/L and 3.8 mg/L, respectively. Also, the combined approach reduced heavy metals to meet the effluent standards and to satisfy the in-house water reuse criteria for the electroplating factory. The reaction constant analysis indicated that the reaction proceeded much more rapidly for the combined process. Hence, it is a more efficient, economic and environmentally friendly process.

Photochemical reactions of aromatic compounds and the concept of the photon as a traceless reagent.

PubMed

Hoffmann, Norbert

2012-11-01

Electronic excitation significantly changes the reactivity of chemical compounds. Compared to ground state reactions, photochemical reactions considerably enlarge the application spectrum of a particular functional group in organic synthesis. Multistep syntheses may be simplified and perspectives for target oriented synthesis (TOS) and diversity oriented synthesis (DOS) are developed. New compound families become available or may be obtained more easily. In contrast to common chemical reagents, photons don't generate side products resulting from the transformation of a chemical reagent. Therefore, they are considered as a traceless reagent. Consequently, photochemical reactions play a central role in the methodology of sustainable chemistry. This aspect has been recognized since the beginning of the 20th century. As with many other photochemical transformations, photochemical reactions of aromatic, benzene-like compounds illustrate well the advantages in this context. Photochemical cycloadditions of aromatic compounds have been investigated for a long time. Currently, they are applied in various fields of organic synthesis. They are also studied in supramolecular structures. The phenomena of reactivity and stereoselectivity are investigated. During recent years, photochemical electron transfer mediated reactions are particularly focused. Such transformations have likewise been performed with aromatic compounds. Reactivity and selectivity as well as application to organic synthesis are studied.

Uptake and effects of a mixture of widely used therapeutic drugs in Eruca sativa L. and Zea mays L. plants.

PubMed

Marsoni, Milena; De Mattia, Fabrizio; Labra, Massimo; Bruno, Antonia; Bracale, Marcella; Vannini, Candida

2014-10-01

Pharmaceutically active compounds (PACs) are continuously dispersed into the environment due to human and veterinary use, giving rise to their potential accumulation in edible plants. In this study, Eruca sativa L. and Zea mays L. were selected to determine the potential uptake and accumulation of eight different PACs (Salbutamol, Atenolol, Lincomycin, Cyclophosphamide, Carbamazepine, Bezafibrate, Ofloxacin and Ranitidine) designed for human use. To mimic environmental conditions, the plants were grown in pots and irrigated with water spiked with a mixture of PACs at concentrations found in Italian wastewaters and rivers. Moreover, 10× and 100× concentrations of these pharmaceuticals were also tested. The presence of the pharmaceuticals was tested in the edible parts of the plants, namely leaves for E. sativa and grains for Z. mays. Quantification was performed by liquid chromatography mass spectroscopy (LC/MS/MS). In the grains of 100× treated Z. mays, only atenolol, lincomycin and carbamazepine were above the limit of detection (LOD). At the same concentration in E. sativa plants the uptake of all PACs was >LOD. Lincomycin and oflaxacin were above the limit of quantitation in all conditions tested in E. sativa. The results suggest that uptake of some pharmaceuticals from the soil may indeed be a potential transport route to plants and that these environmental pollutants can reach different edible parts of the selected crops. Measurements of the concentrations of these pharmaceuticals in plant materials were used to model potential adult human exposure to these compounds. The results indicate that under the current experimental conditions, crops exposed to the selected pharmaceutical mixture would not have any negative effects on human health. Moreover, no significant differences in the growth of E. sativa or Z. mays plants irrigated with PAC-spiked vs. non-spiked water were observed. Copyright © 2014 Elsevier Inc. All rights reserved.

Selective Oxidation of Lignin Model Compounds.

PubMed

Gao, Ruili; Li, Yanding; Kim, Hoon; Mobley, Justin K; Ralph, John

2018-05-02

Lignin, the planet's most abundant renewable source of aromatic compounds, is difficult to degrade efficiently to welldefined aromatics. We developed a microwave-assisted catalytic Swern oxidation system using an easily prepared catalyst, MoO 2 Cl 2 (DMSO) 2 , and DMSO as the solvent and oxidant. It demonstrated high efficiency in transforming lignin model compounds containing the units and functional groups found in native lignins. The aromatic ring substituents strongly influenced the selectivity of β-ether phenolic dimer cleavage to generate sinapaldehyde and coniferaldehyde, monomers not usually produced by oxidative methods. Time-course studies on two key intermediates provided insight into the reaction pathway. Owing to the broad scope of this oxidation system and the insight gleaned with regard to its mechanism, this strategy could be adapted and applied in a general sense to the production of useful aromatic chemicals from phenolics and lignin. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Activity of selected aromatic amino acids in biological systems.

PubMed

Krzyściak, Wirginia

2011-01-01

Besides the structural function in proteins, aromatic amino acids are precursors of many important biological compounds essential for normal functioning of the human organism. Many of these compounds may be used as markers for identification of specific pathological states. Comprehensive knowledge about the metabolism of aromatic amino acids and mechanisms of action of their metabolites made it possible to develop effective treatments for many disorders. However, it should not be forgotten that in some pathological conditions, these compounds could not only be involved in the pathogenesis of many disease entities but could also be used as an important tool in prediction of many diseases. This paper contains a review of published literature on aromatic amino acids in the context of physiological processes of the human body and chosen social disorders, such as cancers; psychiatric disorders: depression, anxiety states, schizophrenia, bipolar affective disorders; neurodegenerative, and cardiovascular diseases; chronic kidney insufficiency or diabetes.

Adsorption of selected pharmaceuticals and an endocrine disrupting compound by granular activated carbon. 2. Model prediction.

PubMed

Yu, Zirui; Peldszus, Sigrid; Huck, Peter M

2009-03-01

The adsorption of two representative pharmaceutically active compounds (PhACs)-naproxen and carbamazepine and one endocrine disrupting compound (EDC)-nonylphenol was studied in pilot-scale granular activated carbon (GAC) adsorbers using post-sedimentation (PS) water from a full-scale drinking water treatment plant. Acidic naproxen broke through fastest while nonylphenol was removed best, which was consistent with the degree to which fouling affected compound removals. Model predictions and experimental data were generally in good agreement for all three compounds, which demonstrated the effectiveness and robustness of the pore and surface diffusion model (PSDM) used in combination with the time-variable parameter approach for predicting removals at environmentally relevant concentrations (i.e., ng/L range). Sensitivity analyses suggested that accurate determination of film diffusion coefficients was critical for predicting breakthrough for naproxen and carbamazepine, in particular when high removals are targeted. Model simulations demonstrated that GAC carbon usage rates (CURs) for naproxen were substantially influenced by the empty bed contact time (EBCT) at the investigated conditions. Model-based comparisons between GAC CURs and minimum CURs for powdered activated carbon (PAC) applications suggested that PAC would be most appropriate for achieving 90% removal of naproxen, whereas GAC would be more suitable for nonylphenol.

Amination of electrophilic aromatic compounds by vicarious nucleophilic substitution

DOEpatents

Mitchell, Alexander R.; Pagoria, Philip F.; Schmidt, Robert D.

2000-01-01

The present invention relates to a process to aminate electrophilic aromatic compounds by vicarious nucleophilic substitution of hydrogen using quaternary hydrazinium salts. The use of trialkylhydrazinium halide, e.g., trimethylhydrazinium iodide, as well as hydroxylamine, alkoxylamines, and 4-amino-1,2,4-triazole to produce aminated aromatic structures, such as 1,3-diamino-2,4,6-trinitrobenzene (DATB), 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) and 3,5-diamino-2,4,6-trinitrotoluene (DATNT), is described. DATB and TATB are useful insensitive high explosives. TATB is also used for the preparation of benzenehexamine, a starting material for the synthesis of novel materials (optical imaging devices, liquid crystals, ferromagnetic compounds).

Influence of polychlorinated aromatic compounds on the biotransformation and toxicity of organophosphorus pesticides (OP) to the Daphnia magna

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tonkopii, V.; Zagrebin, A.; Sherstneva, L.

1995-12-31

The effect of different polychlorinated aromatics (DDT, Aroclor 1254, certain polychlorinated biphenyls and dibenzofurans) on the toxicity of OP (DDVP paraoxon, malaoxon) to Daphnia magna was studied. Pretreatment of daphnids with chlorinated compounds during 72 hours in nontoxic concentrations (1/5--1/20 CL{sub 50}) has been shown to reduce the toxicity of OP for hydrobionts. For study of influence of chlorinated compounds on biotransformation of OP the activity of enzymes which are hydrolyzing the OP was investigated in Daphnia`s homogenates or microsomes. The activity of carboxylesterase (tributyrinase, aliesterase) and arylesterase (phosphorylphosphatase) with usage as substrates accordingly {alpha}-naphthylacetate and paraoxon was measured. Besidesmore » that the activity of cholinesterase with application of propionylthiocholine as substrate was determined. After polychlorinated aromatic compounds treatment of daphnids activities of both aryl-and carboxylesterase increased markedly. It decreased the inhibition of Daphnia`s cholinesterase caused by incubation with OP in concentrations 0.5--1.0 CL{sub 50}. Thus the induction by chlorinate aromatics of OP metabolizing enzymes seems to play the important role in reduction of OP toxicity to Daphnia magna. Perhaps the aryl- and carboxylesterase of Daphnia can be used as biomarkers of pollution by polychlorinated aromatics in water.« less

Embryotoxic and teratogenic effects of petroleum hydrocarbons in mallards (Anas platyrhynchos)

USGS Publications Warehouse

Hoffman, D.J.

1979-01-01

Egg surface applications of microliter quantities of crude and refined oils of high aromatic content are embryotoxic to mallards (Anas platyrhynchos) and other avian species; applications of aliphatic hydrocarbons have virtually no effect. Mallard eggs at 72 h of development were exposed to a mixture of aromatic hydrocarbons or to aromatic compounds representative to those present in crude oil to assess their toxicity. The class composition of the mixture was similar to that of South Louisiana crude oil, an American Petroleum Institute reference oil. Application of 20 microliter of the mixture reduced embryonic survival by nearly 70%. The temporal pattern of embryonic death was similar to that after exposure to South Louisiana crude oil. Embryonic growth was stunted, as reflected by weight, crown-rump length, and bill length, and there was a significant increase in the incidence of abnormal survivors. When individual classes of aromatic hydrocarbons were tested, tetracyclics caused some embryonic death at the concentrations in the mixture. When classes were tested in all possible combinations of two, no combination appeared to be as toxic as the entire mixture. Addition of the tetracyclic compound chrysene to the aromatic mixture considerably enhanced embryotoxicity, but could not completely account for the toxicity of the crude oil. The presence of additional unidentified polycyclic aromatic hydrocarbons as well as methylated derivatives of polycyclic aromatic compounds such as chrysene may further account for the embryotoxicity of the crude oil.

Studies on in vitro biostability and blood compatibility of polyurethane potting compound based on aromatic polymeric MDI for extracorporeal devices.

PubMed

Hridya, V K; Jayabalan, M

2009-12-01

Polyurethane potting compound based on aromatic isocyanurate of polymeric MDI, poly propylene glycol (PPG400) and trimethylol propane (TMP) has significant favourable properties, good pot life and setting characteristics. The cured potting compound of this formulation has appreciable thermal stability and mechanical properties. In vitro biostability of cured potting compound has been found to be excellent without any significant degradation in simulated physiological media and chemical environment. Studies on blood-material interaction and cytotoxicity reveal in vitro blood compatibility and compatibility with cells of this potting compound.

Structure-activity relationship and docking studies of thiazolidinedione-type compounds with monoamine oxidase B.

PubMed

Carroll, Richard T; Dluzen, Dean E; Stinnett, Hilary; Awale, Prabha S; Funk, Max O; Geldenhuys, Werner J

2011-08-15

The neuroprotective activity of pioglitazone and rosiglitazone in the MPTP parkinsonian mouse prompted us to evaluate a set of thiazolidinedione (TZD) type compounds for monoamine oxidase A and B inhibition activity. These compounds were able to inhibit MAO-B over several log units of magnitude (82 nM to 600 μM). Initial structure-activity relationship studies identified key areas to modify the aromatic substituted TZD compounds. Primarily, substitutions on the aromatic group and the TZD nitrogen were key areas where activity was enhanced within this group of compounds. Copyright © 2011 Elsevier Ltd. All rights reserved.

Novel chemoselective hydrogenation of aromatic nitro compounds over ferric hydroxide supported nanocluster gold in the presence of CO and H2O.

PubMed

Liu, Lequan; Qiao, Botao; Chen, Zhengjian; Zhang, Juan; Deng, Youquan

2009-02-14

Chemoselective hydrogenation of aromatic nitro compounds were first efficiently achieved over Au/Fe(OH)(x) at 100-120 degrees C for 1.5-6 h (depending on different substrates) in the presence of CO and H(2)O.

BINDING OF CARCINOGENS TO DNA AND COVALENT ADDUCTS DNA DAMAGE - PAH, AROMATIC AMINES, NITRO-AROMATIC COMPOUNDS, AND HALOGENATED COMPOUNDS

EPA Science Inventory

DNA adducts are the covalent addition products resulting from binding of reactive chemical species to DNA bases. The cancer initiating role of DNA adducts is well-established, and is clearly reflected in the high cancer incidence observed in individuals with deficiencies in any o...

Theoretical investigation of the interaction between aromatic sulfur compounds and [BMIM](+)[FeCl4](-) ionic liquid in desulfurization: A novel charge transfer mechanism.

PubMed

Li, Hongping; Zhu, Wenshuai; Chang, Yonghui; Jiang, Wei; Zhang, Ming; Yin, Sheng; Xia, Jiexiang; Li, Huaming

2015-06-01

In this work, interaction nature between a group of aromatic sulfur compounds and [BMIM](+)[FeCl4](-) have been investigated by density functional theory (DFT). A coordination structure is found to be critical to the mechanism of extractive desulfurization. Interaction energy and extractive selectivity follow the order: thiophene (TH)

Influence of silicon defects on the adsorption of thiophene-like compounds on polycyclic aromatic hydrocarbons: a theoretical study using thiophene + coronene as the simplest model.

PubMed

Galano, Annia

2007-03-08

Physisorption and chemisorption processes of thiophene on coronene and 2Si-coronene have been studied using density functional theory and MP2 methods. These systems have been chosen as the simplest models to describe the adsorption of thiophene-like compounds on polycyclic aromatic hydrocarbons (PAHs). The calculated data suggest that the presence of silicon atoms in PAHs could favor their interaction with thiophene and similar compounds. Small stabilization energies have been found for several physisorbed complexes. The thiophene chemisorption on coronene seems very unlikely to occur, while that on 2Si-coronene leads to addition products which are very stable, with respect to the isolated reactants. These chemisorption processes were found to be exoergic (DeltaG < 0) in the gas phase and in the nonpolar liquid phase. The results reported in this work suggest that silicon defects on extended polycyclic aromatic hydrocarbons, such as graphite, soot, and large-diameter carbon nanotubes, could make them useful in the removal processes of aromatic sulfur compounds from oil hydrocarbons.

Substituent effect on the oxidation of phenols and aromatic amines by horseradish peroxidase compound I.

PubMed

Job, D; Dunford, H B

1976-07-15

A stopped-flow kinetic study shows that the reduction rate of horseradish peroxidase compound I by phenols and aromatic amines is greatly dependent upon the substituent effect on the benzene ring. Morever it has been possible to relate the reduction rate constants of monosubstituted substrates by a linear free-energy relationship (Hammett equation). The correlation of log (rate constants) with sigma values (Hammett equation) and the absence of correlation with sigma+ values (Okamoto-Brown equation) can be explained by a mechanism of aromatic substrate oxidations, in which the substrate gives an electron to the enzyme compound I and simultaneously loses a proton. The analogy which has been made with oxidation potentials of phenols or anilines strengthens the view that the reaction is only dependent on the relative ease of oxidation of the substrate. The rate constant obtained for p-aminophenol indicates that a value of 2.3 X 10(8) M-1 S-1 probably approaches the diffusion-controlled limit for a bimolecular reaction involving compound I and an aromatic substrate.

Shape-selective adsorption of aromatic molecules from water by tetramethylammonium-smectite

USGS Publications Warehouse

Lee, J.; Mortland, M.M.; Boyd, S.A.; Chiou, C.T.

1989-01-01

The adsorption of aromatic compounds by smectite exchanged with tetramethylammonium (TMA) has been studied. Aromatic compounds adsorbed by TMA-smectite are assumed to adopt a tilted orientation in a face-to-face arrangment with the TMA tetrahedra. The sorptive characteristics of TMA-smectite were influenced strongly by the presence of water. The dry TMA-smectite showed little selectivity in the uptake of benzen, toluene and xylene. In the presence of water, TMA-smectite showed a high degree of selectivity based on molecular size/shape, resulting in high uptake of benzene and progressively lower uptake of larger aromatic molecules. This selectivity appeared to result from the shrinkage of interlamellar cavities by water.

Polybenzimidazole via aromatic nucleophilic displacement

NASA Technical Reports Server (NTRS)

Connell, John W. (Inventor); Hergenrother, Paul M. (Inventor); Smith, Joseph G. (Inventor)

1994-01-01

Di(hydroxyphenyl)benzimidazole monomers were prepared from phenyl-4-hydroxybenzoate and aromatic bis(o-diamine)s. These monomers were used in the synthesis of soluble polybenzimidazoles. The reaction involved the aromatic nucleophilic displacement of various di(hydroxyphenyl)benzimidazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds in the presence of an alkali metal base. These polymers exhibited lower glass transition temperatures, improved solubility, and better compression moldability over their commercial counterparts.

Physico-chemical processes for landfill leachate treatment: Experiments and mathematical models

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xing, W.; Ngo, H.H.; Kim, S.H.

2008-07-01

In this study, the adsorption of synthetic landfill leachate onto four kinds of activated carbon has been investigated. From the equilibrium and kinetics experiments, it was observed that coal based PAC presented the highest organic pollutants removal efficiency (54%), followed by coal based GAC (50%), wood based GAC (33%) and wood based PAC (14%). The adsorption equilibrium of PAC and GAC was successfully predicted by Henry-Freundlich adsorption model whilst LDFA + Dual isotherm Kinetics model could describe well the batch adsorption kinetics. The flocculation and flocculation-adsorption experiments were also conducted. The results indicated that flocculation did not perform well onmore » organics removal because of the dominance of low molecular weight organic compounds in synthetic landfill leachate. Consequently, flocculation as pretreatment to adsorption and a combination of flocculation-adsorption could not improve much the organic removal efficiency for the single adsorption process.« less

Remarkably selective iridium catalysts for the elaboration of aromatic C-H bonds.

PubMed

Cho, Jian-Yang; Tse, Man Kin; Holmes, Daniel; Maleczka, Robert E; Smith, Milton R

2002-01-11

Arylboron compounds have intriguing properties and are important building blocks for chemical synthesis. A family of Ir catalysts now enables the direct synthesis of arylboron compounds from aromatic hydrocarbons and boranes under "solventless" conditions. The Ir catalysts are highly selective for C-H activation and do not interfere with subsequent in situ transformations, including Pd-mediated cross-couplings with aryl halides. By virtue of their favorable activities and exceptional selectivities, these Ir catalysts impart the synthetic versatility of arylboron reagents to C-H bonds in aromatic and heteroaromatic hydrocarbons.

BIODEGRADATION OF AROMATIC COMPOUNDS UNDER MIXED OXYGEN/DENITRIFYING CONDITIONS: A REVIEW

EPA Science Inventory

Bioremediation of aromatic hydrocarbons in groundwater and sediments is often limited by dissolved oxygen. Many aromatic hydrocarbons degrade very slowly or not at all under anaerobic conditions. Nitrate is a good alternative electron acceptor to oxygen, and denitrifying bacteria...

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wear, Jr., John Edmund

The objective of this study was to examine the hypothesis that select functional groups of bacteria from pristine sites have an innate ability to degrade synthetic aromatics that often contaminate groundwater environments,due to exposure to naturally occurring recalcitrant aromatics in their environment. This study demonstrates that subsurface microbial communities are capable of utilizing lignin and humic acid breakdown products. Utilizers of these compounds were found to be present in most all the wells tested. Even the deepest aquifer tested had utilizers present for all six of the aromatics tested. Highest counts for the aromatics tested were observed with the naturallymore » occurring breakdown products of either lignin or humic acid. Carboxylic acids were found to be an important sole carbon source for groundwater bacteria possibly explained by the fact that they are produced by the oxidative cleavage of aromatic ring structures. The carbohydrate sole carbon sources that demonstrated the greatest densities were ones commonly associated with humics. This study indicates that utilization of naturally occurring aromatic compounds in the subsurface is an important nutritional source for groundwater bacteria. In addition, it suggests that adaptation to naturally occurring recalcitrant substrates is the origin of degradative pathways for xenobiotic compounds with analogous structure. This work has important implications for in situ bioremediation as a method of environmental cleanup.« less

High-field FT-ICR-MS and aromaticity equivalent approach for structural identification of water soluble organic compounds (WSOC)

NASA Astrophysics Data System (ADS)

Harir, Mourad; Yassine, Mahmoud M.; Dabek-Zlotorzynska, Ewa; Hertkorn, Norbert; Schmitt-Kopplin, Philippe

2015-04-01

Organic aerosol (OA) makes up a large and often dominant fraction, (20 to 90%) of the submicron atmospheric particulate mass, and its effects are becoming increasingly important in determining climatic and health effects of atmospheric aerosols. Despite the abundance of OA, our understanding of the sources, formation processes and atmospheric properties of OA is limited. Atmospheric OA has both primary (directly emitted) and secondary (formed in the atmosphere from precursor gases) sources, which can be natural (e.g. vegetation) and/or anthropogenic (e.g. fossil-based vehicle exhaust or biomass burning). A significant fraction of OA contains as much as 20-70% of water soluble organic compounds (WSOC). The WSOC fraction is a very complex mixture of low volatility, polyfunctional aliphatic and aromatic compounds containing carboxyl, alcohol, carbonyl, sulfo, nitro, and other functionalities. This high degree of chemical complexity of atmospheric organics has inspired a number of sophisticated approaches that are capable of identifying and detecting a variety of different analytes in OA. Accordingly, one of the most challenging areas of atmospheric particulate matter (PM) analysis is to comprehend the molecular complexity of the OA, especially WSOC fraction, a significant component of atmospheric fine PM (PM2.5). The sources of WSOC are not well understood, especially the relative contributions of primary vs. secondary organic aerosol. Therefore, the molecular characterization of WSOC is important because it allows gaining insight into aerosol sources and underlying mechanisms of secondary organic aerosols (SOA) formation and transformation. In this abstract, molecular characterization of WSOC was achieved using high-field mass spectrometry FT-ICR-MS and aromaticity equivalent approach. Aromaticity equivalent (Xc), defined recently as a new parameter calculated from the assigned molecular formulas (complementary to the aromaticity index [1]), is introduced to improve identification and characterization of aromatic and condensed aromatic compounds in WSOC [2]. We proposed threshold values of Xc≥ 2.5000 and Xc≥ 2.7143 as ambiguous minimum criteria for the presence of aromatic structure and condensed aromatic compounds, respectively. The advantage of employing this parameter is that Xc would have a constant value for each proposed core structure regardless the degree of alkylation, and thus visual representation and structural interpretations of the spectra become advantageous for characterizing and comparing complex samples. Diesel particulate matter (DPM) and two atmospheric aerosols collected in the industrial area affected by biomass burning events were used to study the applicability of the proposed criteria for the improved identification of aromatic and condensed aromatic structures in complex mixtures in the FT-ICR mass spectra. References [1] Koch.BP, Dittmar.T. From mass to structure: an aromaticity index for high-resolution mass data of natural organic matter. Rapid Commun. Mass Spectrom. 2006, 20, 926-932 [2] Yassine.MM, Harir.M, Dabek-Zlotorzynska.E, Schmitt-Kopplin.Ph. Structural characterization of organic aerosol using Fourier transform ion cyclotron resonance mass spectrometry: Aromaticity equivalent approach. Rapid Commun. Mass Spectrom. 2014. 28. 2445-2454

Cyclic terpenoids of contemporary resinous plant detritus and of fossil woods, ambers and coals

USGS Publications Warehouse

Simoneit, B.R.T.; Grimalt, J.O.; Wang, T.-G.; Cox, R.E.; Hatcher, P.G.; Nissenbaum, A.

1986-01-01

Cyclic terpenoids present in the solvent extractable material of fossil woods, ambers and brown coals have been analyzed. The sample series chosen consisted of wood remains preserved in Holocene to Jurassic sediments and a set of of ambers from the Philippines (copalite), Israel, Canada and Dominican Republic. The brown coals selected were from the Fortuna Garsdorf Mine and Miocene formations on Fiji. The fossil wood extracts contained dominant diterpenoid or sesquiterpenoid skeletons, and aromatized species were present at high concentrations, with a major amount of two-ring aromatic compounds. Tricyclic diterpenoids were the predominant compounds in the ambers. Aromatized derivatives were the major components, consisting of one or two aromatic ring species with the abietane and occasionally pimarane skeletons. The saturated structures were comprised primarily of the abietane and pimarane skeletons having from three to five carbon (C1, C2, etc.) substituents. Kaurane and phyllocladane isomers were present in only minor amounts. Bicyclic sesquiterpenoids as saturated and partial or fully aromatized forms were also common in these samples, but only traces of sesterterpenoids and triterpenoid derivatives were found. The brown coal extracts were composed of major amounts of one- and two-ring aromatized terpenoids, with a greater proportion of triterpenoid derivatives than in the case of the woods and ambers. This was especially noticeable for the German coal, where the triterpenoids were predominant. Open C-ring aromatized structures were also present in this coal. Steroid compounds were not detectable, but some hopanes were found as minor components in the German brown coal. An overview of the skeletal structure classes identified in each sample, as well as the general mass spectrometric characteristics of the unknown compounds are included in the present paper. It can be concluded from these structural distributions that aromatization is the main process for the transformation of terrestrial cyclic terpenoids during diagenesis, constituting a general pathway for all terpenoids. ?? 1986 Pergamon Journals Ltd.

Composition of the black crusts from the Saint Denis Basilica, France, as revealed by gas chromatography-mass spectrometry.

PubMed

Gaviño, Maria; Hermosin, Bernardo; Vergès-Belmin, Véronique; Nowik, Witold; Saiz-Jimenez, Cesareo

2004-05-01

The organic fraction of black crusts from Saint Denis Basilica, France, is composed of a complex mixture of aliphatic and aromatic compounds. These compounds were studied by two different analytical approaches: tetramethyl ammonium hydroxide (TMAH) thermochemolysis in combination with gas chromatography-mass spectrometry (GC-MS), and solvent extraction, fractionation by silica column, and identification of the fraction components by GC-MS. The first approach, feasible at the microscale level, is able to supply fairly general information on a wide range of compounds. Using the second approach, we were able to separate the complex mixture of compounds into four fractions, enabling a better identification of the extractable compounds. These compounds belong to different classes: aliphatic hydrocarbons (nalkanes, n-alkenes), aliphatic and aromatic carboxylic acids (n-fatty acids, alpha,omega-dicarboxylic acids, and benzenecarboxylic acids), polycyclic aromatic hydrocarbons (PAH), and molecular biomarkers (isoprenoid hydrocarbons, diterpenoids, and triterpenoids). With each approach, similar classes of compounds were identified, although TMAH thermochemolysis failed to identify compounds present at low concentrations in black crusts. The two proposed methodological approaches are complementary, particularly in the study of polar fractions.

Remedial Investigation/Feasibility Study/Interim Response Actions

DTIC Science & Technology

1988-03-25

organosulfur compounds (CC/FP), organophosphorus compounds (CC/FPD), hydrocarbons (CC/FID), volatile aromatic compounds (GC/ PID ), volatile halogenated...ICP metals, mercury and arsenic (AA). Water samples are being analyzed for volatile halogenated organics (GC/CON), volatile aromatic organics (GC/ PID ...Feb Mar Apr May Jun Jul Aug SepSI - I I I I I • .. I I I ----+----- 685 27-90 so ONSITE DISPOSAL FACILITY .i * 686 27-01 Prep FLUE Plan Fz=m8u> 6e7

Microbial reductive dehalogenation.

PubMed Central

Mohn, W W; Tiedje, J M

1992-01-01

A wide variety of compounds can be biodegraded via reductive removal of halogen substituents. This process can degrade toxic pollutants, some of which are not known to be biodegraded by any other means. Reductive dehalogenation of aromatic compounds has been found primarily in undefined, syntrophic anaerobic communities. We discuss ecological and physiological principles which appear to be important in these communities and evaluate how widely applicable these principles are. Anaerobic communities that catalyze reductive dehalogenation appear to differ in many respects. A large number of pure cultures which catalyze reductive dehalogenation of aliphatic compounds are known, in contrast to only a few organisms which catalyze reductive dehalogenation of aromatic compounds. Desulfomonile tiedjei DCB-1 is an anaerobe which dehalogenates aromatic compounds and is physiologically and morphologically unusual in a number of respects, including the ability to exploit reductive dehalogenation for energy metabolism. When possible, we use D. tiedjei as a model to understand dehalogenating organisms in the above-mentioned undefined systems. Aerobes use reductive dehalogenation for substrates which are resistant to known mechanisms of oxidative attack. Reductive dehalogenation, especially of aliphatic compounds, has recently been found in cell-free systems. These systems give us an insight into how and why microorganisms catalyze this activity. In some cases transition metal complexes serve as catalysts, whereas in other cases, particularly with aromatic substrates, the catalysts appear to be enzymes. Images PMID:1406492

Gondola-shaped tetra-rhenium metallacycles modified evanescent wave infrared chemical sensors for selective determination of volatile organic compounds.

PubMed

Huang, Genin Gary; Lee, Chung-Jay; Tsai, Bo-Chan; Yang, Jyisy; Sathiyendiran, Malaichamy; Lu, Kuang-Lieh

2011-07-15

Water-stable and cavity-contained rhenium metallacycles were synthesized, and their ability to selectively interact with volatile organic compounds (VOCs) systematically studied using attenuated total reflection infrared (ATR-IR) spectroscopy. Integrating the unique properties of rhenium metallacycles into optical sensing technologies significantly improves selectivity in detecting aromatic compounds. To explore the interaction of rhenium metallacycles with VOCs, the surface of ATR sensing elements was modified with the synthesized rhenium metallacycles and used to detect VOCs. The results indicate that rhenium metallacycles have crown ether-like recognition sites, which can selectively interact with aromatic compounds, especially those bearing polar functional groups. The IR absorption bands of rhenium metallacycles shift significantly upon adsorption of aromatic VOCs, revealing a strong interaction between the tetra-rhenium metallacycles and guest aromatic compounds. Optimizing the thickness of the metallacycles coated on the surface of the sensing element led to rapid response in detection. The dynamic range of response was generally up to 30 mg/L with detection limits ca. 30 μg/L. Further studies of the effect of interferences indicate that recovery can be higher than 95% for most of the compounds tested. The results on the flow-cell device indicated that the performances were similar to a static detection system but the detection of VOCs can be largely simplified. Copyright © 2011 Elsevier B.V. All rights reserved.

Characterization of selected volatile organic compounds, polycyclic aromatic hydrocarbons and carbonyl compounds at a roadside monitoring station

NASA Astrophysics Data System (ADS)

Ho, K. F.; Lee, S. C.; Chiu, Gloria M. Y.

Volatile organic compounds (VOCs), PAHs and carbonyl compounds are the major toxic components in Hong Kong. Emissions from motor vehicles have been one of the primary pollution sources in the metropolitan areas throughout Hong Kong for a long time. A 1-yr monitoring program for VOCs, PAHs and carbonyl compounds had been performed at a roadside urban station at Hong Kong Polytechnic University in order to determine the variations and correlations of each selected species (VOCs, PAHs and carbonyl compounds). This study is aimed to analyze toxic volatile organic compounds (benzene, toluene, ethylbenzene and xylene), two carbonyl compounds (formaldehyde, acetaldehyde), and selective polycyclic aromatic hydrocarbons. The monitoring program started from 16 April 1999 to 30 March 2000. Ambient VOC concentrations, many of which originate from the same sources as particulate PAHs and carbonyls compounds, show significant quantities of benzene, toluene and xylenes. Correlations and multivariate analysis of selected gaseous and particulate phase organic pollutants were performed. Source identification by principle component analysis and hierarchical cluster analysis allowed the identification of four sources (factors) for the roadside monitoring station. Factor 1 represents the effect of diesel vehicle exhaust. Factor 2 shows the contribution of aromatic compounds. Factor 3 explains photochemical products—formaldehyde and acetaldehyde. Factor 4 explains the effect of gasoline vehicle exhaust.

The chemistry and beneficial bioactivities of carvacrol (4-isopropyl-2-methylphenol), a component of essential oils produced by aromatic plants and spices

USDA-ARS?s Scientific Manuscript database

Aromatic plants produce organic compounds that may be involved in the defense of plants against phytopathogenic insects, bacteria, fungi, and viruses. One of these compounds called carvacrol that is found in high concentrations in essential oils such as oregano has been reported to exhibit numerous...

Alkylation of organic aromatic compounds

DOEpatents

Smith, L.A. Jr.

1989-07-18

Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 fig.

Alkylation of organic aromatic compounds

DOEpatents

Smith, Jr., Lawrence A.; Arganbright, Robert P.; Hearn, Dennis

1994-01-01

Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C.sub.2 to C.sub.10 olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80.degree. C. to 500.degree. C., using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms.

Alkylation of organic aromatic compounds

DOEpatents

Smith, Jr., Lawrence A.

1989-01-01

Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C.sub.2 to C.sub.10 olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80.degree. C. to 500.degree. C., using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms.

Alkylation of organic aromatic compounds

DOEpatents

Smith, L.A. Jr.; Arganbright, R.P.; Hearn, D.

1994-06-14

Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a molecular sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 fig.

Aromatic hydrocarbons from the Middle Jurassic fossil wood of the Polish Jura

NASA Astrophysics Data System (ADS)

Smolarek, Justyna; Marynowski, Leszek

2013-09-01

Aromatic hydrocarbons are present in the fossil wood samples in relatively small amounts. In almost all of the tested samples the dominating aromatic hydrocarbon is perylene and its methyl and dimethyl derivatives. The most important biomarkers present in the aromatic fraction are dehydroabietane, siomonellite and retene, compounds characteristic for conifers. The distribution of discussed compounds is highly variable due to such early diagenetic processes affecting the wood as oxidation and the activity of microorganisms. MPI1 parameter values (methylphenanthrene index) for the majority of the samples are in the range of 0.1 to 0.5, which results in the highly variable values of Rc (converted value of vitrinite reflectance) ranging from 0.45 to 0.70%. Such values suggest that MPI1 parameter is not useful as maturity parameter in case of Middle Jurassic ore-bearing clays, even if measured strictly on terrestrial organic matter (OM). As a result of weathering processes (oxidation) the distribution of aromatic hydrocarbons changes. In the oxidized samples the amount of aromatic hydrocarbons, both polycyclic as well as aromatic biomarkers decreases.

Site occupation of indium and jump frequencies of cadmium in FeGa 3

NASA Astrophysics Data System (ADS)

Newhouse, Randal; Collins, Gary S.; Zacate, Matthew O.

2016-12-01

Perturbed angular correlation (PAC) measurements using the In-111 probe were carried out on FeGa3 as part of a broader investigation of indium site occupation and cadmium diffusion in intermetallic compounds. One PAC signal was observed with hyperfine parameters ω 1= 513.8(1) Mrad/s and η= 0.939(2) at room temperature. By comparison with quadrupole frequencies observed in PAC measurements on isostructural RuIn3, it was determined that indium occupies only the 8j site in the FeGa3 structure, denoted Ga(2) below because two out of the three Ga sites have this point symmetry. PAC spectra at elevated temperature exhibited damping characteristic of electric field gradients (EFGs) that fluctuate as Cd probes jump among Ga(2) sites within the lifetime of the excited PAC level. A stochastic model for the EFG fluctuations based on four conceivable, single-step jump-pathways connecting one Ga(2) site to neighboring Ga(2) sites was developed and used to fit PAC spectra. The four pathways lead to two observable EFG reorientation rates, and these reorientation rates were found to be strongly dependent on EFG orientation. Calculations using density functional theory were used to reduce the number of unknowns in the model with respect to EFG orientation. This made it possible to determine with reasonable precision the total jump rate of Cd among Ga(2) sites that correspond to a change in mirror plane orientation of site-symmetry. This total jump rate was found to be thermally activated with an activation enthalpy of 1.8 ±0.1 eV.

MICROBIAL METABOLISM OF AROMATIC COMPOUNDS I.

PubMed Central

Tabak, Henry H.; Chambers, Cecil W.; Kabler, Paul W.

1964-01-01

Tabak, Henry H. (Robert A. Taft Sanitary Engineering Center, Cincinnati, Ohio), Cecil W. Chambers, and Paul W. Kabler. Microbial metabolism of aromatic carbon compounds. I. Decomposition of phenolic compounds and aromatic hydrocarbons by phenol-adapted bacteria. J. Bacteriol. 87:910–919. 1964.—Bacteria from soil and related environments were selected or adapted to metabolize phenol, hydroxy phenols, nitrophenols, chlorophenols, methylphenols, alkylphenols, and arylphenols when cultured in mineral salts media with the specific substrate as the sole source of carbon. A phenol-adapted culture (substrate-induced enzyme synthesis proven) was challenged in respirometric tests with 104 related compounds; probable significant oxidative activity occurred with 65. Dihydric phenols were generally oxidized; trihydric phenols were not. Cresols and dimethylphenols were oxidized; adding a chloro group increased resistance. Benzoic and hydroxybenzoic acids were oxidized; sulfonated, methoxylated, nitro, and chlorobenzoic acids were not; m-toluic acid was utilized but not the o- and p-isomers. Benzaldehyde and p-hydroxybenzaldehyde were oxidized. In general, nitro- and chloro-substituted compounds and the benzenes were difficult to oxidize. PMID:14137630

Graphene and graphene nanocomposites for the removal of aromatic organic compounds from the water: systematic review

NASA Astrophysics Data System (ADS)

Monsores Paixão, Monique; Tadeu Gomes Vianna, Marco; Marques, Marcia

2018-01-01

Aromatic organic pollutants are highly toxic to the human and environmental health and are considered as priority pollutants by regulatory agencies. Managing contaminated sites with organic pollutants is one of the major environmental challenges today. Of all technologies that have been proposed to remove contaminants, adsorption is recognized worldwide as an attractive option due to its versatility, wide applicability and economic viability. Recent studies report the use of graphene (GN), a recently carbon nanomaterial, and its derivatives in sorption processes for the removal of aromatic organic compounds. The present review has shown that GN structures are a promising alternative to traditional adsorbent materials, with excellent results in the removal of organic compounds from water, due to their unique structural characteristics and great adsorption capacity for organic compounds. Although, there is still a long way to go until that practical applications can be implemented.

Detecting aromatic compounds on planetary surfaces using ultraviolet time-resolved fluorescence spectroscopy

NASA Astrophysics Data System (ADS)

Eshelman, E.; Daly, M. G.; Slater, G.; Cloutis, E.

2018-02-01

Many aromatic organic molecules exhibit strong and characteristic fluorescence when excited with ultraviolet radiation. As laser excitation in the ultraviolet generates both fluorescence and resonantly enhanced Raman scattering of aromatic vibrational modes, combined Raman and fluorescence instruments have been proposed to search for organic compounds on Mars. In this work the time-resolved fluorescence of a suite of 24 compounds composed of 2-5 ringed alternant, non-alternant, and heterocyclic PAHs was measured. Fluorescence instrumentation with similar specifications to a putative flight instrument was capable of observing the fluorescence decay of these compounds with a sub-ns resolution. Incorporating time-resolved capabilities was also found to increase the ability to discriminate between individual PAHs. Incorporating time-resolved fluorescence capabilities into an ultraviolet gated Raman system intended for a rover or lander can increase the ability to detect and characterize PAHs on planetary surfaces.

Lignin solubilization and aqueous phase reforming for the production of aromatic chemicals and hydrogen.

PubMed

Zakzeski, Joseph; Weckhuysen, Bert M

2011-03-21

The solubilization and aqueous phase reforming of lignin, including kraft, soda, and alcell lignin along with sugarcane bagasse, at low temperatures (T≤498 K) and pressures (P≤29 bar) is reported for the first time for the production of aromatic chemicals and hydrogen. Analysis of lignin model compounds and the distribution of products obtained during the lignin aqueous phase reforming revealed that lignin was depolymerized through disruption of the abundant β-O-4 linkages and, to a lesser extent, the 5-5' carbon-carbon linkages to form monomeric aromatic compounds. The alkyl chains contained on these monomeric compounds were readily reformed to produce hydrogen and simple aromatic platform chemicals, particularly guaiacol and syringol, with the distribution of each depending on the lignin source. The methoxy groups present on the aromatic rings were subject to hydrolysis to form methanol, which was also readily reformed to produce hydrogen and carbon dioxide. The composition of the isolated yields of monomeric aromatic compounds and overall lignin conversion based on these isolated yields varied from 10-15% depending on the lignin sample, with the balance consisting of gaseous products and residual solid material. Furthermore, we introduce the use of a high-pressure autoclave with optical windows and an autoclave with ATR-IR sentinel for on-line in situ spectroscopic monitoring of biomass conversion processes, which provides direct insight into, for example, the solubilization process and aqueous phase reforming reaction of lignin. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of gasoline aromatic content on emissions of volatile organic compounds and aldehydes from a four-stroke motorcycle.

PubMed

Yao, Yung-Chen; Tsai, Jiun-Horng

2013-01-01

A new four-stroke carburettor motorcycle engine without any engine adjustments was used to study the impact of fuel aromatic content on the exhaust emissions of organic air pollutants (volatile organic compounds and carbonyls). Three levels of aromatic content, i.e. 15, 25, and 50% (vol.) aromatics mixed with gasoline were tested. The emissions of aromatic fuel were compared with those of commercial unleaded gasoline. The results indicated that the A 15 (15 vol% aromatics in gasoline) fuel exhibited the greatest total organic emission improvement among these three aromatic fuels as compared with commercial gasoline, reaching 59%. The highest emission factors of alkanes, alkenes, and carbonyl groups appeared in the reference fuel (RF) among all of the test fuels. A 15 showed the highest emission reduction in alkanes (73%), aromatics (36%), and carbonyls (28%), as compared to those of the RF. The highest emission reduction ofalkenes was observed when using A25 as fuel. A reduction in fuel aromatic content from 50 to 25 and 15 vol% in gasoline decreased benzene and toluene emissions, but increased the aldehyde emissions. In general, the results showed that the highest emission reductions for the most of measured organic pollutants appeared when using A 15 as the fuel.

Aromatic-degrading Sphingomonas isolates from the deep subsurface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fredrickson, J.K.; Romine, M.F.; Balkwill, D.L.

An obligately aerobic chemoheterotrophic bacterium (strain F199) previously isolated from Southeast Coastal Plain subsurface sediments and shown to degrade toluene, naphthalene, and other aromatic compounds was characterized by analysis of its 16S rRNA nucleotide base sequence and cellular lipid composition. Strain F199 contained 2-OH14:0 and 18:1{omega}7c as the predominant cellular fatty acids and sphingolipids that are characteristic of the genus Sphingomonas. Phylogenetic analysis of its 16SrRNA sequence indicated that F199 was most closely related to Sphingomonas capsulata among the bacteria currently in the Ribosomal Database. Five additional isolates from deep Southeast Coastal Plain sediments were determined by 16S rRNA sequencemore » analysis to be closely related to F199. These strains also contained characteristic sphingolipids. Four of these five strains could also grow on a broad range of aromatic compounds and could mineralize [{sup 14C}]toluene and [{sup 14C}]naphthalene. S. capsulata (ATCC 14666), Sphingomonas paucimobiolis (ATCC 29837), and one of the subsurface isolates were unable to grow on any of the aromatic compounds or mineralize toluene or naphthalene. These results indicate that bacteria within the genus Sphingomonas are present in Southeast Coastal Plain subsurface sediments and that the capacity for degrading a broad range of substituted aromatic compounds appears to be common among Sphingomonas species from this environment. 41 refs., 2 figs., 5 tabs.« less

Pistachio oil (Pistacia vera L. cv. Uzun): Characterization of key odorants in a representative aromatic extract by GC-MS-olfactometry and phenolic profile by LC-ESI-MS/MS.

PubMed

Sonmezdag, Ahmet Salih; Kelebek, Hasim; Selli, Serkan

2018-02-01

Volatile, aroma-active, and phenolic compounds of pistachio oil obtained from cv. Uzun were investigated in the current study. To obtain a representative aromatic extract, three of the most widely used extraction methods were compared using a representative test; the solvent-assisted flavour extraction (SAFE) aromatic extract from pistachio oil was found to be the most representative. A total of 50 aroma compounds were determined in pistachio oil and it was found that terpenes, aldehydes, and alcohols were the most abundant volatile compounds. Applying GC-MS-olfactometry and aroma extract dilution analysis (AEDA) resulted in a total of 14 aroma-active areas being detected in the extract of pistachio oil. In the phenolic fraction obtained by the LC-ESI-MS/MS method, a total of 12 phenolic compounds was found in the pistachio oil, of which seven compounds were reported for the first time. Eriodictyol-7-O-glucoside and protocatechuic acid were the most dominant phenolic compounds. Copyright © 2017 Elsevier Ltd. All rights reserved.

Fusing porphyrins with polycyclic aromatic hydrocarbons and heterocycles for optoelectronic applications

DOEpatents

Thompson, Mark E.; Diev, Viacheslav; Hanson, Kenneth; Forrest, Stephen R.

2015-08-18

A compound that can be used as a donor material in organic photovoltaic devices comprising a non-activated porphyrin fused with one or more non-activated polycyclic aromatic rings or one or more non-activated heterocyclic rings can be obtained by a thermal fusion process. The compounds can include structures of Formula I: ##STR00001## By heating the reaction mixture of non-activated porphyrins with non-activated polycyclic aromatic rings or heterocyclic rings to a fusion temperature and holding for a predetermined time, fusion of one or more polycyclic rings or heterocyclic rings to the non-activated porphyrin core in meso,.beta. fashion is achieved resulting in hybrid structures containing a distorted porphyrin ring with annulated aromatic rings. The porphyrin core can be olygoporphyrins.

Formation of highly oxygenated organic molecules from aromatic compounds

NASA Astrophysics Data System (ADS)

Molteni, Ugo; Bianchi, Federico; Klein, Felix; El Haddad, Imad; Frege, Carla; Rossi, Michel J.; Dommen, Josef; Baltensperger, Urs

2018-02-01

Anthropogenic volatile organic compounds (AVOCs) often dominate the urban atmosphere and consist to a large degree of aromatic hydrocarbons (ArHCs), such as benzene, toluene, xylenes, and trimethylbenzenes, e.g., from the handling and combustion of fuels. These compounds are important precursors for the formation of secondary organic aerosol. Here we show that the oxidation of aromatics with OH leads to a subsequent autoxidation chain reaction forming highly oxygenated molecules (HOMs) with an O : C ratio of up to 1.09. This is exemplified for five single-ring ArHCs (benzene, toluene, o-/m-/p-xylene, mesitylene (1,3,5-trimethylbenzene) and ethylbenzene), as well as two conjugated polycyclic ArHCs (naphthalene and biphenyl). We report the elemental composition of the HOMs and show the differences in the oxidation patterns of these ArHCs. A potential pathway for the formation of these HOMs from aromatics is presented and discussed. We hypothesize that AVOCs may contribute substantially to new particle formation events that have been detected in urban areas.

Biodegradation of trichloroethylene and involvement of an aromatic biodegradative pathway.

PubMed Central

Nelson, M J; Montgomery, S O; Mahaffey, W R; Pritchard, P H

1987-01-01

Biodegradation of trichloroethylene (TCE) by bacterial strain G4 resulted in complete dechlorination of the compound, as indicated by the production of inorganic chloride. A component of the water from which strain G4 was isolated that was required for TCE degradation was identified as phenol. Strain G4 degraded TCE in the presence of chloramphenicol only when preinduced with phenol. Toluene, o-cresol. and m-cresol could replace the phenol requirement. Two of the inducers of TCE metabolism, phenol and toluene, apparently induced the same aromatic degradative pathway that cleaved the aromatic ring by meta fission. Cells induced with either phenol or toluene had similar oxidation rates for several aromatic compounds and had similar levels of catechol-2,3-dioxygenase. The results indicate that one or more enzymes of an inducible pathway for aromatic degradation in strain G4 are responsible for the degradation of TCE. PMID:3606099

Portable spotter for fluorescent contaminants on surfaces

DOEpatents

Schuresko, Daniel D.

1980-01-01

A portable fluorescence-based spotter for polynuclear aromatic hydrocarbon contamination on personnel and work area surfaces under ambient lighting conditions is provided. This instrument employs beam modulation and phase sensitive detection for discriminating between fluorescence from organic materials from reflected background light and inorganic fluorescent material. The device uses excitation and emission filters to provide differentiation between classes of aromatic organic compounds. Certain inorganic fluorescent materials, including heavy metal compounds, may also be distinguished from the organic compounds, despite both having similar optical properties.

Electrochemical methods for monitoring of environmental carcinogens.

PubMed

Barek, J; Cvacka, J; Muck, A; Quaiserová, V; Zima, J

2001-04-01

The use of modern electroanalytical techniques, namely differential pulse polarography, differential pulse voltammetry on hanging mercury drop electrode or carbon paste electrode, adsorptive stripping voltammetry and high performance liquid chromatography with electrochemical detection for the determination of trace amounts of carcinogenic N-nitroso compounds, azo compounds, heterocyclic compounds, nitrated polycyclic aromatic hydrocarbons and aromatic and heterocyclic amines is discussed. Scope and limitations of these methods are described and some practical applications based on their combination with liquid-liquid or solid phase extraction are given.

Evaluation on simultaneous removal of particles and off-flavors using population balance for application of powdered activated carbon in dissolved air flotation process.

PubMed

Kwak, D H; Yoo, S J; Lee, E J; Lee, J W

2010-01-01

Most of the water treatment plants applying the DAF process are faced with off-flavors control problems. For simultaneous control of particles of impurities and dissolved organics that cause pungent taste and odor in water, an effective method would be the simple application of powdered activated carbon (PAC) in the DAF process. A series of experiments were carried out to explore the feasibility for simultaneous removal of kaolin particles and organic compounds that produce off-flavors (2-MIB and geosmin). In addition, the flotation efficiency of kaolin and PAC particles adsorbing organics in the DAF process was evaluated by employing the population balance theory. The removal efficiency of 2-MIB and geosmin under the treatment condition with kaolin particles for simultaneous treatment was lower than that of the individual treatment. The decrease in the removal efficiency was probably caused by 2-MIB and geosmin remaining in the PAC particle in the treated water of DAF after bubble flotation. Simulation results obtained by the population balance model indicate, that the initial collision-attachment efficiency of PAC particles was lower than that of kaolin particles.

Identification of Genes and Pathways Related to Phenol Degradation in Metagenomic Libraries from Petroleum Refinery Wastewater

PubMed Central

Silva, Cynthia C.; Hayden, Helen; Sawbridge, Tim; Mele, Pauline; De Paula, Sérgio O.; Silva, Lívia C. F.; Vidigal, Pedro M. P.; Vicentini, Renato; Sousa, Maíra P.; Torres, Ana Paula R.; Santiago, Vânia M. J.; Oliveira, Valéria M.

2013-01-01

Two fosmid libraries, totaling 13,200 clones, were obtained from bioreactor sludge of petroleum refinery wastewater treatment system. The library screening based on PCR and biological activity assays revealed more than 400 positive clones for phenol degradation. From these, 100 clones were randomly selected for pyrosequencing in order to evaluate the genetic potential of the microorganisms present in wastewater treatment plant for biodegradation, focusing mainly on novel genes and pathways of phenol and aromatic compound degradation. The sequence analysis of selected clones yielded 129,635 reads at an estimated 17-fold coverage. The phylogenetic analysis showed Burkholderiales and Rhodocyclales as the most abundant orders among the selected fosmid clones. The MG-RAST analysis revealed a broad metabolic profile with important functions for wastewater treatment, including metabolism of aromatic compounds, nitrogen, sulphur and phosphorus. The predicted 2,276 proteins included phenol hydroxylases and cathecol 2,3- dioxygenases, involved in the catabolism of aromatic compounds, such as phenol, byphenol, benzoate and phenylpropanoid. The sequencing of one fosmid insert of 33 kb unraveled the gene that permitted the host, Escherichia coli EPI300, to grow in the presence of aromatic compounds. Additionally, the comparison of the whole fosmid sequence against bacterial genomes deposited in GenBank showed that about 90% of sequence showed no identity to known sequences of Proteobacteria deposited in the NCBI database. This study surveyed the functional potential of fosmid clones for aromatic compound degradation and contributed to our knowledge of the biodegradative capacity and pathways of microbial assemblages present in refinery wastewater treatment system. PMID:23637911

Self-Assembly and Drug Release Capacities of Organogels via Some Amide Compounds with Aromatic Substituent Headgroups

PubMed Central

Zhang, Lexin; Jiao, Tifeng; Ma, Kai; Xing, Ruirui; Liu, Yamei; Xiao, Yong; Zhou, Jingxin; Zhang, Qingrui; Peng, Qiuming

2016-01-01

In this work, some amide compounds with different aromatic substituent headgroups were synthesized and their gelation self-assembly behaviors in 22 solvents were characterized as new gelators. The obtained results indicated that the size of aromatic substituent headgroups in molecular skeletons in gelators showed crucial effect in the gel formation and self-assembly behavior of all compounds in the solvents used. Larger aromatic headgroups in molecular structures in the synthesized gelator molecules are helpful to form various gel nanostructures. Morphological investigations showed that the gelator molecules can self-assembly and stack into various organized aggregates with solvent change, such as wrinkle, belt, rod, and lamella-like structures. Spectral characterizations suggested that there existed various weak interactions including π-π stacking, hydrogen bonding, and hydrophobic forces due to aromatic substituent headgroups and alkyl substituent chains in molecular structures. In addition, the drug release capacities experiments demonstrated that the drug release rate in present obtained gels can be tuned by adjusting the concentrations of dye. The present work would open up enormous insight to design and investigate new kind of soft materials with designed molecular structures and tunable drug release performance. PMID:28773663

Single kernel method for detection of 2-acetyl-1-pyrroline in aromatic rice germplasm using SPME-GC/MS

USDA-ARS?s Scientific Manuscript database

INTRODUCTION Aromatic rice or fragrant rice, (Oryza sativa L.), has a strong popcorn-like aroma due to the presence of a five-membered N-heterocyclic ring compound known as 2-acetyl-1-pyrroline (2-AP). To date, existing methods for detecting this compound in rice require the use of several kernels. ...

2,4,5-trihydroxy-3-methylacetophenone: A cellulosic chromophore as a case study of aromaticity

Treesearch

Nele Sophie Zwirchmayr; Thomas Elder; Markus Bacher; Andreas Hofinger-Horvath; Paul Kosma; Thomas Rosenau

2017-01-01

The title compound (2,4,5-trihydroxy-3-methylacetophenone, 1) was isolated as chromophore from aged cellulosic pulps. The peculiar feature of the compound is its weak aromatic system that can be converted into nonaromatic (quinoid or cyclic aliphatic) tautomers, depending on the conditions and reaction partners. In alkaline media, the participation of quinoid canonic...

Influence of extraction methodologies on the analysis of five major volatile aromatic compounds of citronella grass (Cymbopogon nardus) and lemongrass (Cymbopogon citratus) grown in Thailand

USDA-ARS?s Scientific Manuscript database

Infusions of citronella grass (Cymbopogon nardus) and lemongrass (Cymbopogon citratus) have been commonly used in folk medicine in Thailand and other Asian countries. This study focuses on a systematic comparison of two extraction methods for major volatile aromatic compounds (VACs) of citronella g...

Aerobic Biodegradation of Trichloroethylene.

DTIC Science & Technology

1987-07-01

into C02 and unidentified nonvolatile products. Phenol, 41 toiin- andq- cresol were found to replace the site water requirement for TCE metabolism...identified as phenol. Other aromatic compounds that could support TCE degradation were toluene, o- cresol , and m- cresol . The degradation could be...Production...... .. .. .. . 17 4. Test for the Catechol Ortho °Ring-Fission Pathway . 18 5. Oxidation of Aromatic Compounds ............. .18 6

The shikimate pathway: review of amino acid sequence, function and three-dimensional structures of the enzymes.

PubMed

Mir, Rafia; Jallu, Shais; Singh, T P

2015-06-01

The aromatic compounds such as aromatic amino acids, vitamin K and ubiquinone are important prerequisites for the metabolism of an organism. All organisms can synthesize these aromatic metabolites through shikimate pathway, except for mammals which are dependent on their diet for these compounds. The pathway converts phosphoenolpyruvate and erythrose 4-phosphate to chorismate through seven enzymatically catalyzed steps and chorismate serves as a precursor for the synthesis of variety of aromatic compounds. These enzymes have shown to play a vital role for the viability of microorganisms and thus are suggested to present attractive molecular targets for the design of novel antimicrobial drugs. This review focuses on the seven enzymes of the shikimate pathway, highlighting their primary sequences, functions and three-dimensional structures. The understanding of their active site amino acid maps, functions and three-dimensional structures will provide a framework on which the rational design of antimicrobial drugs would be based. Comparing the full length amino acid sequences and the X-ray crystal structures of these enzymes from bacteria, fungi and plant sources would contribute in designing a specific drug and/or in developing broad-spectrum compounds with efficacy against a variety of pathogens.

The influence of the Tbeta level upon fluorescence and laser properties of aromatic compounds.

PubMed

Nijegorodov, N; Winkoun, D P; Nkoma, J S

2004-07-01

The fluorescence and laser properties of seven specially chosen aromatic compounds are studied at 293 degrees C. The quantum yield of fluorescence, gamma, decay times, tauf, of the deaerated and non-deaerated solutions are measured. The oscillator strength, fe, fluorescence rate constants, kf, natural lifetimes, tauT0, and intersystem crossing rate constants, kST, are calculated. Some laser parameters are calculated or measured experimentally. It is found that the position of the Tbeta level plays an important role in the fluorescence and laser properties of aromatic compounds. If the Tbeta level is situated below the Sp level, it decreases the quantum yield of fluorescence and the decay time and increases the threshold of laser action. If, due to some structural changes of a molecule, the Tbeta level is situated higher than the Sp level, then the quantum yield of fluorescence and the decay times are increasing and the threshold of laser action is decreasing. Such influence of the position of the Tbeta level upon fluorescence and laser properties of aromatic compound is explained by the fact that the Sp level mixes with the Tbeta level more readily than with other taupipi* levels.

Adsorption of selected pharmaceuticals and an endocrine disrupting compound by granular activated carbon. 2. Model prediction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Z.; Peldszus, S.; Huck, P.M.

The adsorption of two representative pharmaceutically active compounds (PhACs) naproxen and carbamazepine and one endocrine disrupting compound (EDC) nonylphenol was studied in pilot-scale granular activated carbon (GAC) adsorbers using post-sedimentation (PS) water from a full-scale drinking water treatment plant. The GAC adsorbents were coal-based Calgon Filtrasorb 400 and coconut shell-based PICA CTIF TE. Acidic naproxen broke through fastest while nonylphenol was removed best, which was consistent with the degree to which fouling affected compound removals. Model predictions and experimental data were generally in good agreement for all three compounds, which demonstrated the effectiveness and robustness of the pore and surfacemore » diffusion model (PSDM) used in combination with the time-variable parameter approach for predicting removals at environmentally relevant concentrations (i.e., ng/L range). Sensitivity analyses suggested that accurate determination of film diffusion coefficients was critical for predicting breakthrough for naproxen and carbamazepine, in particular when high removals are targeted. Model simulations demonstrated that GAC carbon usage rates (CURs) for naproxen were substantially influenced by the empty bed contact time (EBCT) at the investigated conditions. Model-based comparisons between GAC CURs and minimum CURs for powdered activated carbon (PAC) applications suggested that PAC would be most appropriate for achieving 90% removal of naproxen, whereas GAC would be more suitable for nonylphenol. 25 refs., 4 figs., 1 tab.« less

Dramatic Influence of Ionic Liquid and Ultrasound Irradiation on the Electrophilic Sulfinylation of Aromatic Compounds by Sulfinic Esters.

PubMed

Nguyen, Ngoc-Lan Thi; Vo, Hong-Thom; Duus, Fritz; Luu, Thi Xuan Thi

2017-09-04

The sulfinylation reaction of aromatic and hetero-aromatic compounds with sulfinic esters as electrophiles has been investigated in different ionic liquids and by means of different Lewis acid salts in order to get moderate to good yields of asymmetrical sulfoxides. Mixtures of 1-butyl-3-methylimidazolium chloride and aluminum chloride were found to be the most efficient and recyclable reaction framework. Ultrasound sonication appeared to be the most useful and green activation method to afford the sulfoxides in yields better than or equivalent to those obtained under the longer-lasting conventional stirring conditions.

[Simultaneous analysis of aromatic aldehydes and coumarins with high pressure liquid chromatography. Application to wines and brandies stored in oak barrels].

PubMed

Salagoity-Auguste, M H; Tricard, C; Sudraud, P

1987-04-17

Aromatic aldehydes (vanillin, syringaldehyde, coniferaldehyde and sinapaldehyde) and coumarins (esculetin, umbelliferone, scopoletin and methylumbelliferone) are natural wood compounds. Storage of wines and brandies in oak barrels increases notably aldehydes and coumarins (particularly scopoletin) concentrations. These compounds were separated by high-performance liquid chromatography, on hydrocarbon bonded reversed-phase packings, with a water-acetonitrile elution gradient. They were first extracted from wines and brandies by diethyl ether and then injected on chromatographic column. A double detection was used to determine simultaneously aromatic aldehydes and coumarins by UV absorption and fluorescence respectively.

Characterization of organic aromatic compounds in soils affected by an uncontrolled tire landfill fire through the use of comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry.

PubMed

Escobar-Arnanz, J; Mekni, S; Blanco, G; Eljarrat, E; Barceló, D; Ramos, L

2018-02-09

Discarded vehicle tires have become an increasing concern worldwide due to the enormous amount of wastes generated and the increasing evidence of health problems associated to their disposal and accidental combustion. Previous studies conducted involving either simulated or open uncontrolled tire fires have identified aromatics belonging to two main classes, volatile organic compounds and polycyclic aromatic compounds (PAHs), as the most relevant chemicals generated in these burning processes. As a consequence, and due to their recognized toxicity, most studies reported up to now have mainly focused on these two categories of compounds being information concerning the possible occurrence of other aromatic classes rather limited. In this study, the enhanced separation power and structural confirmation capabilities provided by comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (GC×GC-ToF MS) has been used, for the first time, for the non-targeted analysis of soils impacted by a tire fire and an ash collected at the scene of the fire. In total, 118 volatile and semi-volatile aromatic compounds have been differentiated. Among them, 104 compounds have been either positively or tentatively identified. PAHs with 3-5 rings and their alkyl-derivatives were the most numerous and relevant classes in the investigated samples. A significant number of sulfur, oxygen- and nitrogen-containing PAHs were also detected in the samples. The application of a script function to the raw GC×GC-ToF MS data allowed the fast filtering and automatic recognition of compounds containing halogens in their structure. This part of the study evidenced that only a limited number of regulated persistent organic pollutants were present in the investigated samples. However, it also revealed the presence of emerging organophosphorous flame retardants, whose levels in tire fire impacted soils are reported for the first time. Copyright © 2017 Elsevier B.V. All rights reserved.

Volatile profiles of aromatic and non-aromatic rice

USDA-ARS?s Scientific Manuscript database

Rice is enjoyed by many people as a staple food because of its flavor and texture. Some scented varieties command a premium in the marketplace because of their distinctive aroma and flavor. The compound most commonly associated with the popcorn or nutty scent of aromatic rice is 2-acetyl-1-pyrroline...

Photocatalytic oxidation of aromatic amines using MnO2@g ...

EPA Pesticide Factsheets

An efficient and direct oxidation of aromatic amines to aromatic azo-compounds has been achieved using a MnO2@g-C3N4 catalyst under visible light as a source of energy at room temperature Prepared for submission to the journal, Advanced Materials Letters.

SIMULTANEOUS DTERMINATION OF CHROMATE AND AROMATIC HYDROCARBONS IN ENVIRONMENTAL SAMPLES BY CAPILLARY ELECTROPHORESIS

EPA Science Inventory

An analytical method was developed to determine simultaneously, the inorganic anion CrO2-4, and organic aromatic compounds including benzoate, 2-Cl-benzoate, phenol, m-cresol and o-/p-cresol by capillary electrophoresis (CE). Chromate and the aromatics were separated in a relativ...

High temperature normal phase liquid chromatography of aromatic hydrocarbons on bare zirconia.

PubMed

Paproski, Richard E; Liang, Chen; Lucy, Charles A

2011-11-04

The normal phase HPLC behavior of a bare zirconia column was studied at temperatures up to 200 °C using a hexane mobile phase. The use of elevated column temperatures significantly decreased the retention of twenty five aromatic model compounds according to the van't Hoff equation (>30-fold decrease for some compounds). Large improvements in peak shape, efficiency (>2.2-fold), aromatic group-type selectivity, and column re-equilibration times (>5-fold) were obtained at elevated temperatures. The thermal decomposition of two polar nitrogen compounds (indole and carbazole) was observed in a hexane/dichloromethane mobile phase at temperatures greater than 100 °C. The first order decomposition of carbazole was studied in further detail. Copyright © 2011 Elsevier B.V. All rights reserved.

Alkylation of organic aromatic compounds

DOEpatents

Smith, L.A. Jr.; Arganbright, R.P.; Hearn, D.

1993-09-07

Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a molecular sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene to about the mid point of the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 figures.

Alkylation of organic aromatic compounds

DOEpatents

Smith, Jr., Lawrence A.; Arganbright, Robert P.; Hearn, Dennis

1993-01-01

Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C.sub.2 to C.sub.10 olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80.degree. C. to 500.degree. C., using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene to about the mid point of the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms.

Determination of total and polycyclic aromatic hydrocarbons in aviation jet fuel.

PubMed

Bernabei, M; Reda, R; Galiero, R; Bocchinfuso, G

2003-01-24

The aviation jet fuel widely used in turbine engine aircraft is manufactured from straight-run kerosene. The combustion quality of jet fuel is largely related to the hydrocarbon composition of the fuel itself; paraffins have better burning properties than aromatic compounds, especially naphthalenes and light polycyclic aromatic hydrocarbons (PAHs), which are characterised as soot and smoke producers. For this reason the burning quality of fuel is generally measured as smoke fermation. This evaluation is carried out with UV spectrophotometric determination of total naphthalene hydrocarbons and a chromatographic analysis to determine the total aromatic compounds. These methods can be considered insufficient to evaluate the human health impact of these compounds due to their inability to measure trace (ppm) amounts of each aromatic hyrcarbon and each PAH in accordance with limitations imposed because of their toxicological properties. In this paper two analytical methods are presented. Both are based on a gas chromatographic technique with a mass detector operating in be selected ion monitoring mode. The first method was able to determine more than 60 aromatic hydrocarbons in a fuel sample in a 35-min chromatographic run, while the second was able to carry out the analysis of more than 30 PAHs in a 40-min chromatographic run. The linearity and sensitivity of the methods in measuring these analytes at trace levels are described.

Sulfur Transformation during Microwave and Conventional Pyrolysis of Sewage Sludge.

PubMed

Zhang, Jun; Zuo, Wei; Tian, Yu; Chen, Lin; Yin, Linlin; Zhang, Jie

2017-01-03

The sulfur distributions and evolution of sulfur-containing compounds in the char, tar and gas fractions were investigated during the microwave and conventional pyrolysis of sewage sludge. Increased accumulation of sulfur in the char and less production of H 2 S were obtained from microwave pyrolysis at higher temperatures (500-800 °C). Three similar conversion pathways were identified for the formation of H 2 S during microwave and conventional pyrolysis. The cracking of unstable mercaptan structure in the sludge contributed to the release of H 2 S below 300 °C. The decomposition of aliphatic-S compounds in the tars led to the formation of H 2 S (300-500 °C). The thermal decomposition of aromatic-S compounds in the tars generated H 2 S from 500 to 800 °C. However, the secondary decomposition of thiophene-S compounds took place only in conventional pyrolysis above 700 °C. Comparing the H 2 S contributions from microwave and conventional pyrolysis, the significant increase of H 2 S yields in conventional pyrolysis was mainly attributed to the decomposition of aromatic-S (increasing by 10.4%) and thiophene-S compounds (11.3%). Further investigation on the inhibition mechanism of H 2 S formation during microwave pyrolysis confirmed that, with the special heating characteristics and relative shorter residence time, microwave pyrolysis promoted the retention of H 2 S on CaO and inhibited the secondary cracking of thiophene-S compounds at higher temperatures.

Functional Group Analysis.

ERIC Educational Resources Information Center

Smith, Walter T., Jr.; Patterson, John M.

1984-01-01

Literature on analytical methods related to the functional groups of 17 chemical compounds is reviewed. These compounds include acids, acid azides, alcohols, aldehydes, ketones, amino acids, aromatic hydrocarbons, carbodiimides, carbohydrates, ethers, nitro compounds, nitrosamines, organometallic compounds, peroxides, phenols, silicon compounds,…

Selective cleavage of the C(α)-C(β) linkage in lignin model compounds via Baeyer-Villiger oxidation.

PubMed

Patil, Nikhil D; Yao, Soledad G; Meier, Mark S; Mobley, Justin K; Crocker, Mark

2015-03-21

Lignin is an amorphous aromatic polymer derived from plants and is a potential source of fuels and bulk chemicals. Herein, we present a survey of reagents for selective stepwise oxidation of lignin model compounds. Specifically, we have targeted the oxidative cleavage of Cα-Cβ bonds as a means to depolymerize lignin and obtain useful aromatic compounds. In this work, we prepared several lignin model compounds that possess structures, characteristic reactivity, and linkages closely related to the parent lignin polymer. We observed that selective oxidation of benzylic hydroxyl groups, followed by Baeyer-Villiger oxidation of the resulting ketones, successfully cleaves the Cα-Cβ linkage in these model compounds.

Chemoenzymatic syntheses of prenylated aromatic small molecules using Streptomyces prenyltransferases with relaxed substrate specificities

PubMed Central

Kumano, Takuto; Richard, Stéphane B.; Noel, Joseph P.; Nishiyama, Makoto; Kuzuyama, Tomohisa

2010-01-01

NphB is a soluble prenyltransferase from Streptomyces sp. strain CL190 that attaches a geranyl group to a 1,3,6,8-tetrahydroxynaphthalene-derived polyketide during the biosynthesis of anti-oxidant naphterpin. Here we report multiple chemoenzymatic syntheses of various prenylated compounds from aromatic substrates including flavonoids using two prenyltransferases NphB and SCO7190, a NphB homolog from Streptomyces coelicolor A3(2), as biocatalysts. NphB catalyzes carbon–carbon-based and carbon–oxygen-based geranylation of a diverse collection of hydroxyl-containing aromatic acceptors. Thus, this simple method using the prenyltransferases can be used to explore novel prenylated aromatic compounds with biological activities. Kinetic studies with NphB reveal that the prenylation reaction follows a sequential ordered mechanism. PMID:18682327

Di(hydroxyphenyl)- benzimidazole monomers

NASA Technical Reports Server (NTRS)

Connell, John W. (Inventor); Hergenrother, Paul M. (Inventor); Smith, Joseph G. (Inventor)

1993-01-01

Di(hydroxyphenyl)benzimidazole monomers were prepared from phenyl-hydroxybenzoate and aromatic bis(o-diamine)s. These monomers were used in the synthesis of soluble polybenzimidazoles. The reaction involved the aromatic nucleophilic displacement of various di(hydroxyphenyl)benzimidazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds in the presence of an alkali metal base. These polymers exhibited lower glass transition temperatures, improved solubility, and better compression moldability over their commercial counterparts.

Heterogeneous Diels–Alder catalysis for biomass-derived aromatic compounds

DOE PAGES

Settle, Amy E.; Berstis, Laura; Rorrer, Nicholas A.; ...

2017-05-17

In this tutorial review, we provide an overview of heterogeneous Diels–Alder catalysis for the production of lignocellulosic biomass-derived aromatic compounds. Diels–Alder reactions afford an extremely selective and efficient route for carbon–carbon cycloadditions to produce intermediates that can readily undergo subsequent dehydration or dehydrogenation reactions for aromatization. As a result, catalysis of Diels–Alder reactions with biomass-derived dienes and dienophiles has seen a growth of interest in recent years; however, significant opportunities remain to (i) tailor heterogeneous catalyst materials for tandem Diels–Alder and aromatization reactions, and (ii) utilize biomass-derived dienes and dienophiles to access both conventional and novel aromatic monomers. As such,more » this review discusses the mechanistic aspects of Diels–Alder reactions from both an experimental and computational perspective, as well as the synergy of Brønsted–Lewis acid catalysts to facilitate tandem Diels–Alder and aromatization reactions. Heterogeneous catalyst design strategies for Diels–Alder reactions are reviewed for two exemplary solid acid catalysts, zeolites and polyoxometalates, and recent efforts for targeting direct replacement aromatic monomers from biomass are summarized. In conclusion, we point out important research directions for progressing Diels–Alder catalysis to target novel, aromatic monomers with chemical functionality that enables new properties compared to monomers that are readily accessible from petroleum.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Edwin S. Olson; Kurt E. Eylands; Daniel J. Stepan

New federal drinking water regulations have been promulgated to restrict the levels of disinfection by-products (DBPs) in finished public water supplies. DBPs are suspected carcinogens and are formed when organic material is partially oxidized by disinfectants commonly used in the water treatment industry. Additional federal mandates are expected in the near future that will also affect public water suppliers with respect to DBPs. These new federal drinking water regulations may require public water suppliers to adjust treatment practices or incorporate additional treatment operations into their existing treatment trains. Many options have been identified, including membrane processes, granular activated carbon, poweredmore » activated carbon (PAC), enhanced coagulation and/or softening, and alternative disinfectants (e.g., chlorine dioxide, ozone, and chloramines). Of the processes being considered, PAC appears to offer an attractive benefit-to-cost advantage for many water treatment plants, particularly small systems (those serving fewer than 10,000 customers). PAC has traditionally been used by the water treatment industry for the removal of compounds contributing to taste and odor problems. PAC also has the potential to remove naturally occurring organic matter (NOM) from raw waters prior to disinfection, thus controlling the formation of regulated DBPs. Many small water systems are currently using PAC for taste and odor control and have the potential to use PAC for controlling DBPs. Activated carbons can be produced from a variety of raw materials, including wood, peat, coconut husks, and numerous types of coal. The Energy & Environmental Research Center (EERC) has been working on the development of a PAC product to remove NOM from surface water supplies to prevent the formation of carcinogenic DBPs during chlorination. During that study, the sodium and calcium content of the lignites showed a significant effect on the sorption capacity of the activated carbon product. As much as a 130% increase in the humic acid sorption capacity of a PAC produced from a high-sodium-content lignite was observed. We hypothesize that the sodium and calcium content of the coal plays a significant role in the development of pore structures and pore-size distribution, ultimately producing activated carbon products that have greater sorption capacity for specific contaminants, depending on molecular size.« less

The swarming motility of Pseudomonas aeruginosa is blocked by cranberry proanthocyanidins and other tannin-containing materials.

PubMed

O'May, Che; Tufenkji, Nathalie

2011-05-01

Bacterial motility plays a key role in the colonization of surfaces by bacteria and the subsequent formation of resistant communities of bacteria called biofilms. Derivatives of cranberry fruit, predominantly condensed tannins called proanthocyanidins (PACs) have been reported to interfere with bacterial adhesion, but the effects of PACs and other tannins on bacterial motilities remain largely unknown. In this study, we investigated whether cranberry PAC (CPAC) and the hydrolyzable tannin in pomegranate (PG; punicalagin) affected the levels of motilities exhibited by the bacterium Pseudomonas aeruginosa. This bacterium utilizes flagellum-mediated swimming motility to approach a surface, attaches, and then further spreads via the surface-associated motilities designated swarming and twitching, mediated by multiple flagella and type IV pili, respectively. Under the conditions tested, both CPAC and PG completely blocked swarming motility but did not block swimming or twitching motilities. Other cranberry-containing materials and extracts of green tea (also rich in tannins) were also able to block or impair swarming motility. Moreover, swarming bacteria were repelled by filter paper discs impregnated with many tannin-containing materials. Growth experiments demonstrated that the majority of these compounds did not impair bacterial growth. When CPAC- or PG-containing medium was supplemented with surfactant (rhamnolipid), swarming motility was partially restored, suggesting that the effective tannins are in part acting by a rhamnolipid-related mechanism. Further support for this theory was provided by demonstrating that the agar surrounding tannin-induced nonswarming bacteria was considerably less hydrophilic than the agar area surrounding swarming bacteria. This is the first study to show that natural compounds containing tannins are able to block P. aeruginosa swarming motility and that swarming bacteria are repelled by such compounds.

The Swarming Motility of Pseudomonas aeruginosa Is Blocked by Cranberry Proanthocyanidins and Other Tannin-Containing Materials▿

PubMed Central

O'May, Che; Tufenkji, Nathalie

2011-01-01

Bacterial motility plays a key role in the colonization of surfaces by bacteria and the subsequent formation of resistant communities of bacteria called biofilms. Derivatives of cranberry fruit, predominantly condensed tannins called proanthocyanidins (PACs) have been reported to interfere with bacterial adhesion, but the effects of PACs and other tannins on bacterial motilities remain largely unknown. In this study, we investigated whether cranberry PAC (CPAC) and the hydrolyzable tannin in pomegranate (PG; punicalagin) affected the levels of motilities exhibited by the bacterium Pseudomonas aeruginosa. This bacterium utilizes flagellum-mediated swimming motility to approach a surface, attaches, and then further spreads via the surface-associated motilities designated swarming and twitching, mediated by multiple flagella and type IV pili, respectively. Under the conditions tested, both CPAC and PG completely blocked swarming motility but did not block swimming or twitching motilities. Other cranberry-containing materials and extracts of green tea (also rich in tannins) were also able to block or impair swarming motility. Moreover, swarming bacteria were repelled by filter paper discs impregnated with many tannin-containing materials. Growth experiments demonstrated that the majority of these compounds did not impair bacterial growth. When CPAC- or PG-containing medium was supplemented with surfactant (rhamnolipid), swarming motility was partially restored, suggesting that the effective tannins are in part acting by a rhamnolipid-related mechanism. Further support for this theory was provided by demonstrating that the agar surrounding tannin-induced nonswarming bacteria was considerably less hydrophilic than the agar area surrounding swarming bacteria. This is the first study to show that natural compounds containing tannins are able to block P. aeruginosa swarming motility and that swarming bacteria are repelled by such compounds. PMID:21378043

Vertical Stratification of Peat Pore Water Dissolved Organic Matter Composition in a Peat Bog in Northern Minnesota: Pore Water DOM composition in a peat bog

DOE PAGES

Tfaily, Malak M.; Wilson, Rachel M.; Cooper, William T.; ...

2018-01-29

Here, we characterized dissolved organic matter (DOM) composition throughout the peat column at the Marcell S1 forested bog in northern Minnesota and tested the hypothesis that redox oscillations associated with cycles of wetting and drying at the surface of the fluctuating water table correlate with increased carbon, sulfur, and nitrogen turn over. We found significant vertical stratification of DOM molecular composition and excitation-emission matrix parallel factor analysis components within the peat column. In particular, the intermediate depth zone (~ 50 cm) was identified as a zone where maximum decomposition and turnover is taking place. Surface DOM was dominated by inputsmore » from surface vegetation. The intermediate depth zone was an area of high organic matter reactivity and increased microbial activity with diagenetic formation of many unique compounds, among them polycyclic aromatic compounds that contain both nitrogen and sulfur heteroatoms. These compounds have been previously observed in coal-derived compounds and were assumed to be responsible for coal's biological activity. Biological processes triggered by redox oscillations taking place at the intermediate depth zone of the peat profile at the S1 bog are assumed to be responsible for the formation of these heteroatomic PACs in this system. Alternatively, these compounds could stem from black carbon and nitrogen derived from fires that have occurred at the site in the past. Surface and deep DOM exhibited more similar characteristics, compared to the intermediate depth zone, with the deep layer exhibiting greater input of microbially degraded organic matter than the surface suggesting that the entire peat profile consists of similar parent material at different degrees of decomposition and that lateral and vertical advection of pore water from the surface to the deeper horizons is responsible for such similarities. Lastly, our findings suggest that molecular composition of DOM in peatland pore water is dynamic and is a function of ecosystem activity, water table, redox oscillation, and pore water advection.« less

Vertical Stratification of Peat Pore Water Dissolved Organic Matter Composition in a Peat Bog in Northern Minnesota: Pore Water DOM composition in a peat bog

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tfaily, Malak M.; Wilson, Rachel M.; Cooper, William T.

Here, we characterized dissolved organic matter (DOM) composition throughout the peat column at the Marcell S1 forested bog in northern Minnesota and tested the hypothesis that redox oscillations associated with cycles of wetting and drying at the surface of the fluctuating water table correlate with increased carbon, sulfur, and nitrogen turn over. We found significant vertical stratification of DOM molecular composition and excitation-emission matrix parallel factor analysis components within the peat column. In particular, the intermediate depth zone (~ 50 cm) was identified as a zone where maximum decomposition and turnover is taking place. Surface DOM was dominated by inputsmore » from surface vegetation. The intermediate depth zone was an area of high organic matter reactivity and increased microbial activity with diagenetic formation of many unique compounds, among them polycyclic aromatic compounds that contain both nitrogen and sulfur heteroatoms. These compounds have been previously observed in coal-derived compounds and were assumed to be responsible for coal's biological activity. Biological processes triggered by redox oscillations taking place at the intermediate depth zone of the peat profile at the S1 bog are assumed to be responsible for the formation of these heteroatomic PACs in this system. Alternatively, these compounds could stem from black carbon and nitrogen derived from fires that have occurred at the site in the past. Surface and deep DOM exhibited more similar characteristics, compared to the intermediate depth zone, with the deep layer exhibiting greater input of microbially degraded organic matter than the surface suggesting that the entire peat profile consists of similar parent material at different degrees of decomposition and that lateral and vertical advection of pore water from the surface to the deeper horizons is responsible for such similarities. Lastly, our findings suggest that molecular composition of DOM in peatland pore water is dynamic and is a function of ecosystem activity, water table, redox oscillation, and pore water advection.« less

Enantioselective simultaneous analysis of selected pharmaceuticals in environmental samples by ultrahigh performance supercritical fluid based chromatography tandem mass spectrometry.

PubMed

Camacho-Muñoz, Dolores; Kasprzyk-Hordern, Barbara; Thomas, Kevin V

2016-08-31

In order to assess the true impact of each single enantiomer of pharmacologically active compounds (PACs) in the environment, highly efficient, fast and sensitive analytical methods are needed. For the first time this paper focuses on the use of ultrahigh performance supercritical fluid based chromatography coupled to a triple quadrupole mass spectrometer to develop multi-residue enantioselective methods for chiral PACs in environmental matrices. This technique exploits the advantages of supercritical fluid chromatography, ultrahigh performance liquid chromatography and mass spectrometry. Two coated modified 2.5 μm-polysaccharide-based chiral stationary phases were investigated: an amylose tris-3,5-dimethylphenylcarbamate column and a cellulose tris-3-chloro-4-methylphenylcarbamate column. The effect of different chromatographic variables on chiral recognition is highlighted. This novel approach resulted in the baseline resolution of 13 enantiomers PACs (aminorex, carprofen, chloramphenicol, 3-N-dechloroethylifosfamide, flurbiprofen, 2-hydroxyibuprofen, ifosfamide, imazalil, naproxen, ofloxacin, omeprazole, praziquantel and tetramisole) and partial resolution of 2 enantiomers PACs (ibuprofen and indoprofen) under fast-gradient conditions (<10 min analysis time). The overall performance of the methods was satisfactory. The applicability of the methods was tested on influent and effluent wastewater samples. To the best of our knowledge, this is the first feasibility study on the simultaneous separation of chemically diverse chiral PACs in environmental matrices using ultrahigh performance supercritical fluid based chromatography coupled with tandem mass spectrometry. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis of photobleachable deep UV resists based on single component nonchemically amplified resist system

NASA Astrophysics Data System (ADS)

Kim, Kyoung-Seon; Kim, Su-Min; Park, Ji-Young; Kim, Jin-Baek

2006-03-01

In a general way, non-CARs consist of the matrix resins and photoactive compounds (PACs), and the dissolution properties of the resists are dependent on the amount of PACs. In common, I-line and G-line resists based on novolac and diazonaphthoquinone (DNQ) are typical non-CARs. But most PACs absorb much light in the deep UV, and they are poorly photobleached by deep UV exposure. This strong absorption of PACs prevents the deep UV light from reaching the bottom of the resist film, leading to scum and sloped pattern profiles. Several PACs which contain diazoketo groups have been reported for deep UV lithography. Our goal in this investigation is to find a proper resist that is processable without photoacid generator and induces both photobleaching in the deep UV regions and polarity change upon exposure. We thought diazoketo groups attached to the polymer side chains could give such effects. There is no necessity for the post-exposure bake step that is the cause of acid-diffusion. The diazoketo groups undergo the Wolff rearrangement upon irradiation in the deep UV, affording ketenes that react with water to provide base soluble photoproducts. The polymers were synthesized by radical copolymerization of 2-(2-diazo-3-oxo-butyryloxy)-ethyl methacrylate, 2-hydroxyethyl methacrylate, and γ-butyrolacton-2-yl methacrylate. The single component resist showed 0.7μm line and space patterns using a mercury-xenon lamp in a contact printing mode.

The Aspergillus niger faeB gene encodes a second feruloyl esterase involved in pectin and xylan degradation and is specifically induced in the presence of aromatic compounds.

PubMed

de Vries, Ronald P; vanKuyk, Patricia A; Kester, Harry C M; Visser, Jaap

2002-04-15

The faeB gene encoding a second feruloyl esterase from Aspergillus niger has been cloned and characterized. It consists of an open reading frame of 1644 bp containing one intron. The gene encodes a protein of 521 amino acids that has sequence similarity to that of an Aspergillus oryzae tannase. However, the encoded enzyme, feruloyl esterase B (FAEB), does not have tannase activity. Comparison of the physical characteristics and substrate specificity of FAEB with those of a cinnamoyl esterase from A. niger [Kroon, Faulds and Williamson (1996) Biotechnol. Appl. Biochem. 23, 255-262] suggests that they are in fact the same enzyme. The expression of faeB is specifically induced in the presence of certain aromatic compounds, but not in the presence of other constituents present in plant-cell-wall polysaccharides such as arabinoxylan or pectin. The expression profile of faeB in the presence of aromatic compounds was compared with the expression of A. niger faeA, encoding feruloyl esterase A (FAEA), and A. niger bphA, the gene encoding a benzoate-p-hydroxylase. All three genes have different subsets of aromatic compounds that induce their expression, indicating the presence of different transcription activating systems in A. niger that respond to aromatic compounds. Comparison of the activity of FAEA and FAEB on sugar-beet pectin and wheat arabinoxylan demonstrated that they are both involved in the degradation of both polysaccharides, but have opposite preferences for these substrates. FAEA is more active than FAEB towards wheat arabinoxylan, whereas FAEB is more active than FAEA towards sugar-beet pectin.

Contaminated sediments from tributaries of the Great Lakes: Chemical characterization and carcinogenic effects in medaka (Oryzias latipes)

USGS Publications Warehouse

Besser, John M.; Schmitt, Christopher J.; Harshbarger, John C.; Peterman, Paul H.; Lebo, Jon A.

1991-01-01

Sediments from four inshore industrial sites and a reference site in the Great Lakes were extracted with organic solvents to produce a crude extract, which was separated on alumina into two fractions: predominantly polycyclic aromatic hydrocarbons; and predominantly nitrogencontaining polycyclic aromatic compounds. Crude extracts were redissolved in acetone and analyzed by gas chromatography and gas chromatography-mass spectrometry. The acetone-redissolved crude extracts from the four industrialized sites contained 5.6–313.3 μg total polycyclic aromatic compounds/g sediment and 3.0–36.4 μg other compounds/g sediment. In addition to the typical EPA priority pollutants, a substantial amount (228.7 μg/g sediment) of alkyl-polycyclic-aromatic compounds was detected in sediments from one of the industrialized sites. Extracts from the reference site contained 1.55 μg total polycyclic aromatic compounds/ g sediment. Medaka (Oryzias latipes) were exposed to multiple pulse doses of acetone-redissolved extracts and fractions. Medaka were also exposed to a known carcinogen, methylazoxymethanol acetate, to verify that chemicals produced tumors in the test fish. Acetone-redissolved extracts and fractions from contaminated sediments were toxic to medaka. Fin erosion and non-neoplastic liver abnormalities were more prevalent in medaka after exposure to acetoneredissolved extracts and fractions from contaminated sediments. Neoplasms previously associated with chemical exposure in wild fishes were induced in medaka exposed to acetone-redissolved extracts and fractions from two of the contaminated sites, but not from the reference site or controls. These findings further support the hypothesis that chemical contaminants in sediments are involved in epizootics of neoplasms in wild fishes at contaminated sites.

The Aspergillus niger faeB gene encodes a second feruloyl esterase involved in pectin and xylan degradation and is specifically induced in the presence of aromatic compounds.

PubMed Central

de Vries, Ronald P; vanKuyk, Patricia A; Kester, Harry C M; Visser, Jaap

2002-01-01

The faeB gene encoding a second feruloyl esterase from Aspergillus niger has been cloned and characterized. It consists of an open reading frame of 1644 bp containing one intron. The gene encodes a protein of 521 amino acids that has sequence similarity to that of an Aspergillus oryzae tannase. However, the encoded enzyme, feruloyl esterase B (FAEB), does not have tannase activity. Comparison of the physical characteristics and substrate specificity of FAEB with those of a cinnamoyl esterase from A. niger [Kroon, Faulds and Williamson (1996) Biotechnol. Appl. Biochem. 23, 255-262] suggests that they are in fact the same enzyme. The expression of faeB is specifically induced in the presence of certain aromatic compounds, but not in the presence of other constituents present in plant-cell-wall polysaccharides such as arabinoxylan or pectin. The expression profile of faeB in the presence of aromatic compounds was compared with the expression of A. niger faeA, encoding feruloyl esterase A (FAEA), and A. niger bphA, the gene encoding a benzoate-p-hydroxylase. All three genes have different subsets of aromatic compounds that induce their expression, indicating the presence of different transcription activating systems in A. niger that respond to aromatic compounds. Comparison of the activity of FAEA and FAEB on sugar-beet pectin and wheat arabinoxylan demonstrated that they are both involved in the degradation of both polysaccharides, but have opposite preferences for these substrates. FAEA is more active than FAEB towards wheat arabinoxylan, whereas FAEB is more active than FAEA towards sugar-beet pectin. PMID:11931668

Organic composition of fogwater in the Texas-Louisiana gulf coast corridor

NASA Astrophysics Data System (ADS)

Raja, Suresh; Raghunathan, Ravikrishna; Kommalapati, Raghava R.; Shen, Xinhua; Collett, Jeffrey L.; Valsaraj, Kalliat T.

Fogwater and air samples were collected in Baton Rouge between November 2004-February 2005 and during February 2006 at Houston. Organic compounds present in the fog samples were detected, quantified and then grouped into different compound classes based on molecular size, solubility and polarity using gas chromatography/mass spectrometry, high performance liquid chromatography with diode array detection and ion chromatography. Organic compounds were grouped as n-alkanes, aromatics and polycyclic aromatics, carbonyls, alcohols, amides and esters. Organic compounds in fog and air samples in Houston indicated clear urban/industrial anthropogenic origin, while compounds detected in Baton Rouge fog and air samples showed a mix of both agricultural and urban/industrial anthropogenic inputs. Among the various polycyclic aromatic compounds detected, the total concentration of naphthalene and its derivatives was 2.8 μg m -3 in Houston and 0.08 μg m -3 in Baton Rouge air. Analysis of concentrations of organic compounds pre- and post- fog revealed that compounds with low vapor pressure had higher scavenging efficiency in fog sampled at the two locations. Concentrations of organic compounds in fog samples were higher than those predicted by conventional air-water Henry's law equilibrium. Observed higher concentrations in the aqueous phase were modeled accounting for surface adsorption and accumulation of gas phase species and the presence of humic-like substances in fogwater.

Comparative study of the affinity and metabolism of type I and type II binding quinoline carboxamide analogs by cytochrome P450 3A4

PubMed Central

Dahal, Upendra P.; Joswig-Jones, Carolyn; Jones, Jeffrey P.

2011-01-01

Compounds that coordinate to the heme-iron of cytochrome P450 (CYP) enzymes are assumed to increase metabolic stability. However, recently we observed that the type II binding quinoline carboxamide (QCA) compounds were metabolically less stable. To test if the higher intrinsic clearance of type II binding compounds relative to type I binding compounds is general for other metabolic transformations, we synthesized a library of QCA compounds that could undergo N-dealkylation, O-dealkylation, benzylic hydroxylation and aromatic hydroxylation. The results demonstrated that type II binding QCA analogs were metabolically less stable (2 to 12 fold) at sub-saturating concentration compared to type I binding counterparts for all the transformations. When the rates of different metabolic transformations between type I and type II binding compounds were compared, they were found to be in the order of N-demethylation>benzylic hydroxylation> O-demethylation> aromatic hydroxylation. Finally, for the QCA analogs with aza-heteroaromatic rings, we did not detect metabolism in aza-aromatic rings (pyridine, pyrazine, pyrimidine) indicating electronegativity of the nitrogen can change regioselectivity in CYP metabolism. PMID:22087535

INORGANIC COORDINATION POLYMERS. IV. THE ATTEMPTED REPLACEMENT OF ACETYLACETONATE LIGANDS WITH PICOLINATE LIGANDS,

DTIC Science & Technology

HETEROCYCLIC COMPOUNDS, PHOSPHENE OXIDES, BENZENE, CHROMIUM COMPOUNDS, CHEMICAL REAC, SYNTHESIS (CHEMISTRY), CHEMICAL ANALY, SPECTRA (INFRARED), ABSORPTION, DISPLACE, POLYMERIZATION, ORGANIC NITROGEN, AROMATIC COMPOUNDS.

Influence of light-curing sources on polymerization reaction kinetics of a restorative system.

PubMed

D'Alpino, Paulo H P; Svizero, Nádia R; Pereira, José C; Rueggeberg, Frederick A; Carvalho, Ricardo M; Pashley, David H

2007-02-01

To determine the effect of using a variety of commercial light-curing units on polymerization of a dentin-bonding agent (Adper Single Bond) and of a resin composite (Filtek Z250). Infrared (IR) spectra were obtained kinetically at one scan/second at 2 cm(-1) resolution for a period of 5 minutes and were analyzed for: maximum conversion rate (%/s), time into exposure when maximum rate occurred (seconds), conversion at maximum rate (%), and total conversion (%) at 300 seconds by comparison of aliphatic-to-aromatic absorption IR peak ratios, before and after polymerization. Light units used were: QTH 540 mW/cm2 (XL3000); LED 750 mW/cm2 (Elipar FreeLight 2); PAC 2,130 mW/cm2 (ARC II). Exposure followed manufacturers' recommendations: dentin bonding agent for 10 seconds, RC for 20 seconds (QTH), and 10 seconds (LED and PAC). Polymerization kinetics was evaluated at the bottom surface (2.5 mm thick) for the resin composite and as a thin film for the dentin bonding agent on the diamond surface of an attenuated total reflectance accessory in the IR spectrometer. Values (n = 5) were compared using ANOVA and Tukey's pairwise post-hoc test: pre-set alpha 0.05. PAC produced the highest total conversion and conversion rate for the resin composite (P < 0.05). Total conversion was lower for dentin bonding adhesive using PAC than with LED or QTH (P < 0.05). LED provided the highest proportion of conversion at the maximum rate with respect to conversion at 300 seconds for both materials. QTH demonstrated the lowest maximum rate value that occurred at a longer time into exposure (P < 0.05). Polymerization kinetic parameters varied greatly between the restorative materials as well as among light-curing unit types when compared to values observed when using a QTH light as control.

Synthetic approaches to aromatic belts: building up strain in macrocyclic polyarenes.

PubMed

Eisenberg, David; Shenhar, Roy; Rabinovitz, Mordecai

2010-08-01

This tutorial review discusses synthetic strategies towards aromatic belts, defined here as double-stranded conjugated macrocycles, such as [n]cyclacenes, [n]cyclophenacenes, Schlüter belt, and Vögtle belt. Their appeal stems, firstly, from the unique nature of their conjugation, having p orbitals oriented radially rather than perpendicular to the plane of the macrocycle. Secondly, as aromatic belts are model compounds of carbon nanotubes of different chiralities, a synthetic strategy towards the buildup of structural strain in these compounds could finally open a route towards rational chemical synthesis of carbon nanotubes. The elusiveness of these compounds has stimulated fascinating and ingenious synthetic strategies over the last decades. The various strategies are classified here by their approach to the buildup of structural strain, which is the main obstacle in the preparation of these curved polyarenes.

Biotransformation of petroleum hydrocarbons and microbial communities in seawater with oil dispersions and copepod feces.

PubMed

Størdal, Ingvild Fladvad; Olsen, Anders Johny; Jenssen, Bjørn Munro; Netzer, Roman; Altin, Dag; Brakstad, Odd Gunnar

2015-12-30

To determine biotransformation of components in crude oil dispersions in the presence of feces from marine copepods, dispersed oil was incubated alone, with the addition of clean or oil-containing feces. We hypothesized that the feces would contribute with nutrients to bacteria, and higher concentrations of oil-degrading bacteria, respectively. Presence of clean feces resulted in higher degradation of aromatic oil compounds, but lower degradation of n-alkanes. Presence of oil-containing feces resulted in higher degradation of n-alkanes. The effect of clean feces on aromatic compounds are suggested to be due to higher concentrations of nutrients in the seawater where aromatic degradation takes place, while the lower degradation of n-alkanes are suggested to be due to a preference by bacteria for feces over these compounds. Large aggregates were observed in oil dispersions with clean feces, which may cause sedimentation of un-weathered lipophilic oil compounds towards the seafloor if formed during oil spills. Copyright © 2015 Elsevier Ltd. All rights reserved.

Immobilized acclimated biomass-powdered activated carbon for the bioregeneration of granular activated carbon loaded with phenol and o-cresol.

PubMed

Toh, Run-Hong; Lim, Poh-Eng; Seng, Chye-Eng; Adnan, Rohana

2013-09-01

The objectives of the study are to use immobilized acclimated biomass and immobilized biomass-powdered activated carbon (PAC) as a novel approach in the bioregeneration of granular activated carbon (GAC) loaded with phenol and o-cresol, respectively, and to compare the efficiency and rate of the bioregeneration of the phenolic compound-loaded GAC using immobilized and suspended biomasses under varying GAC dosages. Bioregeneration of GAC loaded with phenol and o-cresol, respectively, was conducted in batch system using the sequential adsorption and biodegradation approach. The results showed that the bioregeneration efficiency of GAC loaded with phenol or o-cresol was basically the same irrespective of whether the immobilized or suspended biomass was used. Nonetheless, the duration for bioregeneration was longer under immobilized biomass. The beneficial effect of immobilized PAC-biomass for bioregeneration is the enhancement of the removal rate of the phenolic compounds via adsorption and the shortening of the bioregeneration duration. Copyright © 2013 Elsevier Ltd. All rights reserved.

Spectroscopic study of proflavine adsorption on the carbon nanotube surface.

PubMed

Buchelnikov, Anatoly S; Dovbeshko, Galina I; Voronin, Dmitry P; Trachevsky, Vladimir V; Kostjukov, Viktor V; Evstigneev, Maxim P

2014-01-01

Despite the fact that non-covalent interactions between various aromatic compounds and carbon nanotubes are being extensively investigated now, there is still a lack of understanding about the nature of such interactions. The present paper sheds light on one of the possible mechanisms of interaction between the typical aromatic dye proflavine and the carbon nanotube surface, namely, π-stacking between aromatic rings of these compounds. To investigate such a complexation, a qualitative analysis was performed by means of ultraviolet visible, infrared, and nuclear magnetic resonance spectroscopy. The data obtained suggest that π-stacking brings the major contribution to the stabilization of the complex between proflavine and the carbon nanotube.

Polyimidazoles Via Aromatic Nucleophilic Displacement

NASA Technical Reports Server (NTRS)

Connell, John W.; Hergenrother, Paul M.

1990-01-01

Experiments show variety of polyimidazoles prepared by aromatic nucleophilic displacement, from reactions of bisphenol imidazoles with activated difluoro compounds. Polyimidazoles have good mechanical properties making them suitable for use as films, moldings, and adhesives.

Synthesis and accumulation of aromatic aldehydes in an engineered strain of Escherichia coli.

PubMed

Kunjapur, Aditya M; Tarasova, Yekaterina; Prather, Kristala L J

2014-08-20

Aromatic aldehydes are useful in numerous applications, especially as flavors, fragrances, and pharmaceutical precursors. However, microbial synthesis of aldehydes is hindered by rapid, endogenous, and redundant conversion of aldehydes to their corresponding alcohols. We report the construction of an Escherichia coli K-12 MG1655 strain with reduced aromatic aldehyde reduction (RARE) that serves as a platform for aromatic aldehyde biosynthesis. Six genes with reported activity on the model substrate benzaldehyde were rationally targeted for deletion: three genes that encode aldo-keto reductases and three genes that encode alcohol dehydrogenases. Upon expression of a recombinant carboxylic acid reductase in the RARE strain and addition of benzoate during growth, benzaldehyde remained in the culture after 24 h, with less than 12% conversion of benzaldehyde to benzyl alcohol. Although individual overexpression results demonstrated that all six genes could contribute to benzaldehyde reduction in vivo, additional experiments featuring subset deletion strains revealed that two of the gene deletions were dispensable under the conditions tested. The engineered strain was next investigated for the production of vanillin from vanillate and succeeded in preventing formation of the byproduct vanillyl alcohol. A pathway for the biosynthesis of vanillin directly from glucose was introduced and resulted in a 55-fold improvement in vanillin titer when using the RARE strain versus the wild-type strain. Finally, synthesis of the chiral pharmaceutical intermediate L-phenylacetylcarbinol (L-PAC) was demonstrated from benzaldehyde and glucose upon expression of a recombinant mutant pyruvate decarboxylase in the RARE strain. Beyond allowing accumulation of aromatic aldehydes as end products in E. coli, the RARE strain expands the classes of chemicals that can be produced microbially via aldehyde intermediates.

[Preliminary determination of organic pollutants in agricultural fertilizers].

PubMed

Mo, Ce-hui; Li, Yun-hui; Cai, Quan-ying; Zeng, Qiao-yun; Wang, Bo-guang; Li, Hai-qin

2005-05-01

Organic pollutants such as polycyclic aromatic hydrocarbons (PAHs) in agricultural fertilizers are new problem deserved more study. Eight kinds of organic pollutants including 43 compounds classified as US EPA priority pollutants in twenty one agricultural fertilizers which were universally used in China were determined by Gas chromatography-mass spectrum (GC-MS). Three kinds of organic pollutants including more than 5 compounds were detected in most fertilizers, composing mainly of phthalic acid esters (PAEs), nitrobenzenes (NBs) and polycyclic aromatic hydrocarbons (PAHs). There were 26 compounds detected in at least one fertilizer, five of them especially PAEs detected in most fertilizer and even in all fertilizers. Benzo(a)pyrene, a strongly carcinogenic compound was detected in two fertilizers. Higher concentrations of compounds were determined in those fertilizers such as multifunction compound fertilizers and coated fertilizers.

Protonation at the aromatic ring of samarium benzophenone dianion species. Isolation and structural characterization of a samarium(III) enolate complex

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hou, Z.; Yoshimura, Takashi; Wakatsuki, Yasuo

1994-11-30

The reduction of aromatic compounds into their dihydro derivatives by dissolving metal/alcohol systems (the Birch reduction) is a useful methodology in organic synthesis. Of particular importance is the reduction of aromatic carbonyl compounds such as aromatic acids, esters, amides, and monoaryl ketones, which usually generates in situ useful metal enolate intermediates that upon further reaction with electrophiles yield a variety of cyclohexadiene derivatives. One of the possible processes to generate these metal enolate intermediates is thought to be the monoprotonation of dianionic species at the para position of the aromatic rings. On the other hand, the reduction of diaryl ketonesmore » by alkali metals in liquid ammonia or by lanthanide metals in THF/HMPA or DME has been well known to afford the corresponding ketone dianions. The first X-ray structure of metal ketone dianion complexes, [Yb([mu]-[eta][sup 1],[eta][sup 2]-OCPh[sub 2]) (HMPA)[sub 2

Metal Triflates for the Production of Aromatics from Lignin.

PubMed

Deuss, Peter J; Lahive, Ciaran W; Lancefield, Christopher S; Westwood, Nicholas J; Kamer, Paul C J; Barta, Katalin; de Vries, Johannes G

2016-10-20

The depolymerization of lignin into valuable aromatic chemicals is one of the key goals towards establishing economically viable biorefineries. In this contribution we present a simple approach for converting lignin to aromatic monomers in high yields under mild reaction conditions. The methodology relies on the use of catalytic amounts of easy-to-handle metal triflates (M(OTf) x ). Initially, we evaluated the reactivity of a broad range of metal triflates using simple lignin model compounds. More advanced lignin model compounds were also used to study the reactivity of different lignin linkages. The product aromatic monomers were either phenolic C2-acetals obtained by stabilization of the aldehyde cleavage products by reaction with ethylene glycol or methyl aromatics obtained by catalytic decarbonylation. Notably, when the method was ultimately tested on lignin, especially Fe(OTf) 3 proved very effective and the phenolic C2-acetal products were obtained in an excellent, 19.3±3.2 wt % yield. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Aromatic derivatives of 1H-2,3-dihydropyrazolo(4,5-b)-1,5-diazepine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Orlov, V.D.; Kiroga, Kh.; Kolos, N.N.

1987-09-01

Aromatic derivatives of 1H-2,3-dihydropyrazole(4,5-b)-1,5-diazepine were obtained by the reaction of 1-phenyl-3-methyl-4,5-diaminopyrazole with chalcones and acetylarenes, catalyzed by acetic or sulfuric acid. The seven-membered ring in these compounds has a conformation of the boat type. The IR, UV, PMR, and mass spectra of the compounds are discussed.

Sorption of the Aircraft Deicing Fluid Component Methyl-Benzotriazole in Soil

DTIC Science & Technology

1999-03-01

Atlas , Ronald M., Bartha , Richard, Microbial Ecology : Fundamentals and Applications. Benjamin Cummings: Redwood City, 1993. Ball, William P., Roberts...cell; transfer of substances from one medium to another [ Atlas and Bartha , 533; Fetter, 117]. (2) The process by which a compound in solution or...oxygen, low redox potential. [ Atlas and Bartha , 534; Schwarzenbach et al, 410] Aromatic compound - Carbon skeletons containing aromatic benzene ring and

Puget Sound Dredged Disposal Analysis: Management Plan Assessment Report. Dredged Material Management Year 1990.

DTIC Science & Technology

1991-03-01

Sulfides BT Bioaccumulation Trigger L LP Ccn tract Laboratory Methods COC Chemical of Concern Corps U.S. Army Corps of Engineers cm centimeter cy cubic... Hydrocarbon (Compound) LOD Limit of Detection LPAH Low Molecular Weight Polynuclear Aromatic Hydrocarbon (Compound) MCLP Modified Contract Laboratory Method...Aromatic Hydrocarbons (HPAHs) (8 samples); * Benzofluoranthenes (7 samples); * Anthracene (6 samples); * Benzo(a)anthracene (6 samples); * Dibenzo(a,h

Al-based metal-organic gels for selective fluorescence recognition of hydroxyl nitro aromatic compounds

NASA Astrophysics Data System (ADS)

Guo, Mao Xia; Yang, Liu; Jiang, Zhong Wei; Peng, Zhe Wei; Li, Yuan Fang

2017-12-01

The novel class of luminescent Al3 +-based metal-organic gels (Al-MOGs) have been developed by mix 4-[2,2‧:6‧,2″-terpyridine]-4‧-ylbenzoic acid (Hcptpy) with Al3 + under mild condition. The as-prepared Al-MOGs have not only multiple stimuli-responsive properties, but selective recognition of hydroxyl nitro aromatic compounds, which can quench the fluorescence of the Al-MOGs, while other nitro aromatic analogues without hydroxyl substitutes cannot. The fluorescence of Al-MOGs at 467 nm was seriously quenched by picric acid (PA) whose lowest unoccupied molecular orbital (LUMO) energy levels are lower than those of three other hydroxyl nitro aromatic compounds including 4-nitrophenol (4-NP), 3,5-dinitrosalicylic acid (3,5-DNTSA) and 2,4-dinitrophenol (2,4-DNP). Thus, PA was chosen as a model compound under optimal conditions and the relative fluorescence intensity of Al-MOGs was proportional to the concentration of PA in the range of 5.0-320.0 μM with a detection limit of 4.64 μM. Furthermore, the fluorescence quenching mechanism has also been investigated and revealed that the quenching was attributed to inner filter effects (IFEs), as well as electron transfer (ET) between Al-MOGs and PA.

Al-based metal-organic gels for selective fluorescence recognition of hydroxyl nitro aromatic compounds.

PubMed

Guo, Mao Xia; Yang, Liu; Jiang, Zhong Wei; Peng, Zhe Wei; Li, Yuan Fang

2017-12-05

The novel class of luminescent Al 3+ -based metal-organic gels (Al-MOGs) have been developed by mix 4-[2,2':6',2″-terpyridine]-4'-ylbenzoic acid (Hcptpy) with Al 3+ under mild condition. The as-prepared Al-MOGs have not only multiple stimuli-responsive properties, but selective recognition of hydroxyl nitro aromatic compounds, which can quench the fluorescence of the Al-MOGs, while other nitro aromatic analogues without hydroxyl substitutes cannot. The fluorescence of Al-MOGs at 467nm was seriously quenched by picric acid (PA) whose lowest unoccupied molecular orbital (LUMO) energy levels are lower than those of three other hydroxyl nitro aromatic compounds including 4-nitrophenol (4-NP), 3,5-dinitrosalicylic acid (3,5-DNTSA) and 2,4-dinitrophenol (2,4-DNP). Thus, PA was chosen as a model compound under optimal conditions and the relative fluorescence intensity of Al-MOGs was proportional to the concentration of PA in the range of 5.0-320.0μM with a detection limit of 4.64μM. Furthermore, the fluorescence quenching mechanism has also been investigated and revealed that the quenching was attributed to inner filter effects (IFEs), as well as electron transfer (ET) between Al-MOGs and PA. Copyright © 2017 Elsevier B.V. All rights reserved.

Organic compounds in produced waters from coalbed natural gas wells in the Powder River Basin, Wyoming, USA

USGS Publications Warehouse

Orem, W.H.; Tatu, C.A.; Lerch, H.E.; Rice, C.A.; Bartos, T.T.; Bates, A.L.; Tewalt, S.; Corum, M.D.

2007-01-01

The organic composition of produced water samples from coalbed natural gas (CBNG) wells in the Powder River Basin, WY, sampled in 2001 and 2002 are reported as part of a larger study of the potential health and environmental effects of organic compounds derived from coal. The quality of CBNG produced waters is a potential environmental concern and disposal problem for CBNG producers, and no previous studies of organic compounds in CBNG produced water have been published. Organic compounds identified in the produced water samples included: phenols, biphenyls, N-, O-, and S-containing heterocyclic compounds, polycyclic aromatic hydrocarbons (PAHs), aromatic amines, various non-aromatic compounds, and phthalates. Many of the identified organic compounds (phenols, heterocyclic compounds, PAHs) are probably coal-derived. PAHs represented the group of organic compounds most commonly observed. Concentrations of total PAHs ranged up to 23 ??g/L. Concentrations of individual compounds ranged from about 18 to <0.01 ??g/L. Temporal variability of organic compound concentrations was documented, as two wells with relatively high organic compound contents in produced water in 2001 had much lower concentrations in 2002. In many areas, including the PRB, coal strata provide aquifers for drinking water wells. Organic compounds observed in produced water are also likely present in drinking water supplied from wells in the coal. Some of the organic compounds identified in the produced water samples are potentially toxic, but at the levels measured in these samples are unlikely to have acute health effects. The human health effects of low-level, chronic exposure to coal-derived organic compounds in drinking water are currently unknown. Continuing studies will evaluate possible toxic effects from low level, chronic exposure to coal-derived organic compounds in drinking water supplies.

University and Secondary School Students' Misconceptions about the Concept of "Aromaticity" in Organic Chemistry

ERIC Educational Resources Information Center

Topal, Giray; Oral, Behcet; Ozden. Mustafa

2007-01-01

Aromaticity concept is given incorrect or incomplete to the student in secondary education and knowledge based on this basic concept has been caused to another misconception in future. How are the achievement levels relating to the comprehension of various characteristics of aromatic compounds for the first and third grade students attending…

Two novel aromatic glucosides, marylaurencinosides D and E, from the fresh flowers of Cymbidium Great Flower 'Marylaurencin'.

PubMed

Yoshikawa, Kazuko; Okahuji, Mariko; Iseki, Kanako; Ito, Takuya; Asakawa, Yoshinori; Kawano, Sachiko; Hashimoto, Toshihiro

2014-04-01

Two novel aromatic glucosides, named marylaurencinosides D (1) and E (2), were isolated from the fresh flowers of Cymbidium Great Flower 'Marylaurencin'. In addition, eight known aromatic compounds (3-10) were isolated. These structures were determined on the basis of NMR experiments as well as chemical evidence.

Doped polycyclic aromatic hydrocarbons as building blocks for nanoelectronics: a theoretical study.

PubMed

Dral, Pavlo O; Kivala, Milan; Clark, Timothy

2013-03-01

Density functional theory (DFT) and semiempirical UHF natural orbital configuration interaction (UNO-CI) calculations are used to investigate the effect of heteroatom substitution at the central position of a model polycyclic aromatic hydrocarbon. The effects of the substitution on structure, strain, electronic and spectral properties, and aromaticity of the compounds are discussed.

Colonic catabolism of dietary phenolic and polyphenolic compounds from Concord grape juice.

PubMed

Stalmach, Angelique; Edwards, Christine A; Wightman, Jolynne D; Crozier, Alan

2013-01-01

After acute ingestion of 350 ml of Concord grape juice, containing 528 μmol of (poly)phenolic compounds, by healthy volunteers, a wide array of phase I and II metabolites were detected in the circulation and excreted in urine. Ingestion of the juice by ileostomists resulted in 40% of compounds being recovered intact in ileal effluent. The current study investigated the fate of these undigested (poly)phenolic compounds on reaching the colon. This was achieved through incubation of the juice using an in vitro model of colonic fermentation and through quantification of catabolites produced after colonic degradation and their subsequent absorption prior to urinary excretion by healthy subjects and ileostomy volunteers. A total of 16 aromatic and phenolic compounds derived from colonic metabolism of Concord grape juice (poly)phenolic compounds were identified by GC-MS in the faecal incubation samples. Thirteen urinary phenolic acids and aromatic compounds were excreted in significantly increased amounts after intake of the juice by healthy volunteers, whereas only two of these compounds were excreted in elevated amounts by ileostomists. The production of phenolic acids and aromatic compounds by colonic catabolism contributed to the bioavailability of Concord grape (poly)phenolic compounds to a much greater extent than phase I and II metabolites originating from absorption in the upper gastrointestinal tract. Catabolic pathways are proposed, highlighting the impact of colonic microbiota and subsequent phase II metabolism prior to excretion of phenolic compounds derived from (poly)phenolic compounds in Concord grape juice, which pass from the small to the large intestine.

δ 13C of free and macromolecular aromatic structures in the murchison meteorite

NASA Astrophysics Data System (ADS)

Sephton, M. A.; Pillinger, C. T.; Gilmour, I.

1998-05-01

Analyses of the organic compounds in the Murchison meteorite have led to a greater understanding of the nature of extraterrestrial organic materials. However, the relationship between low and high molecular weight material remains poorly understood. To investigate this relationship, untreated Murchison was subjected to supercritical fluid extraction (SFE) to obtain the free organic components in the meteorite. Toluene and other volatile aromatic hydrocarbons dominated the extract, and the carbon isotopic composition of these molecules was determined by gas chromatography-isotope ratio-mass spectrometry (GCIRMS). δ 13C values of the aromatic hydrocarbons ranged from -28.8 to -5.8‰. These compounds displayed a 13C-enrichment with increasing carbon number suggesting an origin by cracking. The high molecular weight organic material in the meteorite was isolated and subjected to hydrous pyrolysis. This procedure produced a number of aromatic products, the majority of which were volatile aromatic hydrocarbons, particularly toluene. SFE was used to extract and successfully retain them. This enabled the first carbon isotopic analysis of this poorly understood material to be performed at the molecular level by GCIRMS. δ 13C values for aromatic pyrolysis products occupied a range from -24.6 to -5.6‰. The trend of 13C-enrichment with increasing carbon number, observed in the free compounds, was also evident in the macromolecular fragments. Furthermore, the organic fragments of the macromolecular material were consistently 13C-enriched when compared to structurally identical free molecules. This suggested that the free aromatic hydrocarbons in Murchison were produced by the preterrestrial degradation of the organic macromolecular material. This natural degradation event was extended by the hydrous pyrolysis experiment.

Safety in the Chemical Laboratory: Nitric Acid, Nitrates, and Nitro Compounds.

ERIC Educational Resources Information Center

Bretherick, Leslie

1989-01-01

Discussed are the potential hazards associated with nitric acid, inorganic and organic nitrate salts, alkyl nitrates, acyl nitrates, aliphatic nitro compounds, aromatic nitro compounds, and nitration reactions. (CW)

Determination of Aromatic Ring Number Using Multi-Channel Deep UV Native Fluorescence

NASA Technical Reports Server (NTRS)

Bhartia, R.; McDonald, G. D.; Salas, E.; Conrad, P.

2004-01-01

The in situ detection of organic material on an extraterrestrial surface requires both effective means of searching a relatively large surface area or volume for possible organic carbon, and a more specific means of identifying and quantifying compounds in indicated samples. Fluorescence spectroscopy fits the first requirement well, as it can be carried out rapidly, with minimal or no physical contact with the sample, and with sensitivity unmatched by any other organic analytical technique. Aromatic organic compounds with know fluorescence signatures have been identified in several extraterrestrial samples, including carbonaceous chondrites, interplanetary dust particles, and Martian meteorites. The compound distributions vary among these sources, however, with clear differences in relative abundances by number of aromatic rings and by degree of alkylation. This relative abundance information, therefore, can be used to infer the source of organic material detected on a planetary surface.

Synthesis and biological evaluation of novel bis-aromatic amides as novel PTP1B inhibitors.

PubMed

Wang, Wen-Long; Huang, Chao; Gao, Li-Xin; Tang, Chun-Lan; Wang, Jun-Qing; Wu, Min-Chen; Sheng, Li; Chen, Hai-Jun; Nan, Fa-Jun; Li, Jing-Ya; Li, Jia; Feng, Bainian

2014-04-15

A series of bis-aromatic amides was designed, synthesized, and evaluated as a new class of inhibitors with IC50 values in the micromolar range against protein tyrosine phosphatase 1B (PTP1B). Among them, compound 15 displayed an IC50 value of 2.34±0.08 μM with 5-fold preference over TCPTP. More importantly, the treatment of CHO/HIR cells with compound 15 resulted in increased phosphorylation of insulin receptor (IR), which suggested extensive cellular activity of compound 15. These results provided novel lead compounds for the design of inhibitors of PTP1B as well as other PTPs. Copyright © 2014 Elsevier Ltd. All rights reserved.

Application of capillary gas chromatography mass spectrometry/computer techniques to synoptic survey of organic material in bed sediment

USGS Publications Warehouse

Steinheimer, T.R.; Pereira, W.E.; Johnson, S.M.

1981-01-01

A bed sediment sample taken from an area impacted by heavy industrial activity was analyzed for organic compounds of environmental significance. Extraction was effected on a Soxhlet apparatus using a freeze-dried sample. The Soxhlet extract was fractionated by silica gel micro-column adsorption chromatography. Separation and identification of the organic compounds was accomplished by capillary gas chromatography/mass spectrometry techniques. More than 50 compounds were identified; these include saturated hydrocarbons, olefins, aromatic hydrocarbons, alkylated polycyclic aromatic hydrocarbons, and oxygenated compounds such as aldehydes and ketones. The role of bed sediments as a source or sink for organic pollutants is discussed. ?? 1981.

Theoretical and experimental study of polycyclic aromatic compounds as β-tubulin inhibitors.

PubMed

Olazarán, Fabian E; García-Pérez, Carlos A; Bandyopadhyay, Debasish; Balderas-Rentería, Isaias; Reyes-Figueroa, Angel D; Henschke, Lars; Rivera, Gildardo

2017-03-01

In this work, through a docking analysis of compounds from the ZINC chemical library on human β-tubulin using high performance computer cluster, we report new polycyclic aromatic compounds that bind with high energy on the colchicine binding site of β-tubulin, suggesting three new key amino acids. However, molecular dynamic analysis showed low stability in the interaction between ligand and receptor. Results were confirmed experimentally in in vitro and in vivo models that suggest that molecular dynamics simulation is the best option to find new potential β-tubulin inhibitors. Graphical abstract Bennett's acceptance ratio (BAR) method.

Tough, high performance, addition-type thermoplastic polymers

NASA Technical Reports Server (NTRS)

Pater, Ruth H. (Inventor)

1992-01-01

A tough, high performance polyimide is provided by reacting a triple bond conjugated with an aromatic ring in a bisethynyl compound with the active double bond in a compound containing a double bond activated toward the formation of a Diels-Adler type adduct, especially a bismaleimide, a biscitraconimide, or a benzoquinone, or mixtures thereof. Addition curing of this product produces a high linear polymeric structure and heat treating the highly linear polymeric structure produces a thermally stable aromatic addition-type thermoplastic polyimide, which finds utility in the preparation of molding compounds, adhesive compositions, and polymer matrix composites.

Alkyne Benzannulation Reactions for the Synthesis of Novel Aromatic Architectures.

PubMed

Hein, Samuel J; Lehnherr, Dan; Arslan, Hasan; J Uribe-Romo, Fernando; Dichtel, William R

2017-11-21

Aromatic compounds and polymers are integrated into organic field effect transistors, light-emitting diodes, photovoltaic devices, and redox-flow batteries. These compounds and materials feature increasingly complex designs, and substituents influence energy levels, bandgaps, solution conformation, and crystal packing, all of which impact performance. However, many polycyclic aromatic hydrocarbons of interest are difficult to prepare because their substitution patterns lie outside the scope of current synthetic methods, as strategies for functionalizing benzene are often unselective when applied to naphthalene or larger systems. For example, cross-coupling and nucleophilic aromatic substitution reactions rely on prefunctionalized arenes, and even directed metalation methods most often modify positions near Lewis basic sites. Similarly, electrophilic aromatic substitutions access single regioisomers under substrate control. Cycloadditions provide a convergent route to densely functionalized aromatic compounds that compliment the above methods. After surveying cycloaddition reactions that might be used to modify the conjugated backbone of poly(phenylene ethynylene)s, we discovered that the Asao-Yamamoto benzannulation reaction is notably efficient. Although this reaction had been reported a decade earlier, its scope and usefulness for synthesizing complex aromatic systems had been under-recognized. This benzannulation reaction combines substituted 2-(phenylethynyl)benzaldehydes and substituted alkynes to form 2,3-substituted naphthalenes. The reaction tolerates a variety of sterically congested alkynes, making it well-suited for accessing poly- and oligo(ortho-arylene)s and contorted hexabenzocoronenes. In many cases in which asymmetric benzaldehyde and alkyne cycloaddition partners are used, the reaction is regiospecific based on the electronic character of the alkyne substrate. Recognizing these desirable features, we broadened the substrate scope to include silyl- and halogen-substituted alkynes. Through a combined experimental and computational approach, we have elucidated mechanistic insight and key principles that govern the regioselectivity outcome of the benzannulation of structurally diverse alkynes. We have applied these methods to prepare sterically hindered, shape-persistent aromatic systems, heterocyclic aromatic compounds, functionalized 2-aryne precursors, polyheterohalogenated naphthalenes, ortho-arylene foldamers, and graphene nanoribbons. As a result of these new synthetic avenues, aromatic structures with interesting properties were uncovered such as ambipolar charge transport in field effect transistors based on our graphene nanoribbons, conformational aspects of ortho-arylene architectures resulting from intramolecular π-stacking, and modulation of frontier molecular orbitals via protonation of heteroatom containing aromatic systems. Given the availability of many substituted 2-(phenylethynyl)benzaldehydes and the regioselectivity of the benzannulation reaction, naphthalenes can be prepared with control of the substitution pattern at seven of the eight substitutable positions. Researchers in a range of fields are likely to benefit directly from newly accessible molecular and polymeric systems derived from polyfunctionalized naphthalenes.

40 CFR 442.2 - General definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

..., organic chemicals including: alcohols, aldehydes, formaldehydes, phenols, peroxides, organic salts, amines, amides, other nitrogen compounds, other aromatic compounds, aliphatic organic chemicals, glycols, glycerines, and organic polymers; refractory organic compounds including: ketones, nitriles, organo-metallic...

Adsorption uptake of synthetic organic chemicals by carbon nanotubes and activated carbons.

PubMed

Brooks, A J; Lim, Hyung-nam; Kilduff, James E

2012-07-27

Carbon nanotubes (CNTs) have shown great promise as high performance materials for adsorbing priority pollutants from water and wastewater. This study compared uptake of two contaminants of interest in drinking water treatment (atrazine and trichloroethylene) by nine different types of carbonaceous adsorbents: three different types of single walled carbon nanotubes (SWNTs), three different sized multi-walled nanotubes (MWNTs), two granular activated carbons (GACs) and a powdered activated carbon (PAC). On a mass basis, the activated carbons exhibited the highest uptake, followed by SWNTs and MWNTs. However, metallic impurities in SWNTs and multiple walls in MWNTs contribute to adsorbent mass but do not contribute commensurate adsorption sites. Therefore, when uptake was normalized by purity (carbon content) and surface area (instead of mass), the isotherms collapsed and much of the CNT data was comparable to the activated carbons, indicating that these two characteristics drive much of the observed differences between activated carbons and CNT materials. For the limited data set here, the Raman D:G ratio as a measure of disordered non-nanotube graphitic components was not a good predictor of adsorption from solution. Uptake of atrazine by MWNTs having a range of lengths and diameters was comparable and their Freundlich isotherms were statistically similar, and we found no impact of solution pH on the adsorption of either atrazine or trichloroethylene in the range of naturally occurring surface water (pH = 5.7-8.3). Experiments were performed using a suite of model aromatic compounds having a range of π-electron energy to investigate the role of π-π electron donor-acceptor interactions on organic compound uptake by SWNTs. For the compounds studied, hydrophobic interactions were the dominant mechanism in the uptake by both SWNTs and activated carbon. However, comparing the uptake of naphthalene and phenanthrene by activated carbon and SWNTs, size exclusion effects appear to be more pronounced with activated carbon materials, perhaps due to smaller pore sizes or larger adsorption surface areas in small pores.

Adsorption uptake of synthetic organic chemicals by carbon nanotubes and activated carbons

NASA Astrophysics Data System (ADS)

Brooks, A. J.; Lim, Hyung-nam; Kilduff, James E.

2012-07-01

Carbon nanotubes (CNTs) have shown great promise as high performance materials for adsorbing priority pollutants from water and wastewater. This study compared uptake of two contaminants of interest in drinking water treatment (atrazine and trichloroethylene) by nine different types of carbonaceous adsorbents: three different types of single walled carbon nanotubes (SWNTs), three different sized multi-walled nanotubes (MWNTs), two granular activated carbons (GACs) and a powdered activated carbon (PAC). On a mass basis, the activated carbons exhibited the highest uptake, followed by SWNTs and MWNTs. However, metallic impurities in SWNTs and multiple walls in MWNTs contribute to adsorbent mass but do not contribute commensurate adsorption sites. Therefore, when uptake was normalized by purity (carbon content) and surface area (instead of mass), the isotherms collapsed and much of the CNT data was comparable to the activated carbons, indicating that these two characteristics drive much of the observed differences between activated carbons and CNT materials. For the limited data set here, the Raman D:G ratio as a measure of disordered non-nanotube graphitic components was not a good predictor of adsorption from solution. Uptake of atrazine by MWNTs having a range of lengths and diameters was comparable and their Freundlich isotherms were statistically similar, and we found no impact of solution pH on the adsorption of either atrazine or trichloroethylene in the range of naturally occurring surface water (pH = 5.7-8.3). Experiments were performed using a suite of model aromatic compounds having a range of π-electron energy to investigate the role of π-π electron donor-acceptor interactions on organic compound uptake by SWNTs. For the compounds studied, hydrophobic interactions were the dominant mechanism in the uptake by both SWNTs and activated carbon. However, comparing the uptake of naphthalene and phenanthrene by activated carbon and SWNTs, size exclusion effects appear to be more pronounced with activated carbon materials, perhaps due to smaller pore sizes or larger adsorption surface areas in small pores.

Photo-oxidation method using MoS2 nanocluster materials

DOEpatents

Wilcoxon, Jess P.

2001-01-01

A method of photo-oxidizing a hydrocarbon compound is provided by dispersing MoS.sub.2 nanoclusters in a solvent containing a hydrocarbon compound contaminant to form a stable solution mixture and irradiating the mixture to photo-oxide the hydrocarbon compound. Hydrocarbon compounds of interest include aromatic hydrocarbon and chlorinated hydrocarbons. MoS.sub.2 nanoclusters with an average diameter less than approximately 10 nanometers are shown to be effective in decomposing potentially toxic aromatic and chlorinated hydrocarbons, such as phenol, pentachlorophenol, chlorinated biphenols, and chloroform, into relatively non-toxic compounds. The irradiation can occur by exposing the MoS.sub.2 nanoclusters and hydrocarbon compound mixture with visible light. The MoS.sub.2 nanoclusters can be introduced to the toxic hydrocarbons as either a MoS.sub.2 solution or deposited on a support material.

Controlled release chamber for dispensing aromatic substances.

PubMed

Cilek, J E; Hallmon, C F

2008-12-01

A novel device for the containment and precise release of aromatic substances is described. The device consists of a threaded-tubular polyvinyl chloride chamber (and screw-top cap) with ports for introduction and release of gaseous compounds. This chamber is inexpensive, easy to assemble, and useful for evaluating the combined release of carbon dioxide and aromatic hygroscopic substances as mosquito attractants in field studies.

Poly(arylene ether)s That Resist Atomic Oxygen

NASA Technical Reports Server (NTRS)

Connell, John W.; Hergenrother, Paul; Smith, Joseph G., Jr.

1994-01-01

Novel poly(arylene ether)s containing phosphine oxide (PAEPO's) made via aromatic nucleophilic displacement reactions of activated aromatic dihalides (or, in some cases, activated aromatic dinitro compounds) with new bisphenol monomers containing phosphine oxide. Exhibited favorable combination of physical and mechanical properties and resistance to monatomic oxygen in oxygen plasma environment. Useful as adhesives, coatings, films, membranes, moldings, and composite matrices.

Mutagenicity of diesel exhaust particle extracts: influence of fuel composition in two diesel engines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clark, C.R.; Henderson, T.R.; Royer, R.E.

The influence of diesel fuel composition on mutagenicity of exhaust particle associated organic compounds has been investigated using nine fuels varying in aromatic content and distillation properties. The tests were conducted with Oldsmobile Delta-88 and Peugot 504 diesel cars operated according to the EPA Federal Test Procedure. The particulate exhaust from each test was collected on a filter, extracted in dichloromethane and the resulting extract evaluated for mutagenicity in Salmonella strain TA-100. Mutagenicity of extracts of particles collected from the Oldsmobile were highest in the higher aromatic content fuels (greater than 30%) but similar for intermediate (20%) and low (13%)more » aromatic content fuels. No influence of aromaticity on mutagenicity was observed in samples collected from the Peugeot under the same conditions. Thus, fuel aromatic content may enhance the production of mutagenic combustion products at higher concentrations, but may be dependent upon engine type. A good correlation was observed between mutagenicity of the particle extracts and the initial boiling point of the fuel (r . 0.89). Gas chromatography/mass spectrometric analysis of the aromatic fraction of the fuels showed that the fuel producing the most mutagenic combustion products was highest in phenanthrene type compounds.« less

The effect of aromatization on the isotopic compositions of hydrocarbons during early diagenesis

NASA Technical Reports Server (NTRS)

Freeman, K. H.; Boreham, C. J.; Summons, R. E.; Hayes, J. M.

1994-01-01

Polycyclic aromatic hydrocarbons with varying degrees of aromatization were isolated from the Eocene Messel Shale (Rheingraben, Germany). The high abundances of these compounds and their structural resemblances to cyclic triterpenoid lipids are consistent with derivation from microbial rather than thermal processes. Compounds structurally related to oleanane contain from five to nine double bonds; those within a series of aromatized hopanoids contain from three to nine. All are products of diagenetic reactions that remove hydrogen or methyl groups, and, in several cases, break carbon-carbon bonds to open rings. Aromatized products are on average depleted in 13C relative to possible precursors by l.2% (range: l.5% enrichment to 4% depletion, n = 9). The dependence of 13C content on the number of double bonds is not, however, statistically significant and it must be concluded that there is no strong evidence for isotopic fractionation accompanying diagenetic aromatization. Isotopic differences between series (structures related to ursane, des-A-ursane, des-A-lupane, des-A-arborane, and possibly, des-A-gammacerane are present) are much greater, indicating that 13C contents are controlled primarily by source effects. Fractionations due to chromatographic isotope effects during HPLC ranged from 0.1 to 2.8%.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, B.D.; Apel, W.A.; Walton, M.R.

Conceptually, biofilters are vapor phase bioreactors that rely on microorganisms in the bed medium to oxidize contaminants in off-gases flowing through the bed to less hazardous compounds. In the most studied and utilized systems reduced compounds such as fuel hydrocarbons are enzymatically oxidized to compounds such as carbon dioxide and water. In these types of reactions the microorganisms in the bed oxidize the contaminant and transfer the electrons to oxygen which is the terminal electron acceptor in the process. In essence the contaminant is the carbon and energy source for the microorganisms in the bed medium and through this catabolicmore » process oxygen is reduced to water. An example of this oxidation process can be seen during the degradation of benzene and similar aromatic compounds. Aromatics are initially attacked by a dioxygenase enzyme which oxidizes the compounds to a labile dihydrodiole which is spontaneously converted to a catechol. The dihydroxylated aromatic rings is then opened by oxidative {open_quotes}ortho{close_quotes} or {open_quotes}meta{close_quotes} cleavage yielding cis, cis-muconic acid or 2-hydroxy-cis, cis-muconic semialdehyde, respectively. These organic compounds are further oxidized to carbon dioxide or are assimilated for cellular material. This paper describes the conversion of carbon tetrachloride using methanol as the primary carbon and energy source.« less

Pseudomonas putida as a platform for the synthesis of aromatic compounds.

PubMed

Molina-Santiago, Carlos; Cordero, Baldo F; Daddaoua, Abdelali; Udaondo, Zulema; Manzano, Javier; Valdivia, Miguel; Segura, Ana; Ramos, Juan-Luis; Duque, Estrella

2016-09-01

Aromatic compounds such as l-phenylalanine, 2-phenylethanol and trans-cinnamate are aromatic compounds of industrial interest. Current trends support replacement of chemical synthesis of these compounds by 'green' alternatives produced in microbial cell factories. The solvent-tolerant Pseudomonas putida DOT-T1E strain was genetically modified to produce up to 1 g l-1 of l-phenylalanine. In order to engineer this strain, we carried out the following stepwise process: (1) we selected random mutants that are resistant to toxic phenylalanine analogues; (2) we then deleted up to five genes belonging to phenylalanine metabolism pathways, which greatly diminished the internal metabolism of phenylalanine; and (3) in these mutants, we overexpressed the pheAfbr gene, which encodes a recombinant variant of PheA that is insensitive to feedback inhibition by phenylalanine. Furthermore, by introducing new genes, we were able to further extend the diversity of compounds produced. Introduction of histidinol phosphate transferase (PP_0967), phenylpyruvate decarboxylase (kdc) and an alcohol dehydrogenase (adh) enabled the strain to produce up to 180 mg l-1 2-phenylethanol. When phenylalanine ammonia lyase (pal) was introduced, the resulting strain produced up to 200 mg l-1 of trans-cinnamate. These results demonstrate that P. putida can serve as a promising microbial cell factory for the production of l-phenylalanine and related compounds.

The Impact of Single Amino Acids on Growth and Volatile Aroma Production by Saccharomyces cerevisiae Strains

PubMed Central

Fairbairn, Samantha; McKinnon, Alexander; Musarurwa, Hannibal T.; Ferreira, António C.; Bauer, Florian F.

2017-01-01

Nitrogen availability and utilization by Saccharomyces cerevisiae significantly influence fermentation kinetics and the production of volatile compounds important for wine aroma. Amino acids are the most important nitrogen source and have been classified based on how well they support growth. This study evaluated the effect of single amino acids on growth kinetics and major volatile production of two phenotypically different commercial wine yeast strains in synthetic grape must. Four growth parameters, lag phase, maximum growth rate, total biomass formation and time to complete fermentation were evaluated. In contrast with previous findings, in fermentative conditions, phenylalanine and valine supported growth well and asparagine supported it poorly. The four parameters showed good correlations for most amino acid treatments, with some notable exceptions. Single amino acid treatments resulted in the predictable production of aromatic compounds, with a linear correlation between amino acid concentration and the concentration of aromatic compounds that are directly derived from these amino acids. With the increased complexity of nitrogen sources, linear correlations were lost and aroma production became unpredictable. However, even in complex medium minor changes in amino acid concentration continued to directly impact the formation of aromatic compounds, suggesting that the relative concentration of individual amino acids remains a predictor of aromatic outputs, independently of the complexity of metabolic interactions between carbon and nitrogen metabolism and between amino acid degradation and utilization pathways. PMID:29312237

The Impact of Single Amino Acids on Growth and Volatile Aroma Production by Saccharomyces cerevisiae Strains.

PubMed

Fairbairn, Samantha; McKinnon, Alexander; Musarurwa, Hannibal T; Ferreira, António C; Bauer, Florian F

2017-01-01

Nitrogen availability and utilization by Saccharomyces cerevisiae significantly influence fermentation kinetics and the production of volatile compounds important for wine aroma. Amino acids are the most important nitrogen source and have been classified based on how well they support growth. This study evaluated the effect of single amino acids on growth kinetics and major volatile production of two phenotypically different commercial wine yeast strains in synthetic grape must. Four growth parameters, lag phase, maximum growth rate, total biomass formation and time to complete fermentation were evaluated. In contrast with previous findings, in fermentative conditions, phenylalanine and valine supported growth well and asparagine supported it poorly. The four parameters showed good correlations for most amino acid treatments, with some notable exceptions. Single amino acid treatments resulted in the predictable production of aromatic compounds, with a linear correlation between amino acid concentration and the concentration of aromatic compounds that are directly derived from these amino acids. With the increased complexity of nitrogen sources, linear correlations were lost and aroma production became unpredictable. However, even in complex medium minor changes in amino acid concentration continued to directly impact the formation of aromatic compounds, suggesting that the relative concentration of individual amino acids remains a predictor of aromatic outputs, independently of the complexity of metabolic interactions between carbon and nitrogen metabolism and between amino acid degradation and utilization pathways.

Classification of the fragrant styles and evaluation of the aromatic quality of flue-cured tobacco leaves by machine-learning methods.

PubMed

Gu, Li; Xue, Lichun; Song, Qi; Wang, Fengji; He, Huaqin; Zhang, Zhongyi

2016-12-01

During commercial transactions, the quality of flue-cured tobacco leaves must be characterized efficiently, and the evaluation system should be easily transferable across different traders. However, there are over 3000 chemical compounds in flue-cured tobacco leaves; thus, it is impossible to evaluate the quality of flue-cured tobacco leaves using all the chemical compounds. In this paper, we used Support Vector Machine (SVM) algorithm together with 22 chemical compounds selected by ReliefF-Particle Swarm Optimization (R-PSO) to classify the fragrant style of flue-cured tobacco leaves, where the Accuracy (ACC) and Matthews Correlation Coefficient (MCC) were 90.95% and 0.80, respectively. SVM algorithm combined with 19 chemical compounds selected by R-PSO achieved the best assessment performance of the aromatic quality of tobacco leaves, where the PCC and MSE were 0.594 and 0.263, respectively. Finally, we constructed two online tools to classify the fragrant style and evaluate the aromatic quality of flue-cured tobacco leaf samples. These tools can be accessed at http://bioinformatics.fafu.edu.cn/tobacco .

Sodium Perborate Oxidation of an Aromatic Amine

ERIC Educational Resources Information Center

Juestis, Laurence

1977-01-01

Describes an experiment involving the oxidation of aromatic primary amines to the corresponding azo compound; suggests procedures for studying factors that influence the yield of such a reaction, including the choice of solvent and the oxidant-amine ratio. (MLH)

Automated analysis of oxidative metabolites

NASA Technical Reports Server (NTRS)

Furner, R. L. (Inventor)

1974-01-01

An automated system for the study of drug metabolism is described. The system monitors the oxidative metabolites of aromatic amines and of compounds which produce formaldehyde on oxidative dealkylation. It includes color developing compositions suitable for detecting hyroxylated aromatic amines and formaldehyde.

PTR-MS Characterization of VOCs Associated with Commercial Aromatic Bakery Yeasts of Wine and Beer Origin.

PubMed

Capozzi, Vittorio; Makhoul, Salim; Aprea, Eugenio; Romano, Andrea; Cappellin, Luca; Sanchez Jimena, Ana; Spano, Giuseppe; Gasperi, Flavia; Scampicchio, Matteo; Biasioli, Franco

2016-04-12

In light of the increasing attention towards "green" solutions to improve food quality, the use of aromatic-enhancing microorganisms offers the advantage to be a natural and sustainable solution that did not negatively influence the list of ingredients. In this study, we characterize, for the first time, volatile organic compounds (VOCs) associated with aromatic bakery yeasts. Three commercial bakery starter cultures, respectively formulated with three Saccharomyces cerevisiae strains, isolated from white wine, red wine, and beer, were monitored by a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS), a direct injection analytical technique for detecting volatile organic compounds with high sensitivity (VOCs). Two ethanol-related peaks (m/z 65.059 and 75.080) described qualitative differences in fermentative performances. The release of compounds associated to the peaks at m/z 89.059, m/z 103.075, and m/z 117.093, tentatively identified as acetoin and esters, are coherent with claimed flavor properties of the investigated strains. We propose these mass peaks and their related fragments as biomarkers to optimize the aromatic performances of commercial preparations and for the rapid massive screening of yeast collections.

Ecology, physiology, and phylogeny of deep subsurface Sphingomonas sp.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fredrickson, Jim K.; Balkwill, David L.; Romine, Margaret F.

Several new species of the genus Sphingomonas including S. aromaticivorans, S. stygia, and S. subterranea that have the capacity for degrading a broad range of aromatic compounds including toluene, naphthalene, xylenes, p-cresol, fluorene, biphenyl, and dibenzothiophene, were isolated from deeply-buried (>200 m) sediments of the US Atlantic coastal plain (ACP). In S. aromaticivorans F199, many of the genes involved in the catabolism of these aromatic compounds are encoded on a 184-kb conjugative plasmid; some of the genes involved in aromatic catabolism are plasmid-encoded in the other strains as well. Members of the genus Sphingomonas were common among aerobic heterotrophic bacteriamore » cultured from ACP sediments and have been detected in deep subsurface environments elsewhere. The major source of organic carbon for heterotrophic metabolism in ACP deep aquifers is lignite that originated from plant material buried with the sediments. We speculate that the ability of the subsurface Sphingomonas strains to degrade a wide array of aromatic compounds represents an adaptation for utilization of sedimentary lignite. These and related subsurface Sphingomonas spp may play an important role in the transformation of sedimentary organic carbon in the aerobic and microaerobic regions of the deep aquifers of the ACP.« less

Remediation of aged diesel contaminated soil by alkaline activated persulfate.

PubMed

Lominchar, M A; Santos, A; de Miguel, E; Romero, A

2018-05-01

The present work studies the efficiency of alkaline activated persulfate (PS) to remediate an aged diesel fuel contaminated soil from a train maintenance facility. The Total Petroleum Hydrocarbon (TPH) concentration in soil was approximately 5000mgkg -1 with a ratio of aliphatic:aromatic compounds of 70:30. Aromatic compounds were mainly naphtalenes and phenanthrenes. The experiments were performed in batch mode where different initial concentrations of persulfate (105mM, 210mM and 420mM) and activator:persulfate ratios (2 and 4) were evaluated, with NaOH used as activator. Runs were carried out during 56days. Complete TPH conversion was obtained with the highest concentration of PS and activator, whereas in the other runs the elimination of fuel ranged between 60 and 77%. Besides, the abatement of napthalenes and phenantrenes was faster than aliphatic reduction (i. e. after 4days of treatment, the conversions of the aromatic compounds were around 0.8 meanwhile the aliphatic abatements were 0.55) and no aromatic oxidation intermediates from naphtalenes or phenantrenes were detected. These results show that this technology is effective for the remediation of aged diesel in soil with alkaline pH. Copyright © 2017 Elsevier B.V. All rights reserved.

Biologically important compounds in synfuels processes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clark, B R; Ho, C; Griest, W H

1980-01-01

Crude products, by-products and wastes from synfuel processes contain a broad spectrum of chemical compounds - many of which are active in biological systems. Discerning which compound classes are most important is necessary in order to establish effective control over release or exposure. Polycyclic aromatic hydrocarbons (PAH), multialkylated PAH, primary aromatic amines and N-heterocyclic PAH are significant contributors to the overall mutagenic activities of a large number of materials examined. Ames test data show that the basic, primary aromatic amine fraction is the most active. PAHs, multialkylated PAHs and N-heterocyclic PAHs are all components of the neutral fraction. In nearlymore » all cases, the neutral fractions contribute the largest portion of the mutagenic activity, while the basic primary aromatic amine fractions have the highest specific activity. Neutral fractions are usually the largest (wt %) whereas the total basic fractions are small by comparison; thus, the overall greater contribution of the neutral fraction to the mutagenic activity of most samples. Biologically active constituents are isolated in preparative scale amounts from complex mixtures utilizing combinations of liquid-liquid extraction and various liquid chromatographic column-eluant combinations. Fractions are characterized using a combination of spectroscopic techniques and gas chromatography/mass spectrometry.« less

Ecology, physiology, and phylogeny of deep subsurface Sphingomonas sp.

PubMed

Fredrickson, J K; Balkwill, D L; Romine, M F; Shi, T

1999-10-01

Several new species of the genus Sphingomonas including S. aromaticivorans, S. stygia, and S. subterranea that have the capacity for degrading a broad range of aromatic compounds including toluene, naphthalene, xylenes, p-cresol, fluorene, biphenyl, and dibenzothiophene, were isolated from deeply-buried (>200 m) sediments of the US Atlantic coastal plain (ACP). In S. aromaticivorans F199, many of the genes involved in the catabolism of these aromatic compounds are encoded on a 184-kb conjugative plasmid; some of the genes involved in aromatic catabolism are plasmid-encoded in the other strains as well. Members of the genus Sphingomonas were common among aerobic heterotrophic bacteria cultured from ACP sediments and have been detected in deep subsurface environments elsewhere. The major source of organic carbon for heterotrophic metabolism in ACP deep aquifers is lignite that originated from plant material buried with the sediments. We speculate that the ability of the subsurface Sphingomonas strains to degrade a wide array of aromatic compounds represents an adaptation for utilization of sedimentary lignite. These and related subsurface Sphingomonas spp may play an important role in the transformation of sedimentary organic carbon in the aerobic and microaerobic regions of the deep aquifers of the ACP.

Engineering Escherichia coli to overproduce aromatic amino acids and derived compounds.

PubMed

Rodriguez, Alberto; Martínez, Juan A; Flores, Noemí; Escalante, Adelfo; Gosset, Guillermo; Bolivar, Francisco

2014-09-09

The production of aromatic amino acids using fermentation processes with recombinant microorganisms can be an advantageous approach to reach their global demands. In addition, a large array of compounds with alimentary and pharmaceutical applications can potentially be synthesized from intermediates of this metabolic pathway. However, contrary to other amino acids and primary metabolites, the artificial channelling of building blocks from central metabolism towards the aromatic amino acid pathway is complicated to achieve in an efficient manner. The length and complex regulation of this pathway have progressively called for the employment of more integral approaches, promoting the merge of complementary tools and techniques in order to surpass metabolic and regulatory bottlenecks. As a result, relevant insights on the subject have been obtained during the last years, especially with genetically modified strains of Escherichia coli. By combining metabolic engineering strategies with developments in synthetic biology, systems biology and bioprocess engineering, notable advances were achieved regarding the generation, characterization and optimization of E. coli strains for the overproduction of aromatic amino acids, some of their precursors and related compounds. In this paper we review and compare recent successful reports dealing with the modification of metabolic traits to attain these objectives.

Identification of genotoxic compounds in crude oil using fractionation according to distillation, polarity and Kow.

PubMed

Park, Shin Yeong; Lee, Hyo Jin; Khim, Jong Seong; Kim, Gi Beum

2017-01-30

We examined the degree of DNA damage caused by fractions of crude oil in accordance with the boiling points, polarity and log K ow . Relatively high DNA damage was observed in the aromatic fraction (290-330°C) and resin and polar fraction (350-400°C). The resin and polar fraction showed relatively high genotoxicity compared with the aliphatic and aromatic fraction at the 1-4 log K ow range. At the 6-7 log K ow range, the aromatic fraction showed relatively high DNA damage compared with the aliphatic and resin and polar fraction. In particular, every detailed fraction in accordance with the log K ow values (aliphatic and aromatic (310-320°C) and resins and polar fractions (370-380°C)) showed one or less than one DNA damage. However, the fractions before separation in accordance with log K ow values (aliphatic and aromatic (310-320°C) and resin and polar (370-380°C) fractions) showed high DNA damage. Thus, we confirm the synergistic action between the detailed compounds. Copyright © 2016 Elsevier Ltd. All rights reserved.

Aromatic volatile organic compounds and their role in ground-level ozone formation in Russia

NASA Astrophysics Data System (ADS)

Berezina, E. V.; Moiseenko, K. B.; Skorokhod, A. I.; Elansky, N. F.; Belikov, I. B.

2017-05-01

This paper reports proton mass spectrometry data on aromatic volatile organic compounds (VOCs) (benzene, toluene, phenol, styrene, xylene, and propylbenzene) obtained in different Russian regions along the Trans-Siberian Railway from Moscow to Vladivostok, based on expedition data retrieved using the TRO-ICA-12 mobile laboratory in the summer of 2008. The contribution of aromatic VOCs to ozone formation in the cities and regions along the measurement route has been estimated quantitatively. The greatest contribution of aromatic VOCs to ozone formation is characteristic of large cities along the Trans-Siberian Railway (up to 7.5 ppbv O3) specified by the highest concentrations of aromatic VOCs (1-1.7 ppbv) and nitrogen oxides (>20 ppbv). The results obtained are indicative of a considerable contribution (30-50%) of anthropogenic emissions of VOCs to photochemical ozone generation in the large cities along the Trans-Siberian Railway in hot and dry weather against the background of a powerful natural factor such as isoprene emissions controlling the regional balance of ground-level ozone in warm seasons.

Process for detoxifying coal tars

DOEpatents

Longwell, John P.; Peters, William A.

1983-01-01

A process for treating liquid hydrocarbons to remove toxic, mutagenic and/or carcinogenic aromatic hydrocarbons comprises feeding the hydrocarbons into a reactor where vapors are thermally treated in contact with a catalyst consisting essentially of calcium oxide or a calcium oxide containing mineral. Thermally treating liquid hydrocarbons in contact with calcium oxide preferentially increases the cracking of aromatics thus producing a product having a reduced amount of aromatic compounds.

Polyphenylquinoxalines via aromatic nucleophilic displacement

NASA Technical Reports Server (NTRS)

Hergenrother, Paul M. (Inventor); Connell, John W. (Inventor)

1990-01-01

Polyphenylquinoxalines are prepared by the nucleophilic displacement reaction of di(hydroxyphenyl)quinoxaline monomers with activated aromatic dihalides or dinitro compounds. The reactions are carried out in polar aprotic solvents using alkali metal bases at elevated temperatures under nitrogen. The di(hydroxyphenyl)quinoxaline monomers are prepared either by reacting stoichiometric quantities of aromatic bis(o-diamines) with a hydroxybenzil or by reacting o-phenylenediamine with a dihydroxybenzil or bis(hydroxyphenylglyoxylyl)benzene.

Polyphenylquinoxalines via aromatic nucleophilic displacement

NASA Technical Reports Server (NTRS)

Hergenrother, Paul M. (Inventor); Connell, John W. (Inventor)

1991-01-01

Polyphenylquinoxalines are prepared by the nucleophilic displacement reaction of di(hydroxyphenyl)quinoxaline monomers with activated aromatic dihalides or dinitro compounds. The reactions are carried out in polar aprotic solvents during alkali metal bases at elevated temperatures under nitrogen. The di(hydroxyphenyl)quinoxaline monomers are prepared either by reacting stoichiometric quantities of aromatic bis(o-diamines) with a hydroxybenzil or by reacting o-phenylenediamine with a dihydroxybenzil or bis(hydroxyphenylglyoxylyl)benzene.

Bioactive Compounds Derived from the Yeast Metabolism of Aromatic Amino Acids during Alcoholic Fermentation

PubMed Central

Guillamon, Jose Manuel; Torija, Maria Jesus; Beltran, Gemma; Troncoso, Ana M.; Garcia-Parrilla, M. Carmen

2014-01-01

Metabolites resulting from nitrogen metabolism in yeast are currently found in some fermented beverages such as wine and beer. Their study has recently attracted the attention of researchers. Some metabolites derived from aromatic amino acids are bioactive compounds that can behave as hormones or even mimic their role in humans and may also act as regulators in yeast. Although the metabolic pathways for their formation are well known, the physiological significance is still far from being understood. The understanding of this relevance will be a key element in managing the production of these compounds under controlled conditions, to offer fermented food with specific enrichment in these compounds or even to use the yeast as nutritional complements. PMID:24895623

Enzymes involved in a novel anaerobic cyclohexane carboxylic acid degradation pathway.

PubMed

Kung, Johannes W; Meier, Anne-Katrin; Mergelsberg, Mario; Boll, Matthias

2014-10-01

The anaerobic degradation of cyclohexane carboxylic acid (CHC) has so far been studied only in Rhodopseudomonas palustris, in which CHC is activated to cyclohexanoyl coenzyme A (cyclohexanoyl-CoA [CHCoA]) and then dehydrogenated to cyclohex-1-ene-1-carboxyl-CoA (CHeneCoA). This intermediate is further degraded by reactions of the R. palustris-specific benzoyl-CoA degradation pathway of aromatic compounds. However, CHeneCoA is not an intermediate in the degradation of aromatic compounds in all other known anaerobic bacteria; consequently, degradation of CHC was mostly unknown in anaerobic bacteria. We identified a previously unknown CHC degradation pathway in the Fe(III)-reducing Geobacter metallireducens by determining the following CHC-induced in vitro activities: (i) the activation of CHC to CHCoA by a succinyl-CoA:CHC CoA transferase, (ii) the 1,2-dehydrogenation of CHCoA to CHeneCoA by CHCoA dehydrogenase, and (iii) the unusual 1,4-dehydrogenation of CHeneCoA to cyclohex-1,5-diene-1-carboxyl-CoA. This last represents a previously unknown joint intermediate of the CHC and aromatic compound degradation pathway in bacteria other than R. palustris. The enzymes catalyzing the three reactions were purified and characterized as specific enzymes after heterologous expression of the encoding genes. Quantitative reverse transcription-PCR revealed that expression of these genes was highly induced during growth with CHC but not with benzoate. The newly identified CHC degradation pathway is suggested to be present in nearly all CHC-degrading anaerobic bacteria, including denitrifying, Fe(III)-reducing, sulfate-reducing, and fermenting bacteria. Remarkably, all three CHC degradation pathways always link CHC catabolism to the catabolic pathways of aromatic compounds. We propose that the capacity to use CHC as a carbon source evolved from already-existing aromatic compound degradation pathways. Copyright © 2014, American Society for Microbiology. All Rights Reserved.

Enzymes Involved in a Novel Anaerobic Cyclohexane Carboxylic Acid Degradation Pathway

PubMed Central

Kung, Johannes W.; Meier, Anne-Katrin; Mergelsberg, Mario

2014-01-01

The anaerobic degradation of cyclohexane carboxylic acid (CHC) has so far been studied only in Rhodopseudomonas palustris, in which CHC is activated to cyclohexanoyl coenzyme A (cyclohexanoyl-CoA [CHCoA]) and then dehydrogenated to cyclohex-1-ene-1-carboxyl-CoA (CHeneCoA). This intermediate is further degraded by reactions of the R. palustris-specific benzoyl-CoA degradation pathway of aromatic compounds. However, CHeneCoA is not an intermediate in the degradation of aromatic compounds in all other known anaerobic bacteria; consequently, degradation of CHC was mostly unknown in anaerobic bacteria. We identified a previously unknown CHC degradation pathway in the Fe(III)-reducing Geobacter metallireducens by determining the following CHC-induced in vitro activities: (i) the activation of CHC to CHCoA by a succinyl-CoA:CHC CoA transferase, (ii) the 1,2-dehydrogenation of CHCoA to CHeneCoA by CHCoA dehydrogenase, and (iii) the unusual 1,4-dehydrogenation of CHeneCoA to cyclohex-1,5-diene-1-carboxyl-CoA. This last represents a previously unknown joint intermediate of the CHC and aromatic compound degradation pathway in bacteria other than R. palustris. The enzymes catalyzing the three reactions were purified and characterized as specific enzymes after heterologous expression of the encoding genes. Quantitative reverse transcription-PCR revealed that expression of these genes was highly induced during growth with CHC but not with benzoate. The newly identified CHC degradation pathway is suggested to be present in nearly all CHC-degrading anaerobic bacteria, including denitrifying, Fe(III)-reducing, sulfate-reducing, and fermenting bacteria. Remarkably, all three CHC degradation pathways always link CHC catabolism to the catabolic pathways of aromatic compounds. We propose that the capacity to use CHC as a carbon source evolved from already-existing aromatic compound degradation pathways. PMID:25112478

Effects of Spray-Drying Parameters on In Vitro Functional Properties of Camu-Camu (Myrciaria dubia Mc. Vaugh): A Typical Amazonian Fruit.

PubMed

Fujita, Alice; Souza, Volnei Brito; Daza, Luis Daniel; Fávaro-Trindade, Carmen Silvia; Granato, Daniel; Genovese, Maria Inés

2017-05-01

Camu-camu (Myrciaria dubia) fruit is a rich source of bioactive compounds but its shelf life is rather short. Therefore, this study was aimed to evaluate the effect of inlet air temperature (T) and concentration (C) of maltodextrin and arabic gum on the spray-drying process of commercial camu-camu pulps (São Paulo and Manaus). Moisture, solubility, total phenolics (TP), ascorbic acid (AA), and proanthocyanidins (PAC) contents, and in vitro antioxidant capacity of the powders (FRAP, DPPH, Folin-Ciocalteu's reducing capacity were measured). Arabic gum resulted in better yields (22% to 30%), powder solubility (84% to 90%), and lower losses of analyzed compounds than the powders manufactured with maltodextrin. Overall, inlet air temperature had a lower impact on the responses studied than the concentration of carrier agents. Polynomial equations were generated for AA (R 2 = 0.993), TP (R 2 = 0.735), PAC (R 2 = 0.946), and for the antioxidant capacity assays (0.867 ≤ R 2  ≤ 0.963). In addition, principal component analysis showed that the lowest concentration of carrier agents (6%) in spray drying resulted in the lowest losses of bioactive compounds and, consequently, the highest antioxidant capacity. © 2017 Institute of Food Technologists®.

PHOTOACTIVATION AND TOXICITY OF MIXTURES OF POLYCYCLIC AROMATIC HYDROCARBON COMPOUNDS IN MARINE SEDIMENT

EPA Science Inventory

The direct toxicity and photoinduced toxicity of sediment-associated acenaphthene, phenanthrene, fluoranthene, and pyrene were determined for the marine amphipod Rhepoxynius abronius. The four polycyclic aromatic hydrocarbons (PAHs) were spiked into sediment in a concentration se...

Combined effects of EPS and HRT enhanced biofouling on a submerged and hybrid PAC-MF membrane bioreactor.

PubMed

Khan, Mohiuddin Md Taimur; Takizawa, Satoshi; Lewandowski, Zbigniew; Habibur Rahman, M; Komatsu, Kazuhiro; Nelson, Sara E; Kurisu, Futoshi; Camper, Anne K; Katayama, Hiroyuki; Ohgaki, Shinichiro

2013-02-01

The goal of this study was to quantify and demonstrate the dynamic effects of hydraulic retention time (HRT), organic carbon and various components of extracellular polymeric substances (EPS) produced by microorganisms on the performance of submersed hollow-fiber microfiltration (MF) membrane in a hybrid powdered activated carbon (PAC)-MF membrane bioreactor (MBR). The reactors were operated continuously for 45 days to treat surface (river) water before and after pretreatment using a biofiltration unit. The real-time levels of organic carbon and the major components of EPS including five different carbohydrates (D(+) glucose and D(+) mannose, D(+) galactose, N-acetyl-D-galactosamine and D-galactose, oligosaccharides and L(-) fucose), proteins, and polysaccharides were quantified in the influent water, foulants, and in the bulk phases of different reactors. The presence of PAC extended the filtration cycle and enhanced the organic carbon adsorption and removal more than two fold. Biological filtration improved the filtrate quality and decreased membrane fouling. However, HRT influenced the length of the filtration cycle and had less effect on organic carbon and EPS component removal and/or biodegradation. The abundance of carbohydrates in the foulants on MF surfaces was more than 40 times higher than in the bulk phase, which demonstrates that the accumulation of carbohydrates on membrane surfaces contributed to the increase in transmembrane pressure significantly and PAC was not a potential adsorbent of carbohydrates. The abundance of N-acetyl-d-galactosamine and d-galactose was the highest in the foulants on membranes receiving biofilter-treated river water. Most of the biological fouling compounds were produced inside the reactors due to biodegradation. PAC inside the reactor enhanced the biodegradation of polysaccharides up to 97% and that of proteins by more than 95%. This real-time extensive and novel study demonstrates that the PAC-MF hybrid MBR is a sustainable technology for treating river water. Copyright © 2012 Elsevier Ltd. All rights reserved.

Organics Captured from Comet Wild 2 by the Stardust Spacecraft

NASA Technical Reports Server (NTRS)

Sandford, Scott A.; Aleon, Jerome; Araki, Tohru; Bajt, Sasa; Baratta, Giuseppe A.; Borg, Janet; Brucato, John R.; Burchell, Mark J.; Busemann, Henner; Butterworth, Anna;

The combination of vemurafenib and procaspase-3 activation is synergistic in mutant BRAF melanomas

PubMed Central

Peh, Jessie; Fan, Timothy M.; Wycislo, Kathryn L.; Roth, Howard S.; Hergenrother, Paul J.

2016-01-01

The development of vemurafenib resistance limits the long-term efficacy of this drug for treatment of metastatic melanomas with the V600EBRAF mutation. Inhibition of downstream MAPK signaling with vemurafenib induces apoptotic cell death mediated by caspase-3, suggesting that addition of a procaspase-3 activator could enhance anticancer effects. Here we show that the combination of PAC-1, a procaspase-activating compound, and vemurafenib is highly synergistic in enhancing caspase-3 activity and apoptotic cell death in melanoma cell lines harboring the V600EBRAF mutation. In vivo, the combination displays a favorable safety profile in mice, and exerts significant antitumor effects. We further demonstrate that addition of PAC-1 to the clinically useful combination of vemurafenib and a MEK inhibitor, trametinib, starkly enhances the caspase-3 activity and proapoptotic effect of the combination. Moreover, addition of low concentration PAC-1 also delays the regrowth of cells following treatment with vemurafenib. Finally, PAC-1 remains potent against vemurafenib-resistant A375VR cells in cell culture and synergizes with vemurafenib to exert antitumor effects on A375VR cell growth in vivo. Collectively, our data suggest that inhibition of MAPK signaling combined with concurrent procaspase-3 activation is an effective strategy to enhance the antitumor activity of vemurafenib and mitigate the development of resistance. PMID:27297867

Aromaticity and Antiaromaticity in Zintl Clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Zhong -Ming; Liu, Chao; Popov, Ivan Aleksandrovich

Originally, the concepts of aromaticity and antiaromaticity were introduced to explain the stability and reactivity of unsaturated organic compounds. Since then, they have been extended to other species with delocalized electrons including various saturated systems, organometallic compounds, and even inorganic clusters and molecules. In this study, we focus on the most recent progress of using these concepts to guide experimental synthesis and rationalize geometrical and electronic structures of a particular family of polyanions composed of Group 14 and 15 elements, namely Zintl clusters.

Aromaticity and Antiaromaticity in Zintl Clusters

DOE PAGES

Sun, Zhong -Ming; Liu, Chao; Popov, Ivan Aleksandrovich; ...

2018-05-18

Originally, the concepts of aromaticity and antiaromaticity were introduced to explain the stability and reactivity of unsaturated organic compounds. Since then, they have been extended to other species with delocalized electrons including various saturated systems, organometallic compounds, and even inorganic clusters and molecules. In this study, we focus on the most recent progress of using these concepts to guide experimental synthesis and rationalize geometrical and electronic structures of a particular family of polyanions composed of Group 14 and 15 elements, namely Zintl clusters.

Radiation-resistant, amorphous, all-aromatic poly(arylene ether sulfones) - Synthesis, physical behavior, and degradation characteristics

NASA Technical Reports Server (NTRS)

Lewis, D. A.; O'Donnell, James H.; Hedrick, J. L.; Ward, T. C.; Mcgrath, J. E.

1989-01-01

The effects of Co-60 gamma radiation on a series of poly(arylene ether sulfones) prepared by nucleophilic activated aromatic substitution are investigated experimentally. The preparation of the test compounds is described, and the test results are presented in extensive tables and graphs. Radiation-induced degradation, as measured by SO2 production, was found to be lowest in compounds based on biphenol rather than bisphenol A; these findings were also well correlated with ultimate-tensile-strain measurements.

Tree nut phytochemicals: composition, antioxidant capacity, bioactivity, impact factors. A systematic review of almonds, Brazils, cashews, hazelnuts, macadamias, pecans, pine nuts, pistachios and walnuts

USDA-ARS?s Scientific Manuscript database

Tree nuts contain an array of phytochemicals including carotenoids, phenolic acids, phytosterols and polyphenolic compounds such as flavonoids, proanthocyanidins (PAC) and stilbenes, all of which are included in nutrient databases, as well as phytates, sphingolipids, alkylphenols and lignans, which ...

Flavonoids and phenolic acids from cranberry juice are bioavailable and bioactive in healthy older adults.

PubMed

McKay, Diane L; Chen, C-Y Oliver; Zampariello, Carly A; Blumberg, Jeffrey B

2015-02-01

Cranberries (Vaccinium macrocarpon) are a rich source of phenolic phytochemicals, which likely contribute to their putative health benefits. A single-dose pharmacokinetic trial was conducted in 10 healthy adults ⩾50y to evaluate the acute (24-h) absorption and excretion of flavonoids, phenolic acids and proanthocyanidins (PACs) from a low-calorie cranberry juice cocktail (54% juice). Inter-individual variability was observed in the Cmax and Tmax of many of these compounds in both plasma and urine. The sum total concentration of phenolics detected in plasma reached a peak of 34.2μg/ml between 8 and 10h, while in urine this peak was 269.8μg/mg creatinine, and appeared 2-4h earlier. The presence of PAC-A2 dimers in human urine has not previously been reported. After cranberry juice consumption, plasma total antioxidant capacity assessed using ORAC and TAP assays correlated with individual metabolites. Our results show phenolic compounds in cranberry juice are bioavailable and exert antioxidant actions in healthy older adults. Copyright © 2014 Elsevier Ltd. All rights reserved.

Polybenzimidazoles Via Aromatic Nucleophilic Displacement

NASA Technical Reports Server (NTRS)

Connell, John W. (Inventor); Hergerrother, Paul M. (Inventor); Smith, Joseph G., Jr. (Inventor)

1997-01-01

Novel molecular weight controlled and endcapped polybenzimidazoles (PBI) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenylbenzimidazole) monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The PBI are endcapped with mono(hydroxyphenyl)benzimidazoles. The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N,N-dimethylacetamide using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. Mono(hydroxyphenyl)benzimidazoles are synthesized by reacting phenyl-4-hydroxybenzoate with aromatic (o-diamine)s in diphenylsulfone. Molecular weight controlled and endcapped PBI of new chemical structures are prepared that exhibit a favorable combination of physical and mechanical properties.

Polybenzimidazoles via aromatic nucleophilic displacement

NASA Technical Reports Server (NTRS)

Connell, John W. (Inventor); Hergenrother, Paul M. (Inventor); Smith, Joseph G., Jr. (Inventor)

1995-01-01

Novel molecular weight controlled and endcapped polybenzimidazoles (PBI) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenyl benzimidazole) monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The PBI are endcapped with mono(hydroxyphenyl) benzimidazoles. The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N,N-dimethylacetamide using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. Mono(hydroxyphenyl) benzimidazoles are synthesizedby reacting phenyl-4-hydroxybenzoate with aromatic (o-diamine)s in diphenylsulfone. Molecular weight controlled and endcapped PBI of new chemical structures are prepared that exhibit a favorable combination of physical and mechanical properties.

Trimerization of aromatic nitriles

NASA Technical Reports Server (NTRS)

Hsu, L. C. (Inventor)

1977-01-01

Triazine compounds and cross-linked polymer compositions were made by heating aromatic nitriles to a temperature in the range of about 100 C to about 700 C, in the presence of a catalyst or mixture of catalysts. Aromatic nitrile-modified (terminated and/or appended) imide, benzimidazole, imidazopyrrolone, quinoxaline, and other condensation type prepolymers or their precopolymers were made which were trimerized with or without a filler by the aforementioned catalytic trimerization process.

Susceptibility of eastern oyster early life stages to road surface polycyclic aromatic hydrocarbons (PAHs).

DOT National Transportation Integrated Search

2012-06-01

Polycyclic aromatic hydrocarbons (PAHs) are a class of chemical compounds that are mostly : anthropogenic in nature, and they can become persistent organic contaminants in aquatic : ecosystems. Runoff from impervious surfaces is one of the many ways ...

CONTROL OF AROMATIC WASTE AIR STREAMS BY SOIL BIOREACTORS

EPA Science Inventory

Three soils were examined for the ability to degrade hydrocarbon vapors of benzene, toluene, ethylbenzene, and o-xylene (BTEX). Each of these compounds are major aromatic constituents of gasolines. The soils examined were Rubicon Sand from Traverse City, Michigan, Durant Loam fro...

[Characteristics of organic pollutants in the sediments from a typical electronics industrial zone].

PubMed

Liu, Jin; Deng, Dai-Yong; Xu, Mei-Ying; Sun, Guo-Ping

2013-03-01

In order to investigate the contamination status of organic pollutants in a river of a typical electrical equipment industrial area, Ronggui, Foshan, the sediments were sampled for the composition, concentration and occurrence analysis of organic pollutants. The polar and non-polar fractionation methods were employed for the fingerprint establishment of organic pollutants. One hundred and seventy-one of organic chemicals including ten categories of alkanes, alkenes, polycyclic aromatic hydrocarbons, benzene, heterocyclic compounds, phthalate esters, aldehydes, ketones, polar compounds, silicon-containing material as well as alkyl esters were examined. The number of different categories of the detected organic pollutants in a descending order was: alkanes > polar compounds > polycyclic aromatic hydrocarbons > aldehydes and ketones > heterocyclic compounds > benzene homologues, phthalate ester > alkyl esters > silicon material > olefins. The abundance of detected organic pollutants in a descending order was: alkanes > polar compounds > alkyl esters > olefins > polycyclic aromatic hydrocarbons > phthalates > silicon material > aldehydes and ketones > heterocyclic compounds > benzene homologues. Among the 51 kinds of alkanes detected, nonadecane accounted for 14.83%, and the persistent organic pollutants accounted for 2.33% of the total organic matter. Compared to similar studies, there were 51 kinds of alkanes and they accounted for 55.5% of the total organic chemicals, showing high diversity and abundance. In addition, some electronics industry-related organic pollutants such as silicone materials were also detected in high frequency.

Photocatalytic degradation of paracetamol: intermediates and total reaction mechanism.

PubMed

Moctezuma, Edgar; Leyva, Elisa; Aguilar, Claudia A; Luna, Raúl A; Montalvo, Carlos

2012-12-01

The advanced oxidation of paracetamol (PAM) promoted by TiO(2)/UV system in aqueous medium was investigated. Monitoring this reaction by HPLC and TOC, it was demonstrated that while oxidation of paracetamol is quite efficient under these conditions, its mineralization is not complete. HPLC indicated the formation of hydroquinone, benzoquinone, p-aminophenol and p-nitrophenol in the reaction mixtures. Further evidence of p-nitrophenol formation was obtained following the reaction by UV-vis spectroscopy. Continuous monitoring by IR spectroscopy demonstrated the breaking of the aromatic amide present in PAM and subsequent formation of several aromatic intermediate compounds such as p-aminophenol and p-nitrophenol. These aromatic compounds were eventually converted into trans-unsaturated carboxylic acids. Based on these experimental results, an alternative deacylation mechanism for the photocatalytic oxidation of paracetamol is proposed. Our studies also demonstrated IR spectroscopy to be a useful technique to investigate oxidative mechanisms of pharmaceutical compounds. Copyright © 2012 Elsevier B.V. All rights reserved.

Stereodynamics and edge-to-face CH-π aromatic interactions in imino compounds containing heterocyclic rings.

PubMed

González-Rosende, M Eugenia; Castillo, Encarna; Jennings, W Brian; Malone, John F

2017-02-07

By comparison with close contact interactions between benzene rings there is a paucity of experimental data available for attractive interactions involving aromatic heterocyclic rings, especially for small molecules in solution. Herein we describe aromatic heterocyclic and carbocyclic edge-to face interactions and conformational stereodynamics of N-1,2-diphenylethyl imines bearing a phenyl group and either a 2-pyridyl, 3-pyridyl, 2-thiophene or 2-furanyl moiety on the imino carbon. X-ray crystal structures have been determined for two compounds. Slow rotation about the phenyl-imino bond in the E-isomers and around the heterocycle-imino bond in the Z-isomers of the pyridyl compounds was observed at low temperatures by NMR. Abnormally large shielding of one ortho hydrogen indicates that both the imino phenyl and heterocycle rings can engage in an edge-to-face interaction with the N-terminal phenyl moiety in the appropriate isomer. Some rotational barriers around the phenyl-imino and heterocycle-imino bonds were measured.

In situ growth of monodispersed Fe3O4 nanoparticles on graphene for the removal of heavy metals and aromatic compounds.

PubMed

Wu, Hai-Xia; Wu, Jia-Wei; Niu, Zhi-Gang; Shang, Xiu-Li; Jin, Jun

2013-01-01

We report on the efficient removal of heavy metal ions and aromatic compounds from simulated wastewater with a nanocomposite. The nanocomposite was obtained via thermal decomposition of the precursor Fe(acac)3 onto the surface of graphene, modified by diethylenetriamine pentaacetic anhydride through dopamine. It was found that the maximum adsorption capacity of the nanocomposite toward Cu(2+) and naphthalene was 207.9 and 72.2 mg g(-1) respectively, displaying a high efficiency for the removal of heavy metal ions as well as aromatic compounds at pH 7.0 and 293 K. The Langmuir for naphthalene and the Freundlich for the Cu(2+) adsorption isotherms were applicable for describing the removal processes. Furthermore, the nanocomposite was carefully examined by transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, Raman spectra, and UV-vis spectroscopy. This work provides a very efficient, fast and convenient approach to exploring a promising nanocomposite for water treatment.

In Vitro Antifungal Activity of New and Known Geranylated Phenols against Phytophthora cinnamomi Rands.

PubMed

Chavez, María I; Soto, Mauricio; Cimino, Franco A; Olea, Andrés F; Espinoza, Luis; Díaz, Katy; Taborga, Lautaro

2018-05-29

A series of new and known geranylated phenol/methoxyphenol derivatives has been tested in vitro as inhibitor agents of mycelial growth of Phytophthora cinnamomi . The activity of tested compounds is correlated with the nature, number, and position of the substituent group on the aromatic ring. Results indicate that the most active geranylated derivatives are those having two hydroxyl groups (or one ⁻OH and one ⁻OCH₃) attached to the aromatic ring. Interestingly, these derivatives are as active as Metalaxil ® , a commonly used commercial fungicide. Thus, our results suggest that some of these compounds might be of agricultural interest due to their potential use as fungicides against P. cinnamomi . The effect of structure on fungicide activity is discussed in terms of electronic distribution on both the aromatic ring and side geranyl chain. All tested compounds have been synthesized by direct coupling of geraniol and the respective phenol. Interestingly, new digeranylated derivatives were obtained by increasing the reaction time.

Synthesis and electronic factors in thermal cyclodimerization of functionalized aromatic trifluorovinyl ethers.

PubMed

Spraul, Bryan K; Suresh, S; Jin, Jianyong; Smith, Dennis W

2006-05-31

A series of 19 p-substituted aromatic trifluorovinyl ether compounds were prepared from versatile intermediate p-Br-C(6)H(4)-O-CF=CF(2) and underwent thermal radical mediated cyclodimerization to new difunctional compounds containing the 1,2-disubstituted perfluorocyclobutyl (PFCB) linkage. The synthetic scope demonstrates the functional group transformation tolerance of the fluorovinyl ether, and the dimers are useful as monomers for traditional step-growth polymerization methods. (19)F NMR spectra confirmed that p-substitution affects the trifluorovinyl ether group chemical shifts. The first kinetic studies and substituent effects on thermal cyclodimerization were performed, and the results indicated that electron-withdrawing groups slow the rate of cyclodimerization. The data were further analyzed using the Hammett equation, and reaction constants (rho) of -0.46 at 120 degrees C and -0.59 at 130 degrees C were calculated. This study presents the first liner free energy relationship reported for the cyclodimerization of aromatic trifluorovinyl ethers to PFCB compounds.

CHEMISTRY OF OXIDATION OF POLYCYCLIC AROMATIC HYDROCARBONS BY SOIL PSEUDOMONADS

PubMed Central

Rogoff, Martin H.

1962-01-01

Rogoff, Martin H. (U.S. Bureau of Mines, Pittsburgh, Pa.). Oxidation of polycyclic aromatic hydrocarbons by soil pseudomonads. J. Bacteriol. 83:998–1004. 1962.—Substitution of phenanthrene by a methyl group at the 9-carbon blocks oxidation of the compound by a resting-cell suspension of a phenanthrene-grown soil pseudomonad. When 2-methylphenanthrene is provided, the oxidation rate is considerably higher; 3-methylphenanthrene is oxidized at a rate intermediate between the other two, even though the methyl group is attached to a carbon directly involved in ring splitting. Cells grown on naphthalene or anthracene oxidize phenanthrene at a much lower rate than cells grown with phenanthrene or 2-methylnaphthalene as the source of carbon. Naphthalene-grown cells also absorb less phenanthrene from aqueous solution than do their phenanthrene-grown counterparts. The data are in keeping with the hypothesis that polynuclear aromatic hydrocarbons attach to the relevant bacterial enzymes at carbon-carbon bonds of high electron density (K regions; localized double bonds), and that the ring-splitting reactions then occur at other bonds on the substrate molecule. The actual bond that undergoes fission is determined by the electronic and steric configurations of the enzyme-substrate complex. When linearly arranged aromatic compounds such as naphthalene or anthracene are attacked, attachment to an enzyme and ring splitting may take place on the same ring; angular aromatic compounds such as phenanthrene afford attachment to an enzyme at a bond in a ring other than the one containing the ring-splitting site. PMID:14493381

Effect of Temperature and Process on Quantity and Composition of Laboratory-generated Bitumen Emissions.

PubMed

Bolliet, Christophe; Kriech, Anthony J; Juery, Catherine; Vaissiere, Mathieu; Brinton, Michael A; Osborn, Linda V

2015-01-01

In this study we investigated the impact of temperature on emissions as related to various bitumen applications and processes used in commercial products. Bitumen emissions are very complex and can be influenced in quantity and composition by differences in crude source, refining processes, application temperature, and work practices. This study provided a controlled laboratory environment to study five bitumen test materials from three European refineries; three paving grade, one used for primarily roofing and some paving applications, and one oxidized industrial specialty bitumen. Emissions were generated at temperatures between 140°C and 230°C based on typical application temperatures of each product. Emissions were characterized by aerodynamic particle size, total organic matter (TOM), simulated distillation, 40 individual PACs, and fluorescence (FL-PACs) spectroscopy. Results showed that composition of bitumen emissions is influenced by temperature under studied experimental conditions. A distinction between the oxidized bitumen with flux oil (industrial specialty bitumen) and the remaining bitumens was observed. Under typical temperatures used for paving (150°C-170°C), the TOM and PAC concentrations in the emissions were low. However, bitumen with flux oil produced significantly higher emissions at 230°C, laden with high levels of PACs. Flux oil in this bitumen mixture enhanced release of higher boiling-ranged compounds during application conditions. At 200°C and below, concentrations of 4-6 ring PACs were ≤6.51 μg/m(3) for all test materials, even when flux oil was used. Trends learned about emission temperature-process relationships from this study can be used to guide industry decisions to reduce worker exposure during processing and application of hot bitumen.

Characteristic analysis for odor gas emitted from food waste anaerobic fermentation in the pretreatment workshop.

PubMed

Di, Yanqiang; Liu, Jiemin; Liu, Jianguo; Liui, Siyuan; Yan, Luchun

2013-10-01

Gas chromatography-mass spectrometry, olfactometry, and other related methods were applied for the qualitative and quantitative analysis of the characteristics of odorous gases in the pretreatment workshop. The composition of odorous gases emitted from municipal food waste was also investigated in this study. The results showed that the tested gases are mainly composed of aromatic gases, which account for 49% of the total volatile organic compounds (VOC) concentrations. The nitrogenous compounds comprise 15% of the total concentration and the other gases comprise the remaining 36%. The level of odor concentration ranged from 2523 odor units (OU) m(-3) to 3577 OU m(-3). The variation of the total chemical composition ranged from 19,725 microg m(-3) to 24,184 microg m(-3). Among the selected four sampling points, the discharge outlet was detected to have the highest concentration in terms of odor, total chemical, sulfur compounds, and aromatics. The correlation analysis showed that the odor concentrations were evidently related to the total chemical composition, sulfur compounds, and aromatics (P < 0.05, n = 5). The odor activity value analysis identified the top three compounds, hydrogen sulfide (91.8), ethyl sulfide (35.8), and trimethylamine (70.6), which contribute to air pollution complaint of waste materials.

Dielectric barrier discharge ionization for liquid chromatography/mass spectrometry.

PubMed

Hayen, Heiko; Michels, Antje; Franzke, Joachim

2009-12-15

An atmospheric pressure microplasma ionization source based on a dielectric barrier discharge with a helium plasma cone outside the electrode region has been developed for liquid chromatography/mass spectrometry (LC/MS). For this purpose, the plasma was realized in a commercial atmospheric pressure ionization source. Dielectric barrier discharge ionization (DBDI) was compared to conventional electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI), and atmospheric pressure photoionization (APPI) in the positive ionization mode. Therefore, a heterogeneous compound library was investigated that covered polar compounds such as amino acids, water-soluble vitamins, and nonpolar compounds like polycyclic aromatic hydrocarbons and functionalized hydrocarbons. It turned out that DBDI can be regarded as a soft ionization technique characterized by only minor fragmentation similar to APCI. Mainly protonated molecules were detected. Additionally, molecular ions were observed for polycyclic aromatic hydrocarbons and derivatives thereof. During DBDI, adduct formation with acetonitrile occurred. For aromatic compounds, addition of one to four oxygen atoms and to a smaller extend one nitrogen and oxygen was observed which delivered insight into the complexity of the ionization processes. In general, compounds covering a wider range of polarities can be ionized by DBDI than by ESI. Furthermore, limits of detection compared to APCI are in most cases equal or even better.

Lipophilic extracts of Cynara cardunculus L. var. altilis (DC): a source of valuable bioactive terpenic compounds.

PubMed

Ramos, Patrícia A B; Guerra, Ângela R; Guerreiro, Olinda; Freire, Carmen S R; Silva, Artur M S; Duarte, Maria F; Silvestre, Armando J D

2013-09-04

Lipophilic extracts of Cynara cardunculus L. var. altilis (DC) from the south of Portugal (Baixo Alentejo) were studied by gas chromatography-mass spectrometry. One sesquiterpene lactone, four pentacyclic triterpenes, and four sterols were reported for the first time as cultivated cardoon components, namely, deacylcynaropicrin, β- and α-amyrin, lupenyl and ψ-taraxasteryl acetates, stigmasterol, 24-methylenecholesterol, campesterol, and Δ(5)-avenasterol. In addition, other new compounds were identified: ten fatty acids, eight long-chain aliphatic alcohols, and six aromatic compounds. Four triterpenyl fatty acid esters were also detected. Sesquiterpene lactones and pentacyclic triterpenes were the major lipophilic families, representing respectively 2-46% and 10-89% of the detected compounds. Cynaropicrin was the most abundant sesquiterpene lactone, while taraxasteryl acetate was the main pentacyclic triterpene. Fatty acids and sterols, mainly hexadecanoic acid and β-sitosterol, were present at lower amounts (1-20% and 1-11% of the detected compounds). Long-chain aliphatic alcohols and aromatic compounds were detected at reduced abundances (1-6% of the detected compounds).

AROMATIC AMINES IN AND NEAR THE BUFFALO RIVER

EPA Science Inventory

Three sediment samples taken from the Buffalo River and two soil samples taken near its bank have been analyzed for 2-propanol-extractable, basic organic compounds by using GC/MS. Eleven aromatic amines related to the commercial production of malachite green and crystal violet we...

QSAR Study for Carcinogenic Potency of Aromatic Amines Based on GEP and MLPs

PubMed Central

Song, Fucheng; Zhang, Anling; Liang, Hui; Cui, Lianhua; Li, Wenlian; Si, Hongzong; Duan, Yunbo; Zhai, Honglin

2016-01-01

A new analysis strategy was used to classify the carcinogenicity of aromatic amines. The physical-chemical parameters are closely related to the carcinogenicity of compounds. Quantitative structure activity relationship (QSAR) is a method of predicting the carcinogenicity of aromatic amine, which can reveal the relationship between carcinogenicity and physical-chemical parameters. This study accessed gene expression programming by APS software, the multilayer perceptrons by Weka software to predict the carcinogenicity of aromatic amines, respectively. All these methods relied on molecular descriptors calculated by CODESSA software and eight molecular descriptors were selected to build function equations. As a remarkable result, the accuracy of gene expression programming in training and test sets are 0.92 and 0.82, the accuracy of multilayer perceptrons in training and test sets are 0.84 and 0.74 respectively. The precision of the gene expression programming is obviously superior to multilayer perceptrons both in training set and test set. The QSAR application in the identification of carcinogenic compounds is a high efficiency method. PMID:27854309

Aromaticity of benzene derivatives: an exploration of the Cambridge Structural Database.

PubMed

Majerz, Irena; Dziembowska, Teresa

2018-04-01

The harmonic oscillator model of aromaticity (HOMA) index, one of the most popular aromaticity indices for solid-state benzene rings in the Cambridge Structural Database (CSD), has been analyzed. The histograms of HOMA for benzene, for benzene derivatives with one formyl, nitro, amino or hydroxy group as well as the histograms for the derivatives with two formyl, nitro, amino or hydroxy groups in ortho, meta and para positions were investigated. The majority of the substituted benzene derivatives in the CSD are characterized by a high value of HOMA, indicating fully aromatic character; however, the distribution of the HOMA value from 1 to about 0 indicates decreasing aromaticity down to non-aromatic character. Among the benzene derivatives investigated, a significant decrease in aromaticity can be related to compounds with diamino and dinitro groups in the meta position.

Effect of counter ions of arginine as an additive for the solubilization of protein and aromatic compounds.

PubMed

Yoshizawa, Shunsuke; Arakawa, Tsutomu; Shiraki, Kentaro

2016-10-01

Arginine is widely used in biotechnological application, but mostly with chloride counter ion. Here, we examined the effects of various anions on solubilization of aromatic compounds and reduced lysozyme and on refolding of the lysozyme. All arginine salts tested increased the solubility of propyl gallate with acetate much more effectively than chloride. The effects of arginine salts were compared with those of sodium or guanidine salts, indicating that the ability of anions to modulate the propyl gallate solubility is independent of the cation. Comparison of transfer free energy of propyl gallate between sodium and arginine salts indicates that the interaction of propyl gallate is more favorable with arginine than sodium. On the contrary, the solubility of aromatic amino acids is only slightly modulated by anions, implying that there is specific interaction between acetic acid and propyl gallate. Unlike their effects on the solubility of small aromatic compounds, the solubility of reduced lysozyme was much higher in arginine chloride than in arginine acetate or sulfate. Consistent with high solubility, refolding of reduced lysozyme was most effective in arginine chloride. These results suggest potential broader applications of arginine modulated by different anions. Copyright © 2016 Elsevier B.V. All rights reserved.

Enhancing trichloroethylene degradation using non-aromatic compounds as growth substrates.

PubMed

Kim, Seungjin; Hwang, Jeongmin; Chung, Jinwook; Bae, Wookeun

2014-06-30

The effect of non-aromatic compounds on the trichloroethylene (TCE) degradation of toluene-oxidizing bacteria were evaluated using Burkholderia cepacia G4 that expresses toluene 2-monooxygenase and Pseudomonas putida that expresses toluene dioxygenase. TCE degradation rates for B. cepacia G4 and P. putida with toluene alone as growth substrate were 0.144 and 0.123 μg-TCE/mg-protein h, respectively. When glucose, acetate and ethanol were fed as additional growth substrates, those values increased up to 0.196, 0.418 and 0.530 μg-TCE/mg-protein h, respectively for B. cepacia G4 and 0.319, 0.219 and 0.373 μg-TCE/mg-protein h, respectively for P. putida. In particular, the addition of ethanol resulted in a high TCE degradation rate regardless of the initial concentration. The use of a non-aromatic compound as an additional substrate probably enhanced the TCE degradation because of the additional supply of NADH that is consumed in co-metabolic degradation of TCE. Also, it is expected that the addition of a non-aromatic substrate can reduce the necessary dose of toluene and, subsequently, minimize the potential competitive inhibition upon TCE co-metabolism by toluene. Copyright © 2014 Elsevier B.V. All rights reserved.

Human Immunodeficiency Virus Type 1 cDNA Integration: New Aromatic Hydroxylated Inhibitors and Studies of the Inhibition Mechanism

PubMed Central

Farnet, C. M.; Wang, B.; Hansen, M.; Lipford, J. R.; Zalkow, L.; Robinson, W. E.; Siegel, J.; Bushman, F.

1998-01-01

Integration of the human immunodeficiency virus type 1 (HIV-1) cDNA is a required step for viral replication. Integrase, the virus-encoded enzyme important for integration, has not yet been exploited as a target for clinically useful inhibitors. Here we report on the identification of new polyhydroxylated aromatic inhibitors of integrase including ellagic acid, purpurogallin, 4,8,12-trioxatricornan, and hypericin, the last of which is known to inhibit viral replication. These compounds and others were characterized in assays with subviral preintegration complexes (PICs) isolated from HIV-1-infected cells. Hypericin was found to inhibit PIC assays, while the other compounds tested were inactive. Counterscreening of these and other integrase inhibitors against additional DNA-modifying enzymes revealed that none of the polyhydroxylated aromatic compounds are active against enzymes that do not require metals (methylases, a pox virus topoisomerase). However, all were cross-reactive with metal-requiring enzymes (restriction enzymes, a reverse transcriptase), implicating metal atoms in the inhibitory mechanism. In mechanistic studies, we localized binding of some inhibitors to the catalytic domain of integrase by assaying competition of binding by labeled nucleotides. These findings help elucidate the mechanism of action of the polyhydroxylated aromatic inhibitors and provide practical guidance for further inhibitor development. PMID:9736543

The Use of Modified Bentonite for Removal of Aromatic Organics from Contaminated Soil.

PubMed

Gitipour; Bowers; Bodocsi

1997-12-15

This study investigates the clay-aromatic interactions with a view to the use of bentonite clay for binding benzene, toluene, ethylbenzene, and o-xylene (BTEX compounds) in contaminated soils. BTEX compounds are the most toxic aromatic constituents of gasoline present in many underground storage tanks. Modified (organophilic) and ordinary bentonites are used to remove these organics. The organophilic bentonites are prepared by replacing the exchangeable inorganic cations present in bentonite particles with a quaternary ammonium salt. Various clay-to-soil ratios were applied to determine the efficiency of the modified bentonite in enhancing the cement-based solidification/stabilization (S/S) of BTEX contaminated soils. Toxicity characteristics leaching procedure (TCLP) tests were performed on soil samples to evaluate the leaching of the organics. In addition, X-ray diffraction analyses were conducted to assess the changes in the basal spacing of the clays as a result of their interaction with BTEX compounds. The findings of this study reveal that organophilic bentonite can act as a successful adsorbent for removing the aromatic organics from contaminated soil. Thus, this material is viable for enhancing the performance of cement-based S/S processes, as an adsorbent for petroleum spills, and for landfill liners and slurry walls. Copyright 1997 Academic Press.

Transformations of Aromatic Compounds by Nitrosomonas europaea

PubMed Central

Keener, William K.; Arp, Daniel J.

1994-01-01

Benzene and a variety of substituted benzenes inhibited ammonia oxidation by intact cells of Nitrosomonas europaea. In most cases, the inhibition was accompanied by transformation of the aromatic compound to a more oxidized product or products. All products detected were aromatic, and substituents were often oxidized but were not separated from the benzene ring. Most transformations were enhanced by (NH4)2SO4 (12.5 mM) and were prevented by C2H2, a mechanism-based inactivator of ammonia monooxygenase (AMO). AMO catalyzed alkyl substituent hydroxylations, styrene epoxidation, ethylbenzene desaturation to styrene, and aniline oxidation to nitrobenzene (and unidentified products). Alkyl substituents were preferred oxidation sites, but the ring was also oxidized to produce phenolic compounds from benzene, ethylbenzene, halobenzenes, phenol, and nitrobenzene. No carboxylic acids were identified. Ethylbenzene was oxidized via styrene to two products common also to oxidation of styrene; production of styrene is suggestive of an electron transfer mechanism for AMO. Iodobenzene and 1,2-dichlorobenzene were oxidized slowly to halophenols; 1,4-dichlorobenzene was not transformed. No 2-halophenols were detected as products. Several hydroxymethyl (-CH2OH)-substituted aromatics and p-cresol were oxidized by C2H2-treated cells to the corresponding aldehydes, benzaldehyde was reduced to benzyl alcohol, and o-cresol and 2,5-dimethylphenol were not depleted. PMID:16349282

Application of UV-visible absorption spectroscopy combined with two-dimensional correlation for insight into DOM fractions from native halophyte soils in a larger estuarine delta.

PubMed

Wei, Huaibin; Yu, Huibin; Pan, Hongwei; Gao, Hongjie

2018-05-01

UV-visible absorption spectroscopy combined with principal component analysis (PCA) and two-dimensional correlation (2D correlation) is used to trace components of dissolved organic matter (DOM) extracted from soils in a larger estuarine delta and to investigate spatial variations of DOM fractions. Soil samples of different depths were collected from native halophyte soils along a saline gradient, i.e., Suaeda salsa Comm. (SSC), Chenopodium album Comm. (CAC), Phragmites australis Comm. (PAC), and Artemisia selengensis Comm. (ASC). Molecular weights of DOM within the SSC soil profile were the lowest, followed by the CAC, PAC, and ASC soil profiles. Humification degree of DOM within the ASC soil profile was the highest, followed by the PAC, SSC, and CAC soil profiles. DOM within the soil profiles mainly contained phenolic, carboxylic, microbial products, and aromatic and alkyl groups through the PCA, which presented the significant differentiation among the four native halophyte soil profiles. The 2D UV correlation spectra of DOM within the SSC soil profile indicated that the variations of the phenolic groups were the largest, followed by the carboxylic groups, microbial products, and humified organic materials according to the band changing order of 285 → 365 → 425 → 520 nm. The 2D UV correlation spectra of DOM within the CAC soil profiles determined that the decreasing order of the variations was phenolic groups > carboxylic groups > microbial products according the band changing order of 285 → 365 → 425 nm. The 2D UV correlation spectra of DOM within the PAC soil profile proved that the variations of the phenolic groups were larger than those of the carboxylic groups according to the band changing order of 285 → 365 nm. The 2D UV correlation spectra of DOM within the ASC soil profile demonstrated that the variations of the phenolic groups were larger than those of the other DOM fractions according to the broad cross-peak at 285/365-700 nm.

Type of litter determines the formation and properties of charred material during wildfires

NASA Astrophysics Data System (ADS)

Chavez, Bruno; Fonturbel, M. Teresa; Salgado, Josefa; García-Oliva, Felipe; Vega, Jose A.; Merino, Agustin

2014-05-01

Wildfire is one of the most important disturbances all over the World, affecting both the amount and composition of forest floor and mineral soils. In comparison with unburnt areas, wildfire-affected forest floor usually shows lower contents of labile C compounds and higher concentrations of recalcitrant aromatic forms. These changes in composition can have important impact on biogeochemical cycles and therefore ecosystem functions. Although burning of different types of litter can lead to different amount and types of pyrogenic compounds, this aspect has not been evaluated yet. The effect of wildfire on SOM composition and stability were evaluated in five major types of non-wood litter in Mediterranean ecosystems: Pinus nigra, E. arborea, P. pinaster, U. europaeus and Eucalyptus globulus. In each of these ecosystems, forest floor samples from different soil burn severities were sampled. Soil burnt severities were based on visual signs of changes in forest floor and deposition of ash. Pyrogenic carbon quality were analysed using elementary analysis, solid-state 13 C nuclear magnetic resonance spectroscopy, Reflectance Infrared Fourier Transform (FTIR) and thermal analysis (simultaneous DSC-TG). The study showed that the different types of litter influenced the formation and characteristics of charred material. They differed in the temperature at which they start to be formed, the amounts of charred compounds and in their chemical composition. The resulting charred materials from the different litter, showed an important variability in the degree of carbonitation/aromatization. Unlike the biochar obtained through pyrolysis of woody sources, which contains exclusively aromatic structures, in the charred material produced in some litter, lignin, cellulose and even cellulose persist even in the high soil burnt severity. Coinciding with increases in aromatic contents, important decreases in atomic H/C and O/C ratios were recorded. However, the values found in some litters, were higher than 0.5, suggesting that low degree of carbonization/aromatization. Although burning also led to compounds of higher thermal recalcitrance (increases in T50 values), values recorded in some litters were lower than those measured in highly polycondensed aromatic compounds. The differences found among the different forest floor cannot be only attributable to the initial SOM composition of the litter. Other aspects, such as the different thermal sensitivity, flammability and different conditions during wildfire (temperatures, combustion duration, oxygen concentrations) could also have contributed.

Aroma characterization based on aromatic series analysis in table grapes

PubMed Central

Wu, Yusen; Duan, Shuyan; Zhao, Liping; Gao, Zhen; Luo, Meng; Song, Shiren; Xu, Wenping; Zhang, Caixi; Ma, Chao; Wang, Shiping

2016-01-01

Aroma is an important part of quality in table grape, but the key aroma compounds and the aroma series of table grapes remains unknown. In this paper, we identified 67 aroma compounds in 20 table grape cultivars; 20 in pulp and 23 in skin were active compounds. C6 compounds were the basic background volatiles, but the aroma contents of pulp juice and skin depended mainly on the levels of esters and terpenes, respectively. Most obviously, ‘Kyoho’ grapevine series showed high contents of esters in pulp, while Muscat/floral cultivars showed abundant monoterpenes in skin. For the aroma series, table grapes were characterized mainly by herbaceous, floral, balsamic, sweet and fruity series. The simple and visualizable aroma profiles were established using aroma fingerprints based on the aromatic series. Hierarchical cluster analysis (HCA) and principal component analysis (PCA) showed that the aroma profiles of pulp juice, skin and whole berries could be classified into 5, 3, and 5 groups, respectively. Combined with sensory evaluation, we could conclude that fatty and balsamic series were the preferred aromatic series, and the contents of their contributors (β-ionone and octanal) may be useful as indicators for the improvement of breeding and cultivation measures for table grapes. PMID:27487935

Influence of Tunisian aromatic plants on the prevention of oxidation in soybean oil under heating and frying conditions.

PubMed

Saoudi, Salma; Chammem, Nadia; Sifaoui, Ines; Bouassida-Beji, Maha; Jiménez, Ignacio A; Bazzocchi, Isabel L; Silva, Sandra Diniz; Hamdi, Moktar; Bronze, Maria Rosário

2016-12-01

The aim of this study was to improve the oxidative stability of soybean oil by using aromatic plants. Soybean oil flavored with rosemary (ROS) and soybean oil flavored with thyme (THY) were subjected to heating for 24h at 180°C. The samples were analyzed every 6h for their total polar compounds, anisidine values, oxidative stability and polyphenols content. The tocopherols content was determined and volatile compounds were also analyzed. After 24h of heating, the incorporation of these plants using a maceration process reduced the polar compounds by 69% and 71% respectively, in ROS and THY compared to the control. Until 6h of heating, the ROS kept the greatest oxidative stability. The use of the two extracts preserves approximately 50% of the total tocopherols content until 18h for the rosemary and 24h for the thyme flavored oils. Volatile compounds known for their antioxidant activity were also detected in the formulated oils. Aromatic plants added to the soybean oil improved the overall acceptability of potato crisps (p<0.05) until the fifteenth frying. Copyright © 2016 Elsevier Ltd. All rights reserved.

Adsorption of aromatic compounds from the biodegradation of azo dyes on activated carbon

NASA Astrophysics Data System (ADS)

Faria, P. C. C.; Órfão, J. J. M.; Figueiredo, J. L.; Pereira, M. F. R.

2008-03-01

The adsorption of three selected aromatic compounds (aniline, sulfanilic acid and benzenesulfonic acid) on activated carbons with different surface chemical properties was investigated at different solution pH. A fairly basic commercial activated carbon was modified by means of chemical treatment with HNO 3, yielding an acid activated carbon. The textural properties of this sample were not significantly changed after the oxidation treatment. Equilibrium isotherms of the selected compounds on the mentioned samples were obtained and the results were discussed in relation to their surface chemistry. The influence of electrostatic and dispersive interactions involved in the uptake of the compounds studied was evaluated. The Freundlich model was used to fit the experimental data. Higher uptakes are attained when the compounds are present in their molecular form. In general, adsorption was disfavoured by the introduction of oxygen-containing groups on the surface of the activated carbon.

Suspect screening of OH-PAHs and non-target screening of other organic compounds in wood smoke particles using HR-Orbitrap-MS.

PubMed

Avagyan, Rozanna; Åberg, Magnus; Westerholm, Roger

2016-11-01

Wood combustion has been shown to contribute significantly to emissions of polycyclic aromatic hydrocarbons and hydroxylated polycyclic aromatic hydrocarbons, compounds with toxic and carcinogenic properties. However, only a small number of hydroxylated polycyclic aromatic hydrocarbons have been determined in particles from wood combustion, usually compounds with available reference standards. In this present study, suspect and non-target screening strategies were applied to characterize the wood smoke particles from four different wood types and two combustion conditions with respect to hydroxylated polycyclic aromatic hydrocarbons and other organic compounds. In the suspect screening, 32 peaks corresponding to 12 monohydroxylated masses were tentatively identified by elemental composition assignments and matching of isotopic pattern and fragments. More than one structure was suggested for most of the measured masses. Statistical analysis was performed on the non-target screening data in order to single out significant peaks having intensities that depend on the wood type and/or combustion condition. Significant peaks were found in both negative and positive ionization modes, with unique peaks for each wood type and combustion condition, as well as a combination of both factors. Furthermore, structural elucidation of some peaks was done by comparing the spectra in the samples with spectra found in the spectral databases. Six compounds were tentatively identified in positive ionization mode, and 19 in negative ionization mode. The results in this present study demonstrate that there are significant overall differences in the chemistry of wood smoke particles that depends on both the wood type and the combustion condition used. Copyright © 2016 Elsevier Ltd. All rights reserved.

[Chromatographic mass spectrometric determination of low-molecular-weight aromatic compounds of microbial origin in the serum from patients with sepsis].

PubMed

Beloborodova, N V; Arkhipova, A S; Beloborodov, D M; Boĭko, N B; Mel'ko, A I; Olenin, A Iu

2006-02-01

The investigation quantitatively determined the content of low-molecular-weight aromatic compounds of microbial origin in the sera of 34 individuals by chromatographic mass spectrometry. An "Agilent Technogies 6890N" gas chromatograph with a 5973 mass selective detector was applied; chromatographic separation of components was effected on an Hp-5MS quartz capillary column. Aromatic small molecules originating from microbes (SMOM) were determined in the sera of 7 patients with sepsis. The diagnosis of sepsis was documented by the presence of the systemic inflammation syndrome and by that of bacteriemia and/or artificial ventilation-associated pneumonia along with the level of procalcitonin of higher than 10 ng/ml. The levels of aromatic SMOM were compared in 10 healthy donors, 8 preoperative cardiosurgical patients, and 9 patients with different abnormalities without sepsis treated in an intensive care unit (ICU). Serum phenylacetic and 3-phenylpropionic acids were found to be prevalent in the healthy donors and postoperative cardiosurgical patients. In ICU patients with different complications without sepsis, more than half the compounds under study were undetectable, the others were found in very low concentrations, which may be accounted for by antibiotic therapy. At the same time, almost the whole spectrum of the test compounds (other than 3-phenylpropionic acid) with the highest concentrations of 3-phenyllactic, p-hydroxyphenylacetic, 3-(p-hydroxyphenyl)lactic and 2-hydroxybutanic acids, was detectable in septic patients receiving a more intensive therapy. The differences were statistically significant (by the Mann-Whitney U-test; p < 0.05). By taking into account the potentially high biological activity of the test compounds, studies are to be continued in this area.

Production of Monomeric Aromatic Compounds from Oil Palm Empty Fruit Bunch Fiber Lignin by Chemical and Enzymatic Methods.

PubMed

Tang, Pei-Ling; Hassan, Osman; Maskat, Mohamad Yusof; Badri, Khairiah

2015-01-01

In this study, oil palm empty fruit bunch (OPEFBF) was pretreated with alkali, and lignin was extracted for further degradation into lower molecular weight phenolic compounds using enzymes and chemical means. Efficiency of monomeric aromatic compounds production from OPEFBF lignin via chemical (nitrobenzene versus oxygen) and enzymatic [cutinase versus manganese peroxidase (MnP)] approaches was investigated. The effects of sodium hydroxide concentration (2, 5, and 10% wt.) and reaction time (30, 90, and 180 minutes) on the yield of aromatic compounds were studied. The results obtained indicated that nitrobenzene oxidation produced the highest yield (333.17 ± 49.44 ppm hydroxybenzoic acid, 5.67 ± 0.25 ppm p-hydroxybenzaldehyde, 25.57 ± 1.64 ppm vanillic acid, 168.68 ± 23.23 ppm vanillin, 75.44 ± 6.71 ppm syringic acid, 815.26 ± 41.77 ppm syringaldehyde, 15.21 ± 2.19 ppm p-coumaric acid, and 44.75 ± 3.40 ppm ferulic acid), among the tested methods. High sodium hydroxide concentration (10% wt.) was needed to promote efficient nitrobenzene oxidation. However, less severe oxidation condition was preferred to preserve the hydroxycinnamic acids (p-coumaric acid and ferulic acid). Cutinase-catalyzed hydrolysis was found to be more efficient than MnP-catalyzed oxidation in the production of aromatic compounds. By hydrolyzed 8% wt. of lignin with 0.625 mL cutinase g(-1) lignin at pH 8 and 55°C for 24 hours, about 642.83 ± 14.45 ppm hydroxybenzoic acid, 70.19 ± 3.31 ppm syringaldehyde, 22.80 ± 1.04 ppm vanillin, 27.06 ± 1.20 ppm p-coumaric acid, and 50.19 ± 2.23 ppm ferulic acid were produced.

Novel Scheme for Biosynthesis of Aryl Metabolites from l-Phenylalanine in the Fungus Bjerkandera adusta

PubMed Central

Lapadatescu, Carmen; Giniès, Christian; Le Quéré, Jean-Luc; Bonnarme, Pascal

2000-01-01

Aryl metabolite biosynthesis was studied in the white rot fungus Bjerkandera adusta cultivated in a liquid medium supplemented with l-phenylalanine. Aromatic compounds were analyzed by gas chromatography-mass spectrometry following addition of labelled precursors (14C- and 13C-labelled l-phenylalanine), which did not interfere with fungal metabolism. The major aromatic compounds identified were benzyl alcohol, benzaldehyde (bitter almond aroma), and benzoic acid. Hydroxy- and methoxybenzylic compounds (alcohols, aldehydes, and acids) were also found in fungal cultures. Intracellular enzymatic activities (phenylalanine ammonia lyase, aryl-alcohol oxidase, aryl-alcohol dehydrogenase, aryl-aldehyde dehydrogenase, lignin peroxidase) and extracellular enzymatic activities (aryl-alcohol oxidase, lignin peroxidase), as well as aromatic compounds, were detected in B. adusta cultures. Metabolite formation required de novo protein biosynthesis. Our results show that l-phenylalanine was deaminated to trans-cinnamic acid by a phenylalanine ammonia lyase and trans-cinnamic acid was in turn converted to aromatic acids (phenylpyruvic, phenylacetic, mandelic, and benzoylformic acids); benzaldehyde was a metabolic intermediate. These acids were transformed into benzaldehyde, benzyl alcohol, and benzoic acid. Our findings support the hypothesis that all of these compounds are intermediates in the biosynthetic pathway from l-phenylalanine to aryl metabolites. Additionally, trans-cinnamic acid can also be transformed via β-oxidation to benzoic acid. This was confirmed by the presence of acetophenone as a β-oxidation degradation intermediate. To our knowledge, this is the first time that a β-oxidation sequence leading to benzoic acid synthesis has been found in a white rot fungus. A novel metabolic scheme for biosynthesis of aryl metabolites from l-phenylalanine is proposed. PMID:10742235

Mutagenicity of diesel exhaust particle extracts: influence of fuel composition in two diesel engines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clark, C.R.; Henderson, T.R.; Royer, R.E.

The influence of diesel fuel composition on mutagenicity of exhaust particle associated organic compounds has been investigated using nine fuels varying in aromatic content and distillation properties. The tests were conducted with Oldsmobile Delta-88 and Peugot 504 diesel cars operated according to the EPA Federal Test Procedure. The particulate exhaust from each test was collected on a filter, extracted in dichloromethane and the resulting extract evaluated for mutagenicity in Salmonella strain TA-100. Mutagenicity of extracts of particles collected from the Oldsmobile were highest in the higher aromatic content fuels (> 30%) but similar for intermediate (20%) and low (13%) aromaticmore » content fuels. No influence of aromaticity on mutagenicity was observed in samples collected from the Peugeot under the same conditions. Thus, fuel aromatic content may enhance the production of mutagenic combustion products at higher concentrations, but may be dependent upon engine type. A good correlation was observed between mutagenicity of the particle extracts and the initial boiling point of the fuel (r = 0.89). Gas chromatography/mass spectrometric analysis of the aromatic fraction of the fuels showed that the fuel producing the most mutagenic combustion products was highest in phenanthrene type compounds.« less

The formation of quasi-alicyclic rings in alkyl-aromatic compounds

NASA Astrophysics Data System (ADS)

Straka, Pavel; Buryan, Petr; Bičáková, Olga

2018-02-01

The alkyl side chains of n-alkyl phenols, n-alkyl benzenes and n-alkyl naphthalenes are cyclised, as demonstrated by GC measurements, FTIR spectroscopy and molecular mechanics calculations. Cyclisation occurs due to the intramolecular interaction between an aromatic ring (-δ) and a hydrogen of the terminal methyl group (+δ) of an alkyl chain. In fact, conventional molecules are not aliphatic-aromatic, but quasi-alicyclic-aromatic. With the aromatic molecules formed with a quasi-alicyclic ring, the effect of van der Waals attractive forces increases not only intramolecularly but also intermolecularly. This effect is strong in molecules with propyl and higher alkyl substituents. The increase of intermolecular van der Waals attractive forces results in bi-linearity in the GC retention time of the compounds in question, observed in the dependence of the logarithm of the relative retention time on the number of carbons in a molecule in both polar and nonpolar stationary phases with both capillary and packed columns. The role of van der Waals forces has been demonstrated using the potential energies of covalent and noncovalent interactions for 2-n-alkyl phenols, n-alkyl benzenes and 1-n-alkyl- and 2-n-alkyl naphthalenes.

Infrared Spectroscopy of Matrix-Isolated Polycyclic Aromatic Nitrogen Heterocycles (PANHs)

NASA Technical Reports Server (NTRS)

Mattioda, A. L.; Hudgins, D. M.; Bauschlicher, C. W.; Allamandola, L. J.; Biemesderfer, C. D.; Rosi, M.

2002-01-01

The mid-infrared spectra of the nitrogen-containing heterocyclic polycyclic aromatic compounds 1-azabenz[a]-anthracene; 2-azabenz[a]anthracene; 1-azachrysene; 2-azachrysene; 4-azachrysene; 2-azapyrene, and 7,8 benzoquinoline in their neutral and cation forms were investigated. The spectra of these species isolated in an argon matrix have been measured. Band frequencies and intensities were tabulated and these data compared with spectra computed using density functional theory at the B3LYP level. The overall agreement between experiment and theory is quite good, in keeping with earlier results on homonuclear polycyclic aromatic hydrocarbons. The differences between the spectral properties of nitrogen bearing aromatics and non-substituted, neutral polycyclic aromatic hydrocarbons will be discussed.

Pyrolysis of humic and fulvic acids

USGS Publications Warehouse

Wershaw, R. L.; Bohner, G.E.

1969-01-01

Pyrolysis of humic and fulvic acids isolated from a North Carolina soil yields a variety of aromatic, heterocyclic and straight chain organ compounds. The pyrolysis products identified by gas chromatography and mass spectrometry indicate that humic and fulvic acids have aromatic and polysaccharide structures in their molecules. ?? 1969.

Reaction of bromine and chlorine with phenolic compounds and natural organic matter extracts--Electrophilic aromatic substitution and oxidation.

PubMed

Criquet, Justine; Rodriguez, Eva M; Allard, Sebastien; Wellauer, Sven; Salhi, Elisabeth; Joll, Cynthia A; von Gunten, Urs

2015-11-15

Phenolic compounds are known structural moieties of natural organic matter (NOM), and their reactivity is a key parameter for understanding the reactivity of NOM and the disinfection by-product formation during oxidative water treatment. In this study, species-specific and/or apparent second order rate constants and mechanisms for the reactions of bromine and chlorine have been determined for various phenolic compounds (phenol, resorcinol, catechol, hydroquinone, phloroglucinol, bisphenol A, p-hydroxybenzoic acid, gallic acid, hesperetin and tannic acid) and flavone. The reactivity of bromine with phenolic compounds is very high, with apparent second order rate constants at pH 7 in the range of 10(4) to 10(7) M(-1) s(-1). The highest value was recorded for the reaction between HOBr and the fully deprotonated resorcinol (k = 2.1 × 10(9) M(-1) s(-1)). The reactivity of phenolic compounds is enhanced by the activating character of the phenolic substituents, e.g. further hydroxyl groups. With the data set from this study, the ratio between the species-specific rate constants for the reactions of chlorine versus bromine with phenolic compounds was confirmed to be about 3000. Phenolic compounds react with bromine or chlorine either by oxidation (electron transfer, ET) or electrophilic aromatic substitution (EAS) processes. The dominant process mainly depends on the relative position of the hydroxyl substituents and the possibility of quinone formation. While phenol, p-hydroxybenzoic acid and bisphenol A undergo EAS, hydroquinone, catechol, gallic acid and tannic acid, with hydroxyl substituents in ortho or para positions, react with bromine by ET leading to quantitative formation of the corresponding quinones. Some compounds (e.g. phloroglucinol) show both partial oxidation and partial electrophilic aromatic substitution and the ratio observed for the pathways depends on the pH. For the reaction of six NOM extracts with bromine, electrophilic aromatic substitution accounted for only 20% of the reaction, and for one NOM extract (Pony Lake fulvic acid) it accounted for <10%. This shows that for natural organic matter samples, oxidation (ET) is far more important than bromine incorporation (EAS). Copyright © 2015 Elsevier Ltd. All rights reserved.

Base-catalyzed efficient tandem [3 + 3] and [3 + 2 + 1] annulation-aerobic oxidative benzannulations.

PubMed

Diallo, Aboubacar; Zhao, Yu-Long; Wang, He; Li, Sha-Sha; Ren, Chuan-Qing; Liu, Qun

2012-11-16

An efficient synthesis of substituted benzenes via a base-catalyzed [3 + 3] aerobic oxidative aromatization of α,β-unsaturated carbonyl compounds with dimethyl glutaconate was reported. All the reactions were carried out under mild, metal-free conditions to afford the products in high to excellent yields with molecular oxygen as the sole oxidant and water as the sole byproduct. Furthermore, a more convenient tandem [3 + 2 + 1] aerobic oxidative aromatization reaction was developed through the in situ generation of the α,β-unsaturated carbonyl compounds from aldehydes and ketones.

Organic compounds leached from fast pyrolysis mallee leaf and bark biochars.

PubMed

Lievens, Caroline; Mourant, Daniel; Gunawan, Richard; Hu, Xun; Wang, Yi

2015-11-01

Characterization of organic compounds leached from biochars is essential in assessing the possible toxicity of the biochar to the soils' biota. In this study the nature of the leached organic compounds from Mallee biochars, produced from pyrolysis of Mallee leaf and bark in a fluidised-bed pyrolyser at 400 and 580°C was investigated. Light bio-oil compounds and aromatic organic compounds were investigated. The 'bio-oil like' light compounds from leaf and bark biochars 'surfaces were obtained after leaching the chars with a solvent, suitable to dissolve the respective bio-oils. GC/MS was implemented to investigate the leachates. Phenolics, which are potentially harmful toxins, were detected and their concentration shown to be dependent on the char's origin and the char production temperature. Further, to simulate biochars amendment to soils, the chars were leached with water. The water-leached aromatic compounds from leaf and bark biochars were characterized using UV-fluorescence spectroscopy. Those results suggested that biochars contain leachable compounds of which the nature and amount is dependent on the biomass feedstock, pyrolysis temperature and leaching time. Copyright © 2014 Elsevier Ltd. All rights reserved.

Aromatic Borozene

PubMed Central

2009-01-01

Based on our comprehensive theoretical investigation and known experimental results for small boron clusters, we predict the existence of a novel aromatic inorganic molecule, B12H6. This molecule, which we refer to as borozene, has remarkably similar properties to the well-known benzene. Borozene is planar, possesses a large first excitation energy, D3hsymmetry, and more importantly is aromatic. Furthermore, the calculated anisotropy of the magnetic susceptibility of borozene is three times larger in absolute value than for benzene. Finally, we show that borozene molecules may be fused together to give larger aromatic compounds with even larger anisotropic susceptibilities. PMID:20596438

Three-component, one-pot synthesis of anthranilamide Schiff bases bearing 4-aminoquinoline moiety as Mycobacterium tuberculosis gyrase inhibitors.

PubMed

Salve, Preeti S; Alegaon, Shankar G; Sriram, Dharmarajan

2017-04-15

An efficient three-component, one-pot protocol is described for the synthesis of biologically interesting 2-(benzylideneamino)-N-(7-chloroquinolin-4-yl)benzohydrazide derivatives from isatoic anhydride, 7-chloro-4-hydrazinylquinoline and aromatic and/or hetero aromatic aldehydes under catalyst free condensation by using water as reaction media. All synthesized compounds were evaluated for their antimycobacterial activity against Mycobacterium tuberculosis (MTB) and cytotoxicity activity against normal VERO cell lines. The synthesized compounds exhibited minimum inhibitory concentration (MIC) ranging from 0.78 to 25μM. Among the tested compounds 4c, 4o, 4r, and 4u exhibited promising inhibitory activity (MIC=3.12μM). Compounds 4h and 4i stand out, showing MIC values of 0.78 and 1.56μM respectively. Both compounds were further screened for their Mycobacterium tuberculosis DNA gyrase inhibitory assay which suggested that these compounds have a great potential for further optimization and development as antitubercular agents. Copyright © 2017 Elsevier Ltd. All rights reserved.

Gas Chromatography-Mass Spectrometry-Olfactometry To Control the Aroma Fingerprint of Extra Virgin Olive Oil from Three Tunisian Cultivars at Three Harvest Times.

PubMed

Ben Brahim, Samia; Amanpour, Asghar; Chtourou, Fatma; Kelebek, Hasim; Selli, Serkan; Bouaziz, Mohamed

2018-03-21

Gas chromatography-mass spectrometry-olfactometry was used for the analysis of volatile compounds and key odorants of three less studied Tunisian olive oil cultivars for the first time. A total of 42 aroma compounds were identified and quantified in extra virgin olive oils. The present study revealed that the most dominant volatiles in olive oil samples qualitatively and quantitatively were aldehydes and alcohols, followed by terpenes and esters. Indeed, chemometric analysis has shown a correlation between chemical compounds and sensory properties. The determination of aroma-active compounds of olive oil samples was carried out using aroma extract dilution analysis. A total of 15 aroma-active compounds were detected in the aromatic extract of extra virgin olive oil, of which 14 were identified. On the basis of the flavor dilution (FD) factor, the most potent aromatic active compound was hexanal (FD = 512) in Fakhari olive oil, (FD = 256) in Touffehi oils, and (FD = 128) in Jemri olive oil.

APPLICATION OF FATE AND TRANSPORT MODELING TO THE REMEDIAL DECISION MAKING PROCESS – INTRODUCTION TO WORKSHOP

EPA Science Inventory

The conventional site conceptual model for Brownfield sites considers that the extent of plumes of aromatic petroleum hydrocarbons (such as the BTEX compounds) in ground water are limited by natural biodegradation of the aromatic hydrocarbons by bacteria that use oxygen, nitrate ...

SOLAR RADIATION DOSE AND PHOTOTOXICITY OF POLYCYCLIC AROMATIC HYDROCARBONS: A CASE STUDY

EPA Science Inventory

The toxicity of polycyclic aromatic hydrocarbons increases by as much as three orders of magnitude in the presence of solar radiation. The risk of this photoactive toxicity is thus based on both tissue concentrations of potentially photo activated compounds and the levels of subs...

Correlations and adsorption mechanisms of aromatic compounds on biochars produced from various biomass at 700 °C.

PubMed

Yang, Kun; Jiang, Yuan; Yang, Jingjing; Lin, Daohui

2018-02-01

Knowledge of adsorption behavior of organic contaminants on high heat temperature treated biochars is essential for application of biochars as adsorbents in wastewater treatment and soil remediation. In this study, isotherms of 25 aromatic compounds adsorption on biochars pyrolyzed at 700 °C from biomass including wood chips, rice straw, bamboo chips, cellulose, lignin and chitin were investigated to establish correlations between adsorption behavior and physicochemical properties of biochars. Isotherms were well fitted by Polanyi theory-based Dubinin-Ashtakhov (DA) model with three parameters, i.e., adsorption capacity (Q 0 ) and adsorption affinity (E and b). Besides the negative correlation of Q 0 with molecular maximum cross-sectional areas (σ) of organic compounds, positive correlations of Q 0 with total pore volume (V total ) and average diameter of micropore (D) of biochars were observed, indicating that adsorption by biochars is captured by the pore-filling mechanism with molecular sieving effect in biochar pores. Linear solvation energy relationships (LSERs) of adsorption affinity (E) with solvatochromic parameters of organic compounds (i. e., α m and π ∗ ) were established, suggesting that hydrophobic effect, π-π interaction and hydrogen-bonding interaction are the main forces responsible for adsorption. The regression coefficient (π 1 ) and intercept (C) of obtained LSERs are correlated with biochar H/C and R micro , respectively, implying that biochars with higher aromaticity and more micropores have stronger π-π bonding potential and hydrophobic effect potential with aromatic molecule, respectively. However, hydrogen-bonding potential of biochars for organic molecules is not changed significantly with properties of biochars. A negative correlation of b with biochar H/C is also obtained. These correlations could be used to predict the adsorption behavior of organic compounds on high heat temperature treated biochars from various biomass for the application of biochars as sorbents and for the estimating of environmental risks of organic compounds in the present of biochars. Copyright © 2017 Elsevier Ltd. All rights reserved.

The Fate of Crude Oil during Photooxidation under Natural Sunlight

NASA Astrophysics Data System (ADS)

Wang, Q.; Evans, M.; Bacosa, H. P.; Hu, X.; Liu, Z.

2016-02-01

Photooxidation plays an important role in removing spilled crude oil, particularly the aromatic fraction, in surface seawater. Even though much research has been done regarding the changes of different oil fractions by photooxidation, including saturate, aromatic, resin and asphaltene (SARA), we know little about how specific aromatic compounds change in the SARA fractions during photooxidation. In this study, we amended 13C-labled phenanthrene in slightly weathered Louisiana light sweet crude, and followed the fates of 13C values of the SARA fractions during a 44-d incubation experiment under the natural sunlight in south Texas. Our results showed that the aromatic fraction of the crude decreased from 25.4% at time zero to 13.5% at the 44th d, while the resin increased from 12.2% to 16.5% and asphaltene from 2.4% to 13.3%, respectively. This result indicates the aromatic was transformed mostly into asphaltene by photooxidation, and most of the changes took place within the first 10 d. In contrast, no significant difference was observed in the SARA fractions in the dark controls. Analyses of 13C values and phenanthrene concentrations in the SARA fractions are currently on going and will be presented. Results from this experiment provide insights into changes of specific aromatic compounds within oil fractions by photochemical oxidation during oil weathering in the ocean.

A Naphtho- p-quinodimethane Exhibiting Baird’s (Anti)Aromaticity, Broken Symmetry, and Attractive Photoluminescence

DOE PAGES

Shokri, Siamak; Li, Jingbai; Manna, Manoj K.; ...

2017-08-24

In this paper, we report a novel reductive desulfurization reaction involving π-acidic naphthalene diimides 1 (NDI) using thionating agents such as Lawesson’s reagent. Along with the expected thionated NDI derivatives 2-6, new heterocyclic naphtho-p-quinodimethane compounds 7 depicting broken/reduced symmetry were successfully isolated and fully characterized. Empirical studies and theoretical modeling suggest that was formed via a six-membered ring oxathiaphosphenine intermediate rather than the usual four-membered ring oxathiaphosphetane of 2-6. Aside from the reduced symmetry in 7 as confirmed by single-crystal XRD analysis, we established that the ground state UV-vis absorption of 7 is red-shifted in comparison to the parent NDImore » 1. This result was expected in the case of thionated polycyclic diimides. However, unusual low energy transitions originate from Baird 4nπ aromaticity of compounds 7 in lieu of the intrinsic Huckel (4n + 2)π aromaticity as encountered in NDI 1. Moreover, complementary theoretical modeling results also corroborate this change in aromaticity of 7. Consequently, photophysical investigations show that, compared to parent NDI 1, 7 can easily access and emit from its T 1 state with a phosphorescence 3(7a)* lifetime of τ P = 395 μs at 77 K indicative of the formation of the corresponding “aromatic triplet” species according to the Baird’s rule of aromaticity.« less

Oxidation of Naphthenoaromatic and Methyl-Substituted Aromatic Compounds by Naphthalene 1,2-Dioxygenase

PubMed Central

Selifonov, S. A.; Grifoll, M.; Eaton, R. W.; Chapman, P. J.

1996-01-01

Oxidation of acenaphthene, acenaphthylene, and fluorene was examined with recombinant strain Pseudomonas aeruginosa PAO1(pRE695) expressing naphthalene dioxygenase genes cloned from plasmid NAH7. Acenaphthene underwent monooxygenation to 1-acenaphthenol with subsequent conversion to 1-acenaphthenone and cis- and trans-acenaphthene-1,2-diols, while acenaphthylene was dioxygenated to give cis-acenaphthene-1,2-diol. Nonspecific dehydrogenase activities present in the host strain led to the conversion of both of the acenaphthene-1,2-diols to 1,2-acenaphthoquinone. The latter was oxidized spontaneously to naphthalene-1,8-dicarboxylic acid. No aromatic ring dioxygenation products were detected from acenaphthene and acenaphthylene. Mixed monooxygenase and dioxygenase actions of naphthalene dioxygenase on fluorene yielded products of benzylic 9-monooxygenation, aromatic ring dioxygenation, or both. The action of naphthalene dioxygenase on a variety of methyl-substituted aromatic compounds, including 1,2,4-trimethylbenzene and isomers of dimethylnaphthalene, resulted in the formation of benzylic alcohols, i.e., methyl group monooxygenation products, which were subsequently converted to the corresponding carboxylic acids by dehydrogenase(s) in the host strain. Benzylic monooxygenation of methyl groups was strongly predominant over aromatic ring dioxygenation and essentially nonspecific with respect to the substitution pattern of the aromatic substrates. In addition to monooxygenating benzylic methyl and methylene groups, naphthalene dioxygenase behaved as a sulfoxygenase, catalyzing monooxygenation of the sulfur heteroatom of 3-methylbenzothiophene. PMID:16535238

The Combination of Vemurafenib and Procaspase-3 Activation Is Synergistic in Mutant BRAF Melanomas.

PubMed

Peh, Jessie; Fan, Timothy M; Wycislo, Kathryn L; Roth, Howard S; Hergenrother, Paul J

2016-08-01

The development of vemurafenib resistance limits the long-term efficacy of this drug for treatment of metastatic melanomas with the (V600E)BRAF mutation. Inhibition of downstream MAPK signaling with vemurafenib induces apoptotic cell death mediated by caspase-3, suggesting that addition of a procaspase-3 activator could enhance anticancer effects. Here, we show that the combination of PAC-1, a procaspase-activating compound, and vemurafenib is highly synergistic in enhancing caspase-3 activity and apoptotic cell death in melanoma cell lines harboring the (V600E)BRAF mutation. In vivo, the combination displays a favorable safety profile in mice and exerts significant antitumor effects. We further demonstrate that addition of PAC-1 to the clinically useful combination of vemurafenib and a MEK inhibitor, trametinib, starkly enhances the caspase-3 activity and proapoptotic effect of the combination. Moreover, addition of low concentration PAC-1 also delays the regrowth of cells following treatment with vemurafenib. Finally, PAC-1 remains potent against vemurafenib-resistant A375VR cells in cell culture and synergizes with vemurafenib to exert antitumor effects on A375VR cell growth in vivo Collectively, our data suggest that inhibition of MAPK signaling combined with concurrent procaspase-3 activation is an effective strategy to enhance the antitumor activity of vemurafenib and mitigate the development of resistance. Mol Cancer Ther; 15(8); 1859-69. ©2016 AACR. ©2016 American Association for Cancer Research.

Effects of recirculation in a three-tank pilot-scale system for pharmaceutical removal with powdered activated carbon.

PubMed

Kårelid, Victor; Larsson, Gen; Björlenius, Berndt

2017-05-15

The removal of pharmaceutically active compounds by powdered activated carbon (PAC) in municipal wastewater is a promising solution to the problem of polluted recipient waters. Today, an efficient design strategy is however lacking with regard to high-level overall, and specific, substance removal in the large scale. The performance of PAC-based removal of pharmaceuticals was studied in pilot-scale with respect to the critical parameters; contact time and PAC dose using one PAC product selected by screening in bench-scale. The goal was a minimum of 95% removal of the pharmaceuticals present in the evaluated municipal wastewater. A set of 21 pharmaceuticals was selected from an initial 100 due to their high occurrence in the effluent water of two selected wastewater treatment plants (WWTPs) in Sweden, whereof candidates discussed for future EU regulation directives were included. By using recirculation of PAC over a treatment system using three sequential contact tanks, a combination of the benefits of powdered and granular carbon performance was achieved. The treatment system was designed so that recirculation could be introduced to any of the three tanks to investigate the effect of recirculation on the adsorption performance. This was compared to use of the setup, but without recirculation. A higher degree of pharmaceutical removal was achieved in all recirculation setups, both overall and with respect to specific substances, as compared to without recirculation. Recirculation was tested with nominal contact times of 30, 60 and 120 min and the goal of 95% removal could be achieved already at the shortest contact times at a PAC dose of 10-15 mg/L. In particular, the overall removal could be increased even to 97% and 99%, at 60 and 120 min, respectively, when the recirculation point was the first tank. Recirculation of PAC to either the first or the second contact tank proved to be comparable, while a slightly lower performance was observed with recirculation to the third tank. With regards to individual substances, clarithromycin and diclofenac were ubiquitously removed according to the set goal and in contrast, a few substances (fluconazole, irbesartan, memantine and venlafaxine) required specific settings to reach an acceptable removal. Copyright © 2017 Elsevier Ltd. All rights reserved.

Method for producing heat-resistant semi-inorganic compounds

NASA Technical Reports Server (NTRS)

Yajima, S.; Okamura, K.; Shishido, T.; Hasegawa, Y.

1983-01-01

The method for producing a heat resistant, semi-inorganic compound is discussed. Five examples in which various alcohols, phenols, and aromatic carbonic acids are used to test heat resistance and solubility are provided.

Effect of iodide on transformation of phenolic compounds by nonradical activation of peroxydisulfate in the presence of carbon nanotube: Kinetics, impacting factors, and formation of iodinated aromatic products.

PubMed

Guan, Chaoting; Jiang, Jin; Pang, Suyan; Luo, Congwei; Yang, Yi; Ma, Jun; Yu, Jing; Zhao, Xi

2018-06-04

Our recent study has demonstrated that iodide (I - ) can be easily and almost entirely oxidized to hypoiodous acid (HOI) but not to iodate by nonradical activation of peroxydisulfate (PDS) in the presence of a commercial carbon nanotube (CNT). In this work, the oxidation kinetics of phenolic compounds by the PDS/CNT system in the presence of I - were examined and potential formation of iodinated aromatic products was explored. Experimental results suggested that I - enhanced the transformation of six selected substituted phenols, primarily attributed to the generation of HOI that was considerably reactive toward these phenolic compounds. More significant enhancement was obtained at higher I - concentrations or lower pH values, while the change of PDS or CNT dosages exhibited a slight impact on the enhancing effect of I - . Product analyses with liquid chromatography tandem mass spectrometry clearly revealed the production of iodinated aromatic products when p-hydroxybenzoic acid (p-HBA, a model phenol) was treated by the PDS/CNT/I - system in both synthetic and real waters. Their formation pathways probably involved the substitution of HOI on aromatic ring of p-HBA, as well as the generation of iodinated p-HBA phenoxyl radicals and subsequent coupling of these radicals. Given the considerable toxicity and harmful effects of these iodinated aromatic products, particular attention should be paid when the novel PDS/CNT oxidation technology is applied for treatment of phenolic contaminants in iodide-containing waters. Copyright © 2018 Elsevier Ltd. All rights reserved.

Aromatic aldehydes at the active site of aldehyde oxidoreductase from Desulfovibrio gigas: reactivity and molecular details of the enzyme-substrate and enzyme-product interaction.

PubMed

Correia, Hugo D; Marangon, Jacopo; Brondino, Carlos D; Moura, Jose J G; Romão, Maria J; González, Pablo J; Santos-Silva, Teresa

2015-03-01

Desulfovibrio gigas aldehyde oxidoreductase (DgAOR) is a mononuclear molybdenum-containing enzyme from the xanthine oxidase (XO) family, a group of enzymes capable of catalyzing the oxidative hydroxylation of aldehydes and heterocyclic compounds. The kinetic studies reported in this work showed that DgAOR catalyzes the oxidative hydroxylation of aromatic aldehydes, but not heterocyclic compounds. NMR spectroscopy studies using (13)C-labeled benzaldehyde confirmed that DgAOR catalyzes the conversion of aldehydes to the respective carboxylic acids. Steady-state kinetics in solution showed that high concentrations of the aromatic aldehydes produce substrate inhibition and in the case of 3-phenyl propionaldehyde a suicide substrate behavior. Hydroxyl-substituted aromatic aldehydes present none of these behaviors but the kinetic parameters are largely affected by the position of the OH group. High-resolution crystallographic structures obtained from single crystals of active-DgAOR soaked with benzaldehyde showed that the side chains of Phe425 and Tyr535 are important for the stabilization of the substrate in the active site. On the other hand, the X-ray data of DgAOR soaked with trans-cinnamaldehyde showed a cinnamic acid molecule in the substrate channel. The X-ray data of DgAOR soaked with 3-phenyl propionaldehyde showed clearly how high substrate concentrations inactivate the enzyme by binding covalently at the surface of the enzyme and blocking the substrate channel. The different reactivity of DgAOR versus aldehyde oxidase and XO towards aromatic aldehydes and N-heterocyclic compounds is explained on the basis of the present kinetic and structural data.

Concentrations and co-occurrence correlations of 88 volatile organic compounds (VOCs) in the ambient air of 13 semi-rural to urban locations in the United States

USGS Publications Warehouse

Pankow, J.F.; Luo, W.; Bender, D.A.; Isabelle, L.M.; Hollingsworth, J.S.; Chen, C.; Asher, W.E.; Zogorski, J.S.

2003-01-01

The ambient air concentrations of 88 volatile organic compounds were determined in samples taken at 13 semi-rural to urban locations in Maine, Massachusetts, New Jersey, Pennsylvania, Ohio, Illinois, Louisiana, and California. The sampling periods ranged from 7 to 29 months, yielding a large data set with a total of 23,191 individual air concentration values, some of which were designated "ND" (not detected). For each compound at each sampling site, the air concentrations (ca, ppbV) are reported in terms of means, medians, and means of the detected values. The analytical method utilized adsorption/thermal desorption with air-sampling cartridges. The analytes included numerous halogenated alkanes, halogenated alkenes, ethers, alcohols, nitriles, esters, ketones, aromatics, a disulfide, and a furan. At some sites, the air concentrations of the gasoline-related aromatic compounds and the gasoline additive methyl tert-butyl ether were seasonally dependent, with concentrations that maximized in the winter. For each site studied here, the concentrations of some compounds were highly correlated one with another (e.g., the BTEX group (benzene, toluene, ethylbenzene, and the xylenes). Other aromatic compounds were also all generally correlated with one another, while the concentrations of other compound pairs were not correlated (e.g., benzene was not correlated with CFC-12). The concentrations found for the BTEX group were generally lower than the values that have been previously reported for urbanized and industrialized areas of other nations. ?? 2003 Elsevier Ltd. All rights reserved.

Frog volatile compounds: application of in vivo SPME for the characterization of the odorous secretions from two species of Hypsiboas treefrogs.

PubMed

Brunetti, Andrés E; Merib, Josias; Carasek, Eduardo; Caramão, Elina B; Barbará, Janaina; Zini, Claudia A; Faivovich, Julián

2015-04-01

A novel in vivo design was used in combination with solid-phase microextraction (SPME) and gas chromatography/mass spectrometry (GC/MS) to characterize the volatile compounds from the skin secretion of two species of tree frogs. Conventional SPME-GC/MS also was used for the analysis of volatiles present in skin samples and for the analysis of volatiles present in the diet and terraria. In total, 40 and 37 compounds were identified in the secretion of Hypsiboas pulchellus and H. riojanus, respectively, of which, 35 were common to both species. Aliphatic aldehydes, a low molecular weight alkadiene, an aromatic alcohol, and other aromatics, ketones, a methoxy pyrazine, sulfur containing compounds, and hemiterpenes are reported here for the first time in anurans. Most of the aliphatic compounds seem to be biosynthesized by the frogs following different metabolic pathways, whereas aromatics and monoterpenes are most likely sequestered from environmental sources. The characteristic smell of the secretion of H. pulchellus described by herpetologists as skunk-like or herbaceous is explained by a complex blend of different odoriferous components. The possible role of the volatiles found in H. pulchellus and H. riojanus is discussed in the context of previous hypotheses about the biological function of volatile secretions in frogs (e.g., sex pheromones, defense secretions against predators, mosquito repellents).

The production of aromatic alcohols in non-Saccharomyces wine yeast is modulated by nutrient availability.

PubMed

González, Beatriz; Vázquez, Jennifer; Morcillo-Parra, M Ángeles; Mas, Albert; Torija, María Jesús; Beltran, Gemma

2018-09-01

Aromatic alcohols (tryptophol, phenylethanol, tyrosol) positively contribute to organoleptic characteristics of wines, and are also described as bioactive compounds and quorum sensing molecules. These alcohols are produced by yeast during alcoholic fermentation via the Erhlich pathway, although in non-Saccharomyces this production has been poorly studied. We studied how different wine yeast species modulate the synthesis patterns of aromatic alcohol production depending on glucose, nitrogen and aromatic amino acid availability. Nitrogen limitation strongly promoted the production of aromatic alcohols in all strains, whereas low glucose generally inhibited it. Increased aromatic amino acid concentrations stimulated the production of aromatic alcohols in all of the strains and conditions tested. Thus, there was a clear association between the nutrient conditions and production of aromatic alcohols in most of the wine yeast species analysed. Additionally, the synthesis pattern of these alcohols has been evaluated for the first time in Torulaspora delbrueckii, Metschnikowia pulcherrima and Starmellera bacillaris. Copyright © 2018 Elsevier Ltd. All rights reserved.

Decoding the Secrets of Carbon Preservation and GHG Flux in Lower-Latitude Peatlands

NASA Astrophysics Data System (ADS)

Richardson, C. J.; Flanagan, N. E.; Wang, H.; Ho, M.; Hodgkins, S. B.; Cooper, W. T.; Chanton, J.; Winton, S.

2017-12-01

The mechanisms regulating peat decomposition and C carbon storage in peatlands are poorly understood, particularly with regard to the importance of the biochemical compounds produced by different plant species and in turn peat quality controls on C storage and GHG flux. To examine the role of carbon quality in C accretion in northern compared to tropical peatlands we completed field and lab studies on bog peats collected in Minnesota, North Carolina, Florida and Peru to answer three fundamental questions; 1) is tropical peat more recalcitrant than northern peat 2) does the addition of aromatic and phenolic C compounds increase towards the tropics 3) do differences in the chemical structure of organic matter explain variances in carbon storage and GHG flux in tropical versus northern peatlands? Our main hypothesize is that high concentrations of phenolics and aromatic C compounds produced in shrub and tree plant communities in peatlands coupled with the fire production of biochar aromatics in peatlands may provide a dual biogeochemical latch mechanism controlling microbial decomposition of peat even under higher temperatures and seasonal drought. By comparing the peat bog soil cores collected from the MN peat bogs, NC Pocosins, FL Everglades and Peru palm swamps we find that the soils in the shrub-dominant Pocosin contain the highest phenolics, which microbial studies indicate have the strongest resistance to microbial decomposition. A chemical comparison of plant driven peat carbon quality along a north to south latitudinal gradient indicates that tropical peatlands have higher aromatic compounds, and enhanced phenolics, especially after light fires, which enhances C storage and affect GHG flux across the latitudinal gradient.

SiRNAs conjugated with aromatic compounds induce RISC-mediated antisense strand selection and strong gene-silencing activity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kubo, Takanori, E-mail: kubo-t@yasuda-u.ac.jp; Yanagihara, Kazuyoshi; Division of Genetics, National Cancer Center Research Institute, 5-1-1 Tsukiji, Chuo-ku, Tokyo 104-0045

2012-10-05

Highlights: Black-Right-Pointing-Pointer SiRNAs conjugated with aromatic compounds (Ar-siRNAs) at 5 Prime -sense strand were synthesized. Black-Right-Pointing-Pointer Ar-siRNAs increased resistance against nuclease degradation. Black-Right-Pointing-Pointer Ar-siRNAs were thermodynamically stable compared with the unmodified siRNA. Black-Right-Pointing-Pointer High levels of cellular uptake and cytoplasmic localization were found. Black-Right-Pointing-Pointer Strong gene-silencing efficacy was exhibited in the Ar-siRNAs. -- Abstract: Short interference RNA (siRNA) is a powerful tool for suppressing gene expression in mammalian cells. In this study, we focused on the development of siRNAs conjugated with aromatic compounds in order to improve the potency of RNAi and thus to overcome several problems with siRNAs, suchmore » as cellular delivery and nuclease stability. The siRNAs conjugated with phenyl, hydroxyphenyl, naphthyl, and pyrenyl derivatives showed strong resistance to nuclease degradation, and were thermodynamically stable compared with unmodified siRNA. A high level of membrane permeability in HeLa cells was also observed. Moreover, these siRNAs exhibited enhanced RNAi efficacy, which exceeded that of locked nucleic acid (LNA)-modified siRNAs, against exogenous Renilla luciferase in HeLa cells. In particular, abundant cytoplasmic localization and strong gene-silencing efficacy were found in the siRNAs conjugated with phenyl and hydroxyphenyl derivatives. The novel siRNAs conjugated with aromatic compounds are promising candidates for a new generation of modified siRNAs that can solve many of the problems associated with RNAi technology.« less

Atmospheric pressure solid analysis probe coupled to quadrupole-time of flight mass spectrometry as a tool for screening and semi-quantitative approach of polycyclic aromatic hydrocarbons, nitro-polycyclic aromatic hydrocarbons and oxo-polycyclic aromatic hydrocarbons in complex matrices.

PubMed

Carrizo, Daniel; Domeño, Celia; Nerín, Isabel; Alfaro, Pilar; Nerín, Cristina

2015-01-01

A new screening and semi-quantitative approach has been developed for direct analysis of polycyclic aromatic hydrocarbons (PAHs) and their nitro and oxo derivatives in environmental and biological matrices using atmospheric pressure solid analysis probe (ASAP) quadrupole-time of flight mass spectrometry (Q-TOF-MS). The instrumental parameters were optimized for the analysis of all these compounds, without previous sample treatment, in soil, motor oil, atmospheric particles (ashes) and biological samples such as urine and saliva of smokers and non-smokers. Ion source parameters in the MS were found to be the key parameters, with little variation within PAHs families. The optimized corona current was 4 µA, sample cone voltage 80 V for PAHs, nitro-PAHs and oxo-PAHs, while the desolvation temperatures varied from 300°C to 500°C. The analytical method performance was checked using a certified reference material. Two deuterated compounds were used as internal standards for semi-quantitative purposes together with the pure individual standard for each compound and the corresponding calibration plot. The compounds nitro PAH 9-nitroanthracene and oxo-PAH 1,4-naphthalenedione, were found in saliva and urine in a range below 1 µg/g while the range of PAHs in these samples was below 2 µg/g. Environmental samples provided higher concentration of all pollutants than urine and saliva. Copyright © 2014 Elsevier B.V. All rights reserved.

Anaerobic/aerobic treatment of a petrochemical wastewater from two aromatic transformation processes by fluidized bed reactors.

PubMed

Estrada-Arriaga, Edson B; Ramirez-Camperos, Esperanza; Moeller-Chavez, Gabriela E; García-Sanchez, Liliana

2012-01-01

An integrated fluidized bed reactor (FBR) has been employed as the treatment for petrochemical industry wastewaters with high organic matter and aromatic compounds, under anaerobic and aerobic conditions. The system was operated at hydraulic residence time (HRT) of 2.7 and 2.2 h in the anaerobic and aerobic reactor, respectively. The degree of fluidization in the beds was 30%. This system showed a high performance on the removal of organic matter and aromatic compounds. At different organic loading rates (OLR), the chemical oxygen demand (COD) removal in the anaerobic reactor was close to 85% and removals of the COD up to 94% were obtained in the aerobic reactor. High removals of benzene, toluene, ethylbenzene, xylenes, styrene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene and naphthalene were achieved in this study.

Interactions between manganese oxides and multiple-ringed aromatic compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Whelan, G.; Sims, R.C.

1992-08-01

Objective is to determine whether Mn reductive dissolution can oxidize multiple-ringed aromatics, such as PAHs, in an oxic environment Research indicated that certain PAHs (eg, dihydrodiols and diones that form free-radical intermediates) are susceptible to oxidation and polymerization. Over 14 days, 83, 76, 54, 70, and 20% of the Mn was reduced by 2,3-, 1,3-, and 1,4-naphthalenediol, quinizarin, and 1,4-naphthoquinone, respectively. 100, 100, and 65% of the first three PAHs were oxidized, respectively. Aromatics with diol functional groups were more easily oxidized than those with only dione groups. Relatively insoluble compounds like quinizarin can be oxidized; insoluble ''humic-like'' material precipitated,more » indicating a polymerization-humification process. Results suggest that electron transfer/organic release from the oxide surface is the rate-limiting step.« less

Interactions between manganese oxides and multiple-ringed aromatic compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Whelan, G.; Sims, R.C.

1992-08-01

Objective is to determine whether Mn reductive dissolution can oxidize multiple-ringed aromatics, such as PAHs, in an oxic environment? Research indicated that certain PAHs (eg, dihydrodiols and diones that form free-radical intermediates) are susceptible to oxidation and polymerization. Over 14 days, 83, 76, 54, 70, and 20% of the Mn was reduced by 2,3-, 1,3-, and 1,4-naphthalenediol, quinizarin, and 1,4-naphthoquinone, respectively. 100, 100, and 65% of the first three PAHs were oxidized, respectively. Aromatics with diol functional groups were more easily oxidized than those with only dione groups. Relatively insoluble compounds like quinizarin can be oxidized; insoluble ``humic-like`` material precipitated,more » indicating a polymerization-humification process. Results suggest that electron transfer/organic release from the oxide surface is the rate-limiting step.« less

Infrared and Raman spectra of N-acetyl- L-amino acid methylamides with aromatic side groups

NASA Astrophysics Data System (ADS)

Matsuura, Hiroatsu; Hasegawa, Kodo; Miyazawa, Tatsuo

Infrared and Raman spectra of N-acetyl- L-phenylalanine methylamide, N-acetyl- L-tyrosine methylamide and N-acetyl- L-tryptophan methylamide, as model compounds of aromatic amino acid residues in proteins, were measured in the solid state and in methanol solutions. Vibrational assignments of the spectra were made by utilizing the deuteration effect and by comparison with the spectra of related compounds which include toluene, p-cresol and 3-methylindole. The amide I, III and IV bands were strong in Raman scattering, but other characteristic amide bands were ill-defined. In the Raman spectra of methanol solutions, only the bands due to the aromatic side group vibrations were markedly observed, but those due to the peptide backbone vibrations were very weak, suggesting the coexistence of various molecular conformations in solution.

PACS industry in Korea

NASA Astrophysics Data System (ADS)

Kim, Hee-Joung

2002-05-01

PACS industry in Korea has been rapidly growing, since government had supported collaborative PACS project between industry and university hospital. In the beginning, PACS industry had focused on developing peripheral PACS solutions, while the Korea PACS society was being formed. A few companies had started developing and installing domestic large-scale full-PACS system for teaching hospitals. Several years later, many hospitals have installed full-PACS system with national policy of reimbursement for PACS exams in November 1999. Both experiences of full-PACS installation and national policy generated tremendous intellectual and technological expertise about PACS at all levels, clinical, hospital management, education, and industrial sectors. There are now more than 20 domestic PACS companies. They have enough experiences which are capable of installing a truly full-PACS system for large-scale teaching hospitals. As an example, a domestic company had installed more than 40 full-PACS systems within 2-3 years. Enough experiences of full-PACS installation in Korea lead PACS industry to start exporting their full-PACS solutions. However, further understanding and timely implementation of continuously evolving international standard and integrated healthcare enterprise concepts may be necessary for international leading of PACS technologies for the future.

Poly(1,3,4-oxadiazoles) via aromatic nucleophilic displacement

NASA Technical Reports Server (NTRS)

Connell, John W. (Inventor); Hergenrother, Paul M. (Inventor); Wolf, Peter (Inventor)

1992-01-01

Poly(1,3,4-oxadiazoles) (POX) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenyl) 1,3,4-oxadiazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The polymerizations are carried out in polar aprotic solvents such as sulfolane or diphenylsulfone using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. The di(hydroxyphenyl) 1,3,4-oxadiazole monomers are synthesized by reacting 4-hydroxybenzoic hydrazide with phenyl 4-hydrobenzoate in the melt and also by reacting aromatic dihydrazides with two moles of phenyl 4-hydroxybenzoate in the melt. This synthetic route has provided high molecular weight POX of new chemical structure, is economically and synthetically more favorable than other routes, and allows for facile chemical structure variation due to the large variety of activated aromatic dihalides which are available.

Monomers for thermosetting and toughening epoxy resins. [glycidyl amine derivatives, propargyl-containing amines, and mutagenic testing of aromatic diamines

NASA Technical Reports Server (NTRS)

Pratt, J. R.

1981-01-01

Eight glycidyl amines were prepared by alkylating the parent amine with epichlorohydrin to form chlorohydrin, followed by cyclization with aqueous NaOH. Three of these compounds contained propargyl groups with postcuring studies. A procedure for quantitatively estimating the epoxy content of these glycidyl amines was employed for purity determination. Two diamond carbonates and several model propargly compounds were prepared. The synthesis of three new diamines, two which contain propargyloxy groups, and another with a sec-butyl group is in progress. These materials are at the dinitro stage ready for the final hydrogenation step. Four aromatic diamines were synthesized for mutagenic testing purposes. One of these compounds rapidly decomposes on exposure to air.

Antioxidant and Anti-Osteoporotic Activities of Aromatic Compounds and Sterols from Hericium erinaceum.

PubMed

Li, Wei; Lee, Sang Hyun; Jang, Hae Dong; Ma, Jin Yeul; Kim, Young Ho

2017-01-11

Hericium erinaceum , commonly called lion's mane mushroom, is a traditional edible mushroom widely used in culinary applications and herbal medicines in East Asian countries. In this study, a new sterol, cerevisterol 6-cinnamate ( 6 ), was isolated from the fruiting bodies of H. erinaceum together with five aromatic compounds 1 - 5 and five sterols 7 - 11 . The chemical structures of these compounds were elucidated using chemical and physical methods and comparison of HRESIMS, ¹D-NMR (¹H, 13 C, and DEPT) and 2D-NMR (COSY, HMQC, HMBC, and NOESY) spectra with previously reported data. The antioxidant and anti-osteoporotic activities of extracts and the isolated compounds 1 - 11 were investigated. All compounds exhibited peroxyl radical-scavenging capacity but only compounds 1 , 3 , and 4 showed potent reducing capacity. Moreover, compounds 1 , 2 , 4 , and 5 showed moderate effects on cellular antioxidant activity and inhibited the receptor activator of nuclear factor κB ligand (RANKL)-induced osteoclastic differentiation. These results suggested that H. erinaceum could be utilized in the development of natural antioxidant and anti-osteoporotic nutraceuticals and functional foods.

pi-Selective stationary phases: (II) Adsorption behavior of substituted aromatic compounds on n-alkyl-phenyl stationary phases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gritti, Fabrice; Guiochon, Georges A; Mayfield, Kirsty

2010-01-01

The frontal analysis method was used to measure the adsorption isotherms of phenol, 4-chlorophenol, p-cresol, 4-methoxyphenol and caffeine on a series of columns packed with home-made alkyl-phenyl bonded silica particles. These ligands consist of a phenyl ring tethered to the silica support via a carbon chain of length ranging from 0 to 4 atoms. The adsorption isotherm models that fit best to the data account for solute-solute interactions that are likely caused by p-p interactions occurring between aromatic compounds and the phenyl group of the ligand. These interactions are the dominant factor responsible for the separation of low molecular weightmore » aromatic compounds on these phenyl-type stationary phases. The saturation capacities depend on whether the spacer of the ligands have an even or an odd number of carbon atoms, with the even alkyl chain lengths having a greater saturation capacity than the odd alkyl chain lengths. The trends in the adsorption equilibrium constant are also significantly different for the even and the odd chain length ligands.« less

Cloning and heterologous expression of two aryl-aldehyde dehydrogenases from the white-rot basidiomycete Phanerochaete chrysosporium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nakamura, Tomofumi; Fukuoka Institute of Health and Environmental Sciences, 39 Mukaizano, Dazaifu-shi, Fukuoka 818-0135; Ichinose, Hirofumi

2010-04-09

We identified two aryl-aldehyde dehydrogenase proteins (PcALDH1 and PcALDH2) from the white-rot basidiomycete Phanerochaete chrysosporium. Both PcALDHs were translationally up-regulated in response to exogenous addition of vanillin, one of the key aromatic compounds in the pathway of lignin degradation by basidiomycetes. To clarify the catalytic functions of PcALDHs, we isolated full-length cDNAs encoding these proteins and heterologously expressed the recombinant enzymes using a pET/Escherichia coli system. The open reading frames of both PcALDH1 and PcALDH2 consisted of 1503 nucleotides. The deduced amino acid sequences of both proteins showed high homologies with aryl-aldehyde dehydrogenases from other organisms and contained ten conservedmore » domains of ALDHs. Moreover, a novel glycine-rich motif 'GxGxxxG' was located at the NAD{sup +}-binding site. The recombinant PcALDHs catalyzed dehydrogenation reactions of several aryl-aldehyde compounds, including vanillin, to their corresponding aromatic acids. These results strongly suggested that PcALDHs metabolize aryl-aldehyde compounds generated during fungal degradation of lignin and various aromatic xenobiotics.« less

The flocculation mechanism and treatment of oily wastewater by flocculation.

PubMed

Zhang, Zhenchao

2017-11-01

In the present study, the performance of compound flocculants composed of different concentrations of polyaluminum chloride (PAC) and cationic polyacrylamide (CPAM), the influencing mechanism of the flocculation process and the effects of temperature, settling time, and speed and time of stirring were investigated. The results show that the poor water quality with high concentrations of oil, suspended solids (SS) and polymer greatly increases the oily wastewater emulsion stability and the difficulty of the flocculation treatment process. The compound flocculant in oily wastewater treatment can achieve best results at optimum conditions of temperature 45 °C, settling time 60 min, and two stirring stages, 250 r·min -1 for 3 min followed by 100 r·min -1 for 7 min. At the PAC dosage of 80 mg·L -1 and the CPAM dosage of 0.8 mg·L -1 , the turbidity of oily wastewater is reduced from 153.8 NTU to 11.2 NTU, and the turbidity removal rate reaches 92.69%. Through further measurements, oil content and SS content are less than 10 mg·L -1 , which meets the requirement of the Daqing oilfield re-injection standard.

Concentrations in human blood of petroleum hydrocarbons associated with the BP/Deepwater Horizon oil spill, Gulf of Mexico.

PubMed

Sammarco, Paul W; Kolian, Stephan R; Warby, Richard A F; Bouldin, Jennifer L; Subra, Wilma A; Porter, Scott A

2016-04-01

During/after the BP/Deepwater Horizon oil spill, cleanup workers, fisherpersons, SCUBA divers, and coastal residents were exposed to crude oil and dispersants. These people experienced acute physiological and behavioral symptoms and consulted a physician. They were diagnosed with petroleum hydrocarbon poisoning and had blood analyses analyzed for volatile organic compounds; samples were drawn 5-19 months after the spill had been capped. We examined the petroleum hydrocarbon concentrations in the blood. The aromatic compounds m,p-xylene, toluene, ethylbenzene, benzene, o-xylene, and styrene, and the alkanes hexane, 3-methylpentane, 2-methylpentane, and iso-octane were detected. Concentrations of the first four aromatics were not significantly different from US National Health and Nutritional Examination Survey/US National Institute of Standards and Technology 95th percentiles, indicating high concentrations of contaminants. The other two aromatics and the alkanes yielded equivocal results or significantly low concentrations. The data suggest that single-ring aromatic compounds are more persistent in the blood than alkanes and may be responsible for the observed symptoms. People should avoid exposure to crude oil through avoidance of the affected region, or utilizing hazardous materials suits if involved in cleanup, or wearing hazardous waste operations and emergency response suits if SCUBA diving. Concentrations of alkanes and PAHs in the blood of coastal residents and workers should be monitored through time well after the spill has been controlled.

N,S,O-Heterocycles in Aged Champagne Reserve Wines and Correlation with Free Amino Acid Concentrations.

PubMed

Le Menn, Nicolas; Marchand, Stephanie; de Revel, Gilles; Demarville, Dominique; Laborde, Delphine; Marchal, Richard

2017-03-22

Champagne regulations allow winegrowers to stock still wines to compensate for quality shifts in vintages, mainly due to climate variations. According to their technical requirements and house style, Champagne producers use these stored wines in their blends to enhance complexity. The presence of lees and aging at low pH (2.95-3.15), as in Champagne wines, lead to several modifications in wine composition. These conditions, combined with extended aging, result in the required environment for the Maillard chemical reaction, involving aromatic molecules, including sulfur, oxygen, and nitrogen heterocycles (such as thiazole, furan, and pyrazine derivatives), which may have a sensory impact on wine. Some aromatic heterocycles in 50 monovarietal wines aged from 1 to 27 years provided by Veuve Clicquot Ponsardin Champagne house were determined by the SPME-GC-MS method. The most interesting result highlighted a strong correlation between certain heterocycle concentrations and wine age. The second revealed a correlation between heterocyclic compound and free amino acid concentrations measured in the wines, suggesting that these compounds are potential aromatic precursors when wine is aged on lees and, thus, potential key compounds in the bouquet of aged Champagnes. The principal outcome of these assays was to reveal, for the first time, that aromatic heterocycle concentrations in Champagne base wines are correlated with wine age.

A concentration-dependent multi-term linear free energy relationship for sorption of organic compounds to soils based on the hexadecane dilute-solution reference state.

PubMed

Zhu, Dongqiang; Pignatello, Joseph J

2005-11-15

A LFER of the type in the title is applied to sorption of numerous compounds to polyethylene and three soils for which sorption to natural organic matter (NOM) is presumed dominant. It provides fractional contributions to the Gibbs free energy of sorption corresponding to hydrophobic effects, dipolar/polarizability (D/P) effects in excess of the reference state, and the sum of possible specific forces such as H-bonding and pi-pi electron donor-acceptor (pi-pi EDA) interactions in excess of the reference state. Minimal inputs are the isotherm, the n-hexadecane-water partition coefficient and the Abraham pi parameter representing D/P effects. Sorption of all compounds to polyethylene can be described by considering only hydrophobic effects. Sorption of a calibration set of apolar compounds (aromatic and aliphatic hydrocarbons and chlorinated hydrocarbons) to the natural sorbents is well-described by a combination of hydrophobic and D/P effects. For the apolar set, D/P contributes approximately 15-40% (2-8% for cyclohexane) of sorption free energy. D/P effects increase with the degree of chlorination for aliphatic compounds. For aromatic compounds D/P effects increase with fused ring size but do not vary with degree of chlorination and chlorine substitution pattern. H-bonding contributes substantially to sorption of alcohols, and similarly for 2-nonanol and 2,4-dichlorophenol (33-44%). pi-pi EDA forces contribute to phenanthrene sorption in one case. The effects of concentration, sorbent aromaticity (literature NMR), and sorbent polarity [(O + N)/C] on hydrophobic and D/P contributions for all compounds indicate that (a) molecules fill sites of progressively greater hydrophilic character; (b) the energy penalty for cavity formation in the solid decreases with concentration due to plasticization and greater intermolecular contact; (c) sorbent aromatic content more than sorbent polarity controls D/P interactions. Basing free energy on an inert electrostatic chemical environment afforded by n-hexadecane permits evaluation of direct electrostatic forces in NOM that contribute to sorption.

PACS development in Asia.

PubMed

Inamura, Kiyonari; Kousaka, Susumu; Yamamoto, Yuichiro; Sukenobu, Yoshiharu; Okura, Yasuhiko; Matsumura, Yasushi; Takeda, Hiroshi

2003-01-01

First, history of PACS in Japan from 1982 to 2002 has been investigated. By 2002 total of 1468 PACS units have been installed. Of these, 1174 are small-size PACS with less than four image display terminals, 203 are medium-size with 5-14 terminals, and 91 are large-size with 15 up to 1300 terminals. The main nine large-size PACS of 91 have been retrospectively investigated from 1984 for PACS experiments and from 1989 for PACS operation. Most of these nine hospitals have increased the number of PACS terminals by installing additional PACS units, instead of reinforcing the existing single PACS. The use of DICOM interfaces has increased the number of modalities connected to PACS and influenced the spreading of PACS installations in Japan. The status of HIS and RIS coupling to PACS, and the use of PACS in primary diagnosis or in image referral are discussed. Assessment of PACS is now in an early stage. Baseline studies of HIS/RIS/PACS effectiveness have been carried out to assess quantitatively the PACS merit. Second, history of PACS development in Korea is described. Very acute climbing up of filmless PACS diffusion was observed from 2000 to 2002. The reasons seem to be lack of domestic X-ray film industry, economic crisis in 1997 and PACS Reimbursement Act in health insurance in Korea. Third, the Hong Kong Wide Area Image Distribution/PACS Project is reported. It is now under phase 1 of design and partial implementation employing the latest and the highest ends of advanced technology such as failure resilience. Copyright 2002 Elsevier Science Ltd.

DEPENDENCY OF POLYCHLORINATED BIPHENYL AND POLYCYCLIC AROMATIC HYDROCARBON BIOACCUMULATION IN MYA ARENARIA ON BOTH WATER COLUMN AND SEDIMENT BED CHEMICAL ACTIVITIES

EPA Science Inventory

The bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) by the filter-feeding soft-shell clam Mya arenaria was evaluated at three sites near Boston (MA, USA) by assessing the chemical activities of those hydrophobic organic compounds (H...

Polybenzimidazoles Via Aromatic Nucleophilic Displacement

NASA Technical Reports Server (NTRS)

Connell, John W.; Hergenrother, Paul M.; Smith, Joseph G.

1994-01-01

Soluble polybenzimidazoles (PBI's) synthesized by nucleophilic displacement reaction of di(hydroxyphenyl)-benzimidazole monomers with activated aromatic difluoride compounds in presence of anhydrous potassium carbonate. These polymers exhibit good thermal, thermo-oxidative, and chemical stability, and high mechanical properties. Using benzimidazole monomers, more economical, and new PBI's processed more easily than commercial PBI, without loss of desirable physical properties.

AROMATIC METABOLISM IN PLANTS. I. A STUDY OF THE PREPHENATE DEHYDROGENASE FROM BEAN PLANTS,

DTIC Science & Technology

achieved in the pH range from 7 to 8. The enzyme is inhibited by sulphydryl complexing compounds. Addition of phenylalanine, tyrosine, or cinnamate ...mung bean (Phaseolus aureus Roxb.). A study was made of the variation in the amount of prephenate dehydrogenase and aromatic amino acid transaminase in

Synthesis of Triarylmethane and Xanthene Dyes Using Electrophilic Aromatic Substitution Reactions

ERIC Educational Resources Information Center

McCullagh, James V.; Daggett, Kelly A.

2007-01-01

The synthesis of dyes has long been a popular topic in organic chemistry laboratory experiments because it allows students to see first hand that reactions learned in class can be used to make compounds with useful applications. In this experiment electrophilic aromatic substitution reactions are used to synthesize several triarylmethane and…

MEASUREMENT OF HIGH-MOLECULAR-WEIGHT POLYCYCLIC AROMATIC HYDROCARBONS IN SOILS BY PARTICLE BEAM HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY-MASS SPECTROMETRY

EPA Science Inventory

Polycyclic aromatic hydrocarbons (PAHs) comprise a class of potentially hazardous compounds of concern to the U.S.EPA. The application of particle-beam (PB) liquid chromatography-mass spectrometry (LC-MS) to the measurement of high-molecular-weight PAHs was investigated. Instrume...

Multiple Cosmic Sources for Meteorite Macromolecules?

PubMed Central

Watson, Jonathan S.; Meredith, William; Love, Gordon D.; Gilmour, Iain; Snape, Colin E.

2015-01-01

Abstract The major organic component in carbonaceous meteorites is an organic macromolecular material. The Murchison macromolecular material comprises aromatic units connected by aliphatic and heteroatom-containing linkages or occluded within the wider structure. The macromolecular material source environment remains elusive. Traditionally, attempts to determine source have strived to identify a single environment. Here, we apply a highly efficient hydrogenolysis method to liberate units from the macromolecular material and use mass spectrometric techniques to determine their chemical structures and individual stable carbon isotope ratios. We confirm that the macromolecular material comprises a labile fraction with small aromatic units enriched in 13C and a refractory fraction made up of large aromatic units depleted in 13C. Our findings suggest that the macromolecular material may be derived from at least two separate environments. Compound-specific carbon isotope trends for aromatic compounds with carbon number may reflect mixing of the two sources. The story of the quantitatively dominant macromolecular material in meteorites appears to be made up of more than one chapter. Key Words: Abiotic organic synthesis—Carbonaceous chondrite—Cosmochemistry—Meteorites. Astrobiology 15, 779–786. PMID:26418568

Laboratory Studies of Stabilities of Heterocyclic Aromatic Molecules: Suggested Gas Phase Ion-Molecule Routes to Production in Interstellar Gas Clouds

NASA Technical Reports Server (NTRS)

Adams, Nigel G.; Fondren, L. Dalila; McLain, Jason L.; Jackson, Doug M.

2006-01-01

Several ring compounds have been detected in interstellar gas clouds, ISC, including the aromatic, benzene. Polycyclic aromatic hydrocarbons, PAHs, have been implicated as carriers of diffuse interstellar bands (DIBs) and unidentified infrared (UIR) bands. Heterocyclic aromatic rings of intermediate size containing nitrogen, possibly PreLife molecules, were included in early searches but were not detected and a recent search for Pyrimidine was unsuccessful. Our laboratory investigations of routes to such molecules could establish their existence in ISC and suggest conditions under which their concentrations would be maximized thus aiding the searches. The stability of such ring compounds (C5H5N, C4H4N2, C5H11N and C4H8O2) has been tested in the laboratory using charge transfer excitation in ion-molecule reactions. The fragmentation paths, including production of C4H4(+), C3H3N(+) and HCN, suggest reverse routes to the parent molecules, which are presently under laboratory investigation as production sources.

[Allergy to cosmetics. I. Fragrances].

PubMed

Kieć-Swierczyńska, Marta; Krecisz, Beata; Swierczyńska-Machura, Dominika

2004-01-01

The authors report current information on allergy to aromatic agents present in cosmetics and products of household chemistry. In the perfume industry, about 3000 aromas are used. Single products may contain from 10 to 300 compounds. The problem of difficulties encountered in the diagnosis of hypersensitivity to odors is addressed. The mixture of 8 such products used in diagnostic screening is able to detect allergy only in about 30% of patients who do not tolerate cosmetics. Changing frequency of allergy to individual aromas is discussed. It has been now observed that cinnamon products are less allergic than chemical compounds present in oak moss. Since the 1990s of the last century, allergy to a synthetic aromatic agent, Lyral is the subject of interest in many research centers involved in studies of contact allergy. Half the cosmetics present in European markets, especially deodorants, after shave cosmetics, hand and body lotions contain this agent. It induces positive reactions in about 10% of patients allergic to aromatic agents. Detection of allergy to Lyral is difficult as it is not included in the set of commercial allergens used to diagnose hypersensitivity to aromatic agents.

Aerobic Heterotrophic Bacterial Populations of Sewage and Activated Sludge

PubMed Central

Prakasam, T. B. S.; Dondero, N. C.

1970-01-01

An activated sludge from a sewage treatment plant and a laboratory activated sludge developed on an artificial waste were compared for their ability to utilize 11 aromatic compounds. There were several significant differences between them. The laboratory sludge contained higher numbers of organisms and metabolized the aromatics to a greater extent. Laboratory activated sludges acclimated to utilization of the aromatics differed from each other in population structure and the pattern of oxygen consumption with aromatic substrates. The oxidative patterns of uncontrolled mixed populations were unreliable for investigating metabolic pathways. Extracts of the various sludges elevated the plate counts of the sludges. PMID:5418946

Ambient cure polyimide foams prepared from aromatic polyisocyanates, aromatic polycarboxylic compounds, furfuryl alcohol, and a strong inorganic acid

NASA Technical Reports Server (NTRS)

Sawko, Paul M. (Inventor); Riccitiello, Salvatore R. (Inventor); Hamermesh, Charles L. (Inventor)

1980-01-01

Flame and temperature resistant polyimide foams are prepared by the reaction of an aromatic dianhydride, e.g., pyromellitic dianhydride, with an aromatic polyisocyanate, e.g., polymethylene polyphenylisocyanate (PAPI) in the presence of an inorganic acid and a lower molecular weight alcohol, e.g., dilute sulfuric acid or phosphoric acid and furfuryl alcohol. The exothermic reaction between the acid and the alcohol provides the heat necessary for the other reactants to polymerize without the application of any external heat. Such mixtures, therefore, are ideally suited for in situ foam formation, especially where the application of heat is not practical or possible.

UV irradiation of polycyclic aromatic hydrocarbons in ices: production of alcohols, quinones, and ethers

NASA Technical Reports Server (NTRS)

Bernstein, M. P.; Sandford, S. A.; Allamandola, L. J.; Gillette, J. S.; Clemett, S. J.; Zare, R. N.

1999-01-01

Polycyclic aromatic hydrocarbons (PAHs) in water ice were exposed to ultraviolet (UV) radiation under astrophysical conditions, and the products were analyzed by infrared spectroscopy and mass spectrometry. Peripheral carbon atoms were oxidized, producing aromatic alcohols, ketones, and ethers, and reduced, producing partially hydrogenated aromatic hydrocarbons, molecules that account for the interstellar 3.4-micrometer emission feature. These classes of compounds are all present in carbonaceous meteorites. Hydrogen and deuterium atoms exchange readily between the PAHs and the ice, which may explain the deuterium enrichments found in certain meteoritic molecules. This work has important implications for extraterrestrial organics in biogenesis.

Volatile and semivolatile organic compounds in laboratory ...

EPA Pesticide Factsheets

Speciated volatile organic compounds (VOCs) and organic fine particulate matter (PM2.5) mass emission factors were determined from laboratory peat fire experiments. Peat samples originated from two wildlife reserves located near the coast of North Carolina, U.S. Gas and particulate organics were quantified by gas chromatography/mass spectrometry and by high pressure liquid chromatography. Hazardous air pollutants (HAPs) accounted for a large fraction (~60 %) of the speciated VOC emissions from peat burning, including large contributions of acetaldehyde, formaldehyde, benzene, toluene, and chloromethane. Speciated organic PM2.5 mass was dominated by the following compound classes: organic acids, levoglucosan, n-alkanes, and n-alkenes. Emission factors for PM2.5 organic acids including n-alkanoic acids, n-alkenoic acids, n-alkanedioic acids, and aromatic acids were reported for the first time for peat burning, representing the largest fraction of organic carbon (OC) mass (11-12 %) of all speciated compound classes measured in this work. Levoglucosan contributed 2-3 % of the OC mass, while methoxyphenols represented 0.2-0.3 % of the OC mass on a carbon mass basis. Retene was the most abundant particulate phase polycyclic aromatic hydrocarbon. Total HAP VOC and particulate polycyclic aromatic hydrocarbon emissions from a 2008 peat wildfire in North Carolina were estimated, suggesting that peat fires can contribute a large fraction of state-wide HAP emissions. This p

Thirty-three years of 2-acetyl-1-pyrroline, a principal basmati aroma compound in scented rice (Oryza sativa L.): a status review.

PubMed

Wakte, Kantilal; Zanan, Rahul; Hinge, Vidya; Khandagale, Kiran; Nadaf, Altafhusain; Henry, Robert

2017-01-01

Rice is the staple food of around 3 billion people, most of them in Asia which accounts for 90% of global rice consumption. Aromatic rices have been preferred over non-aromatic rice for hundreds of years. They have a premium value in national as well as international market owing to their unique aroma and quality. Many researchers were involved in identifying the compound responsible for the pleasant aroma in aromatic rice in the 20th century. However, due to its unstable nature, 2-acetyl-1-pyrroline (2AP) was discovered very late, in 1982. Buttery and co-workers found 2AP to be the principal compound imparting the pleasant aroma to basmati and other scented rice varieties. Since then, 2AP has been identified in all fragrant rice (Oryza sativa L.) varieties and a wide range of plants, animals, fungi, bacteria and various food products. The present article reviews in detail biochemical and genetic aspects of 2AP in living systems. The site of synthesis, site of storage and stability in plant systems in vivo is of interest. This compound requires more research on stability to facilitate use as a food additive. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Occupational exposure to rubber vulcanization products during repair of rubber conveyor belts in a brown coal mine.

PubMed

Gromiec, Jan P; Wesołowski, Wiktor; Brzeźnicki, Sławomir; Wróblewska-Jakubowska, Krystyna; Kucharska, Małgorzata

2002-12-01

Several hundred chemical compounds were found in workroom environments in the rubber industry, but most of the published exposure data relate to the production of tyres; information from the "non-tyre" sections are very limited, if any. This study was carried out to identify chemical substances and measure their air concentrations in the repair shop of a brown coal mine in which damaged rubber conveyor belts were repaired. GC-MS and HPLC analysis of stationary air samples resulted in identification of aliphatic and aromatic hydrocarbons to C12, PAHs, alcohols, phenols, ketones, heterocyclic nitrogen and sulfur compounds. Quantitative evaluation of occupational exposure included determination of organic compound vapours collected on charcoal (GC-MSD), polycyclic aromatic hydrocarbons (HPLC), N-nitrosoamines and other amines (GC-NPD) and DNPH derivatives of aldehydes (HPLC) in the breathing zone of workers representing all job titles. The concentrations of investigated compounds were very low. Carcinogenic substances: N-nitrosoamines, benzene, PAHs were not present in workroom air in concentrations exceeding limits of detection of the analytical methods being applied; concentrations of methylisobutylketone, tetrachloroethylene, naphtha, aromatic hydrocarbons, phthalates and aldehydes were much lower than the respective occupational exposure limit values. The results indicate much lower exposure than that reported in the production of tyres and other fabricated rubber products.

Study of adsorption process of iron colloid substances on activated carbon by ultrasound

NASA Astrophysics Data System (ADS)

Machekhina, K. I.; Shiyan, L. N.; Yurmazova, T. A.; Voyno, D. A.

2015-04-01

The paper reports on the adsorption of iron colloid substances on activated carbon (PAC) Norit SA UF with using ultrasound. It is found that time of adsorption is equal to three hours. High-frequency electrical oscillation is 35 kHz. The adsorption capacity of activated carbon was determined and it is equal to about 0.25 mg iron colloid substances /mg PAC. The iron colloid substances size ranging from 30 to 360 nm was determined. The zeta potential of iron colloid substances which consists of iron (III) hydroxide, silicon compounds and natural organic substances is about (-38mV). The process of destruction iron colloid substances occurs with subsequent formation of a precipitate in the form of Fe(OH)3 as a result of the removal of organic substances from the model solution.

Regioselctive Thiocyanation of Aromatic and Heteroaromatic Compounds Using a Novel Bronsted Acidic Ionic Liquid.

PubMed

Rezayati, Sobhan; Sheikholeslami-Farahani, Fatemeh; Hossaini, Zinatossadat; Hajinasiri, Rahimeh; Abad, Saeid Afshari Sharif

2016-01-01

A convenient procedure for the preparation of 1-(1-Propylsulfonic)-3- methylimidazolium thiocyanate as a novel Brønsted acidic ionic liquid thiocyanation agent and highly efficient heterogeneous catalytic is described. This catalyst is used in regioselective thiocyanation of indoles, anilines, pyrroles and their derivatives (aromatic and heteroaromatic organic compounds) in the presence of H2O2 as a mild and oxidant in EtOH:H2O (1:1 v/v). These reactions are performed under mild and simple conditions and give regioselective products in high yields and short reaction time.

Beta-galactosidase catalyzed selective galactosylation of aromatic compounds.

PubMed

Bridiau, Nicolas; Taboubi, Selma; Marzouki, Nejib; Legoy, Marie Dominique; Maugard, Thierry

2006-01-01

A new approach to galacto-oligosaccharides and galacto-conjugates synthesis performed by the beta-galactosidase from Kluyveromyces lactis is reported. The enzymatic galactosylation of eight kinds of adsorbed aromatic primary alcohols, in particular the two drugs guaifenesin and chlorphenesin, gave the corresponding beta-D-galacto-pyranosides in yields ranging between approximately 10% and 96%. For the first time, we have showed that the adsorption of acceptor substrates onto solid supports such as silica gel influences the yield and the selectivity of galacto-conjugates synthesis. In particular, we observed that adsorption of acceptor favored the synthesis of digalactosylated compounds.

Measured and Predicted Vapor Liquid Equilibrium of Ethanol-Gasoline Fuels with Insight on the Influence of Azeotrope Interactions on Aromatic Species Enrichment and Particulate Matter Formation in Spark Ignition Engines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ratcliff, Matthew A; McCormick, Robert L; Burke, Stephen

A relationship has been observed between increasing ethanol content in gasoline and increased particulate matter (PM) emissions from direct injection spark ignition (DISI) vehicles. The fundamental cause of this observation is not well understood. One potential explanation is that increased evaporative cooling as a result of ethanol's high HOV may slow evaporation and prevent sufficient reactant mixing resulting in the combustion of localized fuel rich regions within the cylinder. In addition, it is well known that ethanol when blended in gasoline forms positive azeotropes which can alter the liquid/vapor composition during the vaporization process. In fact, it was shown recentlymore » through a numerical study that these interactions can retain the aromatic species within the liquid phase impeding the in-cylinder mixing of these compounds, which would accentuate PM formation upon combustion. To better understand the role of the azeotrope interactions on the vapor/liquid composition evolution of the fuel, distillations were performed using the Advanced Distillation Curve apparatus on carefully selected samples consisting of gasoline blended with ethanol and heavy aromatic and oxygenated compounds with varying vapor pressures, including cumene, p-cymene, 4-tertbutyl toluene, anisole, and 4-methyl anisole. Samples collected during the distillation indicate an enrichment of the heavy aromatic or oxygenated additive with an increase in initial ethanol concentration from E0 to E30. A recently developed distillation and droplet evaporation model is used to explore the influence of dilution effects versus azeotrope interactions on the aromatic species enrichment. The results suggest that HOV-cooling effects as well as aromatic species enrichment behaviors should be considered in future development of predictive indices to forecast the PM potential of fuels containing oxygenated compounds with comparatively high HOV.« less

Synthesis and Anticancer Activities of Novel Guanylhydrazone and Aminoguanidine Tetrahydropyran Derivatives.

PubMed

Silva, Fábio Pedrosa Lins; Dantas, Bruna Braga; Faheina Martins, Gláucia Veríssimo; de Araújo, Demétrius Antônio Machado; Vasconcellos, Mário Luiz Araújo de Almeida

2016-06-21

In this paper we present the convenient syntheses of six new guanylhydrazone and aminoguanidine tetrahydropyran derivatives 2-7. The guanylhydrazone 2, 3 and 4 were prepared in 100% yield, starting from corresponding aromatic ketones 8a-c and aminoguanidine hydrochloride accessed by microwave irradiation. The aminoguanidine 5, 6 and 7 were prepared by reduction of guanylhydrazone 2-4 with sodium cyanoborohydride (94% yield of 5, and 100% yield of 6 and 7). The aromatic ketones 8a-c were prepared from the Barbier reaction followed by the Prins cyclization reaction (two steps, 63%-65% and 95%-98%). Cytotoxicity studies have demonstrated the effects of compounds 2-7 in various cancer and normal cell lines. That way, we showed that these compounds decreased cell viabilities in a micromolar range, and from all the compounds tested we can state that, at least, compound 3 can be considered a promising molecule for target-directed drug design.

Refining the pH response in A spergillus nidulans: a modulatory triad involving PacX, a novel zinc binuclear cluster protein

PubMed Central

Bussink, Henk‐Jan; Bignell, Elaine M.; Múnera‐Huertas, Tatiana; Lucena‐Agell, Daniel; Scazzocchio, Claudio; Espeso, Eduardo A.; Bertuzzi, Margherita; Rudnicka, Joanna; Negrete‐Urtasun, Susana; Peñas‐Parilla, Maria M.; Rainbow, Lynne; Peñalva, Miguel Á.; Arst, Herbert N.

2015-01-01

Summary The A spergillus nidulans PacC transcription factor mediates gene regulation in response to alkaline ambient pH which, signalled by the Pal pathway, results in the processing of PacC72 to PacC27 via PacC53. Here we investigate two levels at which the pH regulatory system is transcriptionally moderated by pH and identify and characterise a new component of the pH regulatory machinery, PacX. Transcript level analysis and overexpression studies demonstrate that repression of acid‐expressed pal F, specifying the Pal pathway arrestin, probably by PacC27 and/or PacC53, prevents an escalating alkaline pH response. Transcript analyses using a reporter and constitutively expressed pac C  trans‐alleles show that pac C preferential alkaline‐expression results from derepression by depletion of the acid‐prevalent PacC72 form. We additionally show that pac C repression requires PacX. pac X mutations suppress PacC processing recalcitrant mutations, in part, through derepressed PacC levels resulting in traces of PacC27 formed by pH‐independent proteolysis. pac X was cloned by impala transposon mutagenesis. PacX, with homologues within the Leotiomyceta, has an unusual structure with an amino‐terminal coiled‐coil and a carboxy‐terminal zinc binuclear cluster. pacX mutations indicate the importance of these regions. One mutation, an unprecedented finding in A . nidulans genetics, resulted from an insertion of an endogenous Fot1‐like transposon. PMID:26303777

Factors causing PAC cake fouling in PAC-MF (powdered activated carbon-microfiltration) water treatment systems.

PubMed

Zhao, P; Takizawa, S; Katayama, H; Ohgaki, S

2005-01-01

Two pilot-scale powdered activated carbon-microfiltration (PAC-MF) reactors were operated using river water pretreated by a biofilter. A high permeate flux (4 m/d) was maintained in two reactors with different particle sizes of PAC. High concentration (20 g/L) in the PAC adsorption zone demonstrated 60-80% of organic removal rates. Analysis on the PAC cake fouling demonstrated that attached metal ions play more important role than organic matter attached on PAC to the increase of PAC cake resistance. Effects of factors which may cause PAC cake fouling in PAC-MF process were investigated and evaluated by batch experiments, further revealing that small particulates and metal ions in raw water impose prominent influence on the PAC cake layer formation. Fe (II) precipitates after being oxidized to Fe (III) during PAC adsorption and thus Fe(ll) colloids display more significant effect than other metal ions. At a high flux, PAC cake layer demonstrated a higher resistance with larger PAC due to association among colloids, metals and PAC particles, and easy migration of small particles in raw water into the void space in the PAC cake layer. Larger PAC possesses much more non-uniform particle size distribution and larger void space, making it easier for small colloids to migrate into the voids and for metal ions to associate with PAC particles by bridge effect, hence speeding up and intensifying the of PAC cake fouling on membrane surface.

Arylglycerol-γ-Formyl Ester as an Aromatic Ring Cleavage Product of Nonphenolic β-O-4 Lignin Substructure Model Compounds Degraded by Coriolus versicolor†

PubMed Central

Kawai, Shingo; Umezawa, Toshiaki; Higuchi, Takayoshi

1985-01-01

4-Ethoxy-3-methoxyphenylglycerol-γ-formyl ester (compound IV) was identified as a degradation product of both 4-ethoxy-3-methoxyphenylglycerol-β-syringaldehyde ether (compound I) and 4-ethoxy-3-methoxyphenylglycerol-β-2,6-dimethoxyphenyl ether (compound II) by a ligninolytic culture of Coriolus versicolor. An isotopic experiment with a 13C-labeled compound (compound II′) indicated that the formyl group of compound IV was derived from the β-phenoxyl group of β-O-4 dimer as an aromatic ring cleavage fragment. However, compound IV was not formed from 4-ethoxy-3-methoxyphenylglycerol-β-guaiacyl ether (compound III). γ-Formyl arylglycerol (compound IV) could be a precursor of 4-ethoxy-3-methoxyphenylglycerol (compound VI), because 3-(4-ethoxy-3-methoxyphenyl)-1-formyloxy propane (compound VII) was cleaved to give 3-(4-ethoxy-3-methoxyphenyl)-1-propanol (compound VIII) by C. versicolor. 4-Ethoxy-3-methoxyphenylglycerol-β,γ-cyclic carbonate (compound V), previously found as a degradation product of compound III by Phanerochaete chrysosporium (T. Umezawa, and T. Higuchi, FEBS Lett., 25:123-126, 1985), was also identified from the cultures with compound I, II, and III and degraded to give the arylglycerol (compound VI). An isotopic experiment with 13C-labeled compounds II′ and III′ indicated that the carbonate carbon of compound V was derived from the β-phenoxyl groups of β-O-4 substructure. PMID:16346950

Homogeneous purification and characterization of LePGT1--a membrane-bound aromatic substrate prenyltransferase involved in secondary metabolism of Lithospermum erythrorhizon.

PubMed

Ohara, Kazuaki; Mito, Koji; Yazaki, Kazufumi

2013-06-01

Membrane-bound type prenyltransferases for aromatic substrates play crucial roles in the biosynthesis of various natural compounds. Lithospermum erythrorhizon p-hydroxybenzoate: geranyltransferase (LePGT1), which contains multiple transmembrane α-helices, is involved in the biosynthesis of a red naphthoquinone pigment, shikonin. Taking LePGT1 as a model membrane-bound aromatic substrate prenyltransferase, we utilized a baculovirus-Sf9 expression system to generate a high yield LePGT1 polypeptide, reaching ~ 1000-fold higher expression level compared with a yeast expression system. Efficient solubilization procedures and biochemical purification methods were developed to extract LePGT1 from the membrane fraction of Sf9 cells. As a result, 80 μg of LePGT1 was purified from 150 mL culture to almost homogeneity as judged by SDS/PAGE. Using purified LePGT1, enzymatic characterization, e.g. substrate specificity, divalent cation requirement and kinetic analysis, was done. In addition, inhibition experiments revealed that aromatic compounds having two phenolic hydroxyl groups effectively inhibited LePGT1 enzyme activity, suggesting a novel recognition mechanism for aromatic substrates. As the first example of solubilization and purification of this membrane-bound protein family, the methods established in this study will provide valuable information for the precise biochemical characterization of aromatic prenyltransferases as well as for crystallographic analysis of this novel enzyme family. © 2013 The Authors Journal compilation © 2013 FEBS.

Polycyclic aromatic hydrocarbon metabolic network in Mycobacterium vanbaalenii PYR-1.

PubMed

Kweon, Ohgew; Kim, Seong-Jae; Holland, Ricky D; Chen, Hongyan; Kim, Dae-Wi; Gao, Yuan; Yu, Li-Rong; Baek, Songjoon; Baek, Dong-Heon; Ahn, Hongsik; Cerniglia, Carl E

2011-09-01

This study investigated a metabolic network (MN) from Mycobacterium vanbaalenii PYR-1 for polycyclic aromatic hydrocarbons (PAHs) from the perspective of structure, behavior, and evolution, in which multilayer omics data are integrated. Initially, we utilized a high-throughput proteomic analysis to assess the protein expression response of M. vanbaalenii PYR-1 to seven different aromatic compounds. A total of 3,431 proteins (57.38% of the genome-predicted proteins) were identified, which included 160 proteins that seemed to be involved in the degradation of aromatic hydrocarbons. Based on the proteomic data and the previous metabolic, biochemical, physiological, and genomic information, we reconstructed an experiment-based system-level PAH-MN. The structure of PAH-MN, with 183 metabolic compounds and 224 chemical reactions, has a typical scale-free nature. The behavior and evolution of the PAH-MN reveals a hierarchical modularity with funnel effects in structure/function and intimate association with evolutionary modules of the functional modules, which are the ring cleavage process (RCP), side chain process (SCP), and central aromatic process (CAP). The 189 commonly upregulated proteins in all aromatic hydrocarbon treatments provide insights into the global adaptation to facilitate the PAH metabolism. Taken together, the findings of our study provide the hierarchical viewpoint from genes/proteins/metabolites to the network via functional modules of the PAH-MN equipped with the engineering-driven approaches of modularization and rationalization, which may expand our understanding of the metabolic potential of M. vanbaalenii PYR-1 for bioremediation applications.

Crystal structures of HIV-1 nonnucleoside reverse transcriptase inhibitors: N-benzyl-4-methyl-benzimidazoles

NASA Astrophysics Data System (ADS)

Ziółkowska, Natasza E.; Michejda, Christopher J.; Bujacz, Grzegorz D.

2009-07-01

HIV-1 nonnucleoside reverse transcriptase inhibitors are potentially specific and effective drugs in AIDS therapy. The presence of two aromatic systems with an angled orientation in the molecule of the inhibitor is crucial for interactions with HIV-1 RT. The inhibitor drives like a wedge into the cluster of aromatic residues of RT HIV-1 and restrains the enzyme in a conformation that blocks the chemical step of nucleotide incorporation. Structural studies provide useful information for designing new, more active inhibitors. The crystal structures of four NNRTIs are presented here. The investigated compounds are derivatives of N-benzyl-4-methyl-benzimidazole with various aliphatic and aromatic substituents at carbon 2 positions and a 2,6-dihalogeno-substituted N-benzyl moiety. Structural data reported here show that the conformation of the investigated compounds is relatively rigid. Such feature is important for the nonnucleoside inhibitor binding to HIV-1 reverse transcriptase.

Use of constant wavelength synchronous spectrofluorimetry for identification of polycyclic aromatic hydrocarbons in air particulate samples

NASA Astrophysics Data System (ADS)

Sharma, Homdutt; Jain, V. K.; Khan, Zahid H.

2013-05-01

We have developed a simple, rapid, inexpensive method for the identification of fluoranthene (Flan), benz(a)anthracene (BaA), benzo(a)pyrene (BaP), benzo(k)fluoranthene (BkF), pyrene (Pyr), benz(ghi)perylene (BghiP) in suspended particulate matter in an urban environment of Delhi. Suspended particulate matter samples of 24 h duration were collected on glass fiber filter papers. Polycyclic aromatic hydrocarbons (PAHs) were extracted from the filter papers using dichloromethane (DCM) and hexane with ultrasonication method. Comparison of the characteristic emission of spectra of PAHs with standard spectra indicated the degree of condensation of aromatic compounds present in investigated mixtures. It was also possible to identify some individual compounds. However, this identification could be more effective with the use of the respective values of Δλ parameter for each particular component of the mixture.

Aromatics and phenols from catalytic pyrolysis of Douglas fir pellets in microwave with ZSM-5 as a catalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Lu; Lei, Hanwu; Ren, Shoujie

Microwave assisted catalytic pyrolysis was investigated to convert Douglas fir pellets to bio-oils by a ZSM-5 Zeolite catalyst. A central composite experimental design (CCD) was used to optimize the catalytic pyrolysis process. The effects of reaction time, temperature and catalyst to biomass ratio on the bio-oil, syngas, and biochar yields were determined. GC/MS analysis results showed that the bio-oil contained a series of important and useful chemical compounds. Phenols, guaiacols, and aromatic hydrocarbons were the most abundant compounds which were about 50-82 % in bio-oil depending on the pyrolysis conditions. Comparison between the bio-oils from microwave pyrolysis with and withoutmore » catalyst showed that the catalyst increased the content of aromatic hydrocarbons and phenols. A reaction pathway was proposed for microwave assisted catalyst pyrolysis of Douglas fir pellets.« less

Development of Chemical and Metabolite Sensors for Rhodococcus opacus PD630.

PubMed

DeLorenzo, Drew M; Henson, William R; Moon, Tae Seok

2017-10-20

Rhodococcus opacus PD630 is a nonmodel, Gram-positive bacterium that possesses desirable traits for biomass conversion, including consumption capabilities for lignocellulose-based sugars and toxic lignin-derived aromatic compounds, significant triacylglycerol accumulation, relatively rapid growth rate, and genetic tractability. However, few genetic elements have been directly characterized in R. opacus, limiting its application for lignocellulose bioconversion. Here, we report the characterization and development of genetic tools for tunable gene expression in R. opacus, including: (1) six fluorescent reporters for quantifying promoter output, (2) three chemically inducible promoters for variable gene expression, and (3) two classes of metabolite sensors derived from native R. opacus promoters that detect nitrogen levels or aromatic compounds. Using these tools, we also provide insights into native aromatic consumption pathways in R. opacus. Overall, this work expands the ability to control and characterize gene expression in R. opacus for future lignocellulose-based fuel and chemical production.

Model compound study of the pathways for aromatic hydrocarbon formation in soot.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tomczyk, N. A.; Hunt, J. E.; Winans, R. E.

2002-04-29

To explore the mechanisms for formation of aromatic hydrocarbons as precursors to soot, a model system using combustion of biphenyl in a fuel rich flame is studied. The soots acquired at three different temperatures are solvent extracted and the extract characterized by both GCMS and high resolution mass spectrometry. A description of the NMR results for the whole soots has been published (1). The production of most products could be rationalized from the coupling of biphenyls and subsequent aromatic species and the addition of acetylenes to existing aromatic molecules. Early work by Badger on pyrolysis of hydrocarbons is used inmore » developing these schemes (2). The reaction schemes to produce larger aromatic hydrocarbons will be discussed. Richter and Howard have discussed in detail potential reaction mechanisms in the formation of aromatics as precursors to soot (3).« less

Biomonitoring of polycyclic aromatic compounds in the urine of mining workers occupationally exposed to diesel exhaust.

PubMed

Seidel, Albrecht; Dahmann, Dirk; Krekeler, Horst; Jacob, Juergen

2002-02-01

Diesel exhaust is considered a probable human carcinogen by the IARC. Biomonitoring of workers occupationally exposed to diesel exhaust was performed to determine their internal burden of diesel associated aromatic compounds. Personal air sampling also allowed to determine the exposure of the miners at their work place towards several polycyclic aromatic hydrocarbons (PAH) and nitro-arenes, the latter of which are thought to be specific constituents of diesel exhaust. For biomonitoring the urine of 18 underground salt miners was collected during and after their shift for 24-hours. half of the 18 miners were smokers. The urinary levels of 1-hydroxypyrene and hydroxylated phenanthrene metabolites were determined as biomarkers of PAH exposure, whereas urinary levels of some aromatic amines were chosen to monitor exposure towards specific nitro-arenes from diesel exhaust like 1-nitropyrene and 3-nitrobenzanthrone and to monitor the human burden by these compounds from inhaled cigarette smoke. Non-smoking workers exposed to diesel exhaust excrete an average level of about 4 micrograms phenanthrene metabolites, whereas the urinary levels in smokers were up to 3-fold higher. In summary the results indicate that (i) diesel exposure led to an increase of PAH metabolism in the workers examined, most probably by an induction of cytochrome P450 (ii) smokers could be identified in accordance with earlier studies by their increased ratio of phenanthrene metabolites derived from 1,2- and 3,4-oxidation and their higher amounts of excreted 1-naphthylamine, and (iii) the excreted amounts of aromatic amines found as metabolites of the nitro-arenes were about 5- to 10-fold higher as one might expect from the levels determined by personal air sampling at the workplace of the individuals.

Solvent-resistant sol-gel polydimethyldiphenylsiloxane coating for on-line hyphenation of capillary microextraction with high-performance liquid chromatography.

PubMed

Segro, Scott S; Malik, Abdul

2008-09-26

A sol-gel polydimethyldiphenylsiloxane (PDMDPS) coating was developed for capillary microextraction on-line hyphenated with high-performance liquid chromatography (HPLC). This coating was created using methyltrimethoxysilane (MTMS) as the sol-gel precursor and di-hydroxy-terminated PDMDPS as the sol-gel active polymer. The methyl and phenyl groups on the sol-gel active polymer and the methyl groups on the sol-gel precursor ultimately turned into pendant groups providing the ability to extract non-polar analytes. A 40-cm segment of 0.25 mm I.D. fused silica capillary containing the sol-gel PDMDPS coating was installed as an external sampling loop in an HPLC injection port. Aqueous samples containing polycyclic aromatic hydrocarbons (PAHs), aromatic compounds, ketones, and aldehydes were passed through this capillary wherein the analytes were extracted by the sol-gel coating. The extracted analytes were then transferred to the HPLC column using isocratic or gradient elution with an acetonitrile/water mobile phase. This capillary demonstrated excellent extraction capability for non-polar (e.g., polycyclic aromatic hydrocarbons and aromatic compounds) as well as moderately polar compounds, such as aromatic amines, ketones, and aldehydes. The test results indicate that PDMDPS can be successfully immobilized into a sol-gel network and that the resulting solvent-resistant sol-gel organic-inorganic hybrid coating can be effectively used for on-line hyphenation of capillary microextraction with high-performance liquid chromatography. The test results also indicate that the sol-gel PDMDPS coated capillary is resistant to high-temperature solvents, making it suitable for applications in high-temperature HPLC. To the best of our knowledge, this is the first report on the creation of a silica-based sol-gel PDMDPS coating used in capillary microextraction on-line hyphenated to HPLC.

Lasiodiplodia sp. ME4-2, an endophytic fungus from the floral parts of Viscum coloratum, produces indole-3-carboxylic acid and other aromatic metabolites.

PubMed

Qian, Chao-Dong; Fu, Yu-Hang; Jiang, Fu-Sheng; Xu, Zheng-Hong; Cheng, Dong-Qing; Ding, Bin; Gao, Cheng-Xian; Ding, Zhi-Shan

2014-11-30

Studies on endophytes, a relatively under-explored group of microorganisms, are currently popular amongst biologists and natural product researchers. A fungal strain (ME4-2) was isolated from flower samples of mistletoe (Viscum coloratum) during a screening program for endophytes. As limited information on floral endophytes is available, the aim of the present study is to characterise fungal endophytes using their secondary metabolites. ME4-2 grew well in both natural and basic synthetic media but produced no conidia. Sequence analysis of its internal transcribed spacer rDNA demonstrated that ME4-2 forms a distinct branch within the genus Lasiodiplodia and is closely related to L. pseudotheobromae. This floral endophyte was thus identified as Lasiodiplodia sp. based on its molecular biological characteristics. Five aromatic compounds, including cyclo-(Trp-Ala), indole-3-carboxylic acid (ICA), indole-3-carbaldehyde, mellein and 2-phenylethanol, were found in the culture. The structures of these compounds were determined using spectroscopic methods combined with gas chromatography. To the best of our knowledge, our work is the first to report isolation of these aromatic metabolites from a floral endophyte. Interestingly, ICA, a major secondary metabolite produced by ME4-2, seemed to be biosynthesized via an unusual pathway. Furthermore, our results indicate that the fungus ME4-2 is a potent producer of 2-phenylethanol, which is a common component of floral essential oils. This study introduces a fungal strain producing several important aromatic metabolites with pharmaceutical or food applications and suggests that endophytic fungi isolated from plant flowers are promising natural sources of aromatic compounds.

PacCYP707A2 negatively regulates cherry fruit ripening while PacCYP707A1 mediates drought tolerance.

PubMed

Li, Qian; Chen, Pei; Dai, Shengjie; Sun, Yufei; Yuan, Bing; Kai, Wenbin; Pei, Yuelin; He, Suihuan; Liang, Bin; Zhang, Yushu; Leng, Ping

2015-07-01

Sweet cherry is a non-climacteric fruit and its ripening is regulated by abscisic acid (ABA) during fruit development. In this study, four cDNAs (PacCYP707A1-4) encoding 8'-hydroxylase, a key enzyme in the oxidative catabolism of ABA, were identified in sweet cherry fruits using tobacco rattle virus-induced gene silencing (VIGS) and particle bombardment approaches. Quantitative real-time PCR confirmed significant down-regulation of target gene transcripts in VIGS-treated cherry fruits. In PacCYP707A2-RNAi-treated fruits, ripening and fruit colouring were promoted relative to control fruits, and both ABA accumulation and PacNCED1 transcript levels were up-regulated by 140%. Silencing of PacCYP707A2 by VIGS significantly altered the transcripts of both ABA-responsive and ripening-related genes, including the ABA metabolism-associated genes NCED and CYP707A, the anthocyanin synthesis genes PacCHS, PacCHI, PacF3H, PacDFR, PacANS, and PacUFGT, the ethylene biosynthesis gene PacACO1, and the transcription factor PacMYBA. The promoter of PacMYBA responded more strongly to PacCYP707A2-RNAi-treated fruits than to PacCYP707A1-RNAi-treated fruits. By contrast, silencing of PacCYP707A1 stimulated a slight increase in fruit colouring and enhanced resistance to dehydration stress compared with control fruits. These results suggest that PacCYP707A2 is a key regulator of ABA catabolism that functions as a negative regulator of fruit ripening, while PacCYP707A1 regulates ABA content in response to dehydration during fruit development. © The Author 2015. Published by Oxford University Press on behalf of the Society for Experimental Biology.

PacCYP707A2 negatively regulates cherry fruit ripening while PacCYP707A1 mediates drought tolerance

PubMed Central

Li, Qian; Chen, Pei; Dai, Shengjie; Sun, Yufei; Yuan, Bing; Kai, Wenbin; Pei, Yuelin; He, Suihuan; Liang, Bin; Zhang, Yushu; Leng, Ping

2015-01-01

Sweet cherry is a non-climacteric fruit and its ripening is regulated by abscisic acid (ABA) during fruit development. In this study, four cDNAs (PacCYP707A1–4) encoding 8′-hydroxylase, a key enzyme in the oxidative catabolism of ABA, were identified in sweet cherry fruits using tobacco rattle virus-induced gene silencing (VIGS) and particle bombardment approaches. Quantitative real-time PCR confirmed significant down-regulation of target gene transcripts in VIGS-treated cherry fruits. In PacCYP707A2-RNAi-treated fruits, ripening and fruit colouring were promoted relative to control fruits, and both ABA accumulation and PacNCED1 transcript levels were up-regulated by 140%. Silencing of PacCYP707A2 by VIGS significantly altered the transcripts of both ABA-responsive and ripening-related genes, including the ABA metabolism-associated genes NCED and CYP707A, the anthocyanin synthesis genes PacCHS, PacCHI, PacF3H, PacDFR, PacANS, and PacUFGT, the ethylene biosynthesis gene PacACO1, and the transcription factor PacMYBA. The promoter of PacMYBA responded more strongly to PacCYP707A2-RNAi-treated fruits than to PacCYP707A1-RNAi-treated fruits. By contrast, silencing of PacCYP707A1 stimulated a slight increase in fruit colouring and enhanced resistance to dehydration stress compared with control fruits. These results suggest that PacCYP707A2 is a key regulator of ABA catabolism that functions as a negative regulator of fruit ripening, while PacCYP707A1 regulates ABA content in response to dehydration during fruit development. PMID:25956880

Pyridine group assisted addition of diazo-compounds to imines in the 3-CC reaction of 2-aminopyridines, aldehydes, and diazo-compounds.

PubMed

Gulevich, Anton V; Helan, Victoria; Wink, Donald J; Gevorgyan, Vladimir

2013-02-15

A novel three-component coupling (3-CC) reaction of 2-aminoazines, aromatic aldehydes, and diazo-compounds producing polyfunctional β-amino-α-diazo-compounds has been developed. The reaction features an unprecedented heterocycle-assisted addition of a diazo-compound to an imine. The obtained diazoesters were efficiently converted into valuable heterocycles as well as β-amino acid derivatives.

Synthesis of Aromatic Aza-metallapentalenes from Metallabenzene via Sequential Ring Contraction/Annulation

NASA Astrophysics Data System (ADS)

Wang, Tongdao; Han, Feifei; Huang, Haiping; Li, Jinhua; Zhang, Hong; Zhu, Jun; Lin, Zhenyang; Xia, Haiping

2015-04-01

The concept of aromaticity has long played an important role in chemistry and continues to fascinate both experimentalists and theoreticians. Among the archetypal aromatic compounds, heteroaromatics are particularly attractive. Recently, substitution of a transition-metal fragment for a carbon atom in the anti-aromatic hydrocarbon pentalene has led to the new heteroaromatic osmapentalenes. However, construction of the aza-homolog of osmapentalenes cannot be accomplished by a similar synthetic manipulation. Here, we report the synthesis of aza-osmapentalenes by sequential ring contraction/annulation reactions of osmabenzenes via osmapentafulvenes. Nuclear magnetic resonance spectra, X-ray crystallographic analysis, and DFT calculations all suggest that these aza-osmapentalenes exhibit aromatic character. Thus, the stepwise transformation of metallabenzenes to metallapentafulvenes and then aza-metallapentalenes provides an efficient and facile synthetic route to these bicyclic heteroaromatics.

Synthesis of tetra- and octa-aurated heteroaryl complexes towards probing aromatic indoliums

PubMed Central

Yuan, Jun; Sun, Tingting; He, Xin; An, Ke; Zhu, Jun; Zhao, Liang

2016-01-01

Polymetalated aromatic compounds are particularly challenging synthetic goals because of the limited thermodynamic stability of polyanionic species arising from strong electrostatic repulsion between adjacent carbanionic sites. Here we describe a facile synthesis of two polyaurated complexes including a tetra-aurated indole and an octa-aurated benzodipyrrole. The imido trinuclear gold(I) moiety exhibits nucleophilicity and undergoes an intramolecular attack on a gold(I)-activated ethynyl to generate polyanionic heteroaryl species. Their computed magnetic properties reveal the aromatic character in the five-membered ring. The incorporation of the aurated substituents at the nitrogen atom can convert non-aromaticity in the parent indolium into aromaticity in the aurated one because of hyperconjugation. Thus, the concept of hyperconjugative aromaticity is extended to heterocycles with transition metal substituents. More importantly, further analysis indicates that the aurated substituents can perform better than traditional main-group substituents. This work highlights the difference in aromaticity between polymetalated aryls and their organic prototypes. PMID:27186982

Process for reducing aromatic compounds in ethylenediamine with calcium

DOEpatents

Benkeser, Robert A.; Laugal, James A.; Rappa, Angela

1985-01-01

Olefins are produced by containing an organic compound having at least one benzene ring with ethylenediamine and calcium metal, the calcium metal being used in large excess or alternatively in conjunction with an inert abrasive particulate substance. Substantially all of the organic compounds are converted to corresponding cyclic olefins, largely mono-olefins.

Process for reducing aromatic compounds in ethylenediamine with calcium

DOEpatents

Benkeser, R.A.; Laugal, J.A.; Rappa, A.

1985-08-06

Olefins are produced by containing an organic compound having at least one benzene ring with ethylenediamine and calcium metal, the calcium metal being used in large excess or alternatively in conjunction with an inert abrasive particulate substance. Substantially all of the organic compounds are converted to corresponding cyclic olefins, largely mono-olefins.

Two new luminescent Zn(II) compounds constructed from guanazole and aromatic polycarboxylate ligands

NASA Astrophysics Data System (ADS)

Zhao, Haixiang; Dong, Yanli; Liu, Haiping

2016-02-01

Two new Zn(II) compounds, namely [(CH3)2NH2]2n[Zn3(bpt)2(datrz)2]n (1) and [(CH3)2NH2)]n[Zn2(bptc)(datrz)]n·n(H2O) (2) (H3bpt = biphenyl-3,4‧,5-tricarboxylic acid, H4bptc = biphenyl-3,3‧,5,5‧-tetracarboxylic acid, Hdatrz = 3,5-diamino-1,2,4-triazole), have been obtained by the self-assemble reactions of Zn(NO3)2, 3,5-diamino-1,2,4-triazole, aromatic polycarboxylate ligands under solvothermal conditions. Single crystal X-ray structural analyses reveal that both compounds display three-dimensional (3D) frameworks. Compound 1 features a trinodal (3, 4, 6)-connected topological network with the point symbol of {4.62}2{4.64.8}{46.64.85}. Compound 2 displays a binodal (4, 6)-connected topological network with the point symbol of {32.62.72}{34.42.64.75}. In addition, the thermal stabilities and luminescent properties of compounds 1 and 2 were also investigated in the solid state at room temperature.

Linear solvation energy relationships (LSER) for adsorption of organic compounds by carbon nanotubes.

PubMed

Ersan, Gamze; Apul, Onur G; Karanfil, Tanju

2016-07-01

The objective of this paper was to create a comprehensive database for the adsorption of organic compounds by carbon nanotubes (CNTs) and to use the Linear Solvation Energy Relationship (LSER) technique for developing predictive adsorption models of organic compounds (OCs) by multi-walled carbon nanotubes (MWCNTs) and single-walled carbon nanotubes (SWCNTs). Adsorption data for 123 OCs by MWCNTs and 48 OCs by SWCNTs were compiled from the literature, including some experimental results obtained in our laboratory. The roles of selected OCs properties and CNT types were examined with LSER models. The results showed that the r(2) values of the LSER models displayed small variability for aromatic compounds smaller than 220 g/mol, after which a decreasing trend was observed. The data available for aliphatics was mainly for molecular weights smaller than 250 g/mol, which showed a similar trend to that of aromatics. The r(2) values for the LSER model on the adsorption of aromatic and aliphatic OCs by SWCNTs and MWCNTs were relatively similar indicating the linearity of LSER models did not depend on the CNT types. Among all LSER model descriptors, V term (molecular volume) for aromatic OCs and B term (basicity) for aliphatic OCs were the most predominant descriptors on both type of CNTs. The presence of R term (excess molar refractivity) in LSER model equations resulted in decreases for both V and P (polarizability) parameters without affecting the r(2) values. Overall, the results demonstrate that successful predictive models can be developed for the adsorption of OCs by MWCNTs and SWCNTs with LSER techniques. Copyright © 2016 Elsevier Ltd. All rights reserved.

Analysis of aromatic catabolic pathways in Pseudomonas putida KT 2440 using a combined proteomic approach: 2-DE/MS and cleavable isotope-coded affinity tag analysis.

PubMed

Kim, Young Hwan; Cho, Kun; Yun, Sung-Ho; Kim, Jin Young; Kwon, Kyung-Hoon; Yoo, Jong Shin; Kim, Seung Il

2006-02-01

Proteomic analysis of Pseudomonas putida KT2440 cultured in monocyclic aromatic compounds was performed using 2-DE/MS and cleavable isotope-coded affinity tag (ICAT) to determine whether proteins involved in aromatic compound degradation pathways were altered as predicted by genomic analysis (Jiménez et al., Environ Microbiol. 2002, 4, 824-841). Eighty unique proteins were identified by 2-DE/MS or MS/MS analysis from P. putida KT2440 cultured in the presence of six different organic compounds. Benzoate dioxygenase (BenA, BenD) and catechol 1,2-dioxygenase (CatA) were induced by benzoate. Protocatechuate 3,4-dixoygenase (PcaGH) was induced by p-hydroxybenzoate and vanilline. beta-Ketoadipyl CoA thiolase (PcaF) and 3-oxoadipate enol-lactone hydrolase (PcaD) were induced by benzoate, p-hydroxybenzoate and vanilline, suggesting that benzoate, p-hydroxybenzoate and vanilline were degraded by different dioxygenases and then converged in the same beta-ketoadipate degradation pathway. An additional 110 proteins, including 19 proteins from 2-DE analysis, were identified by cleavable ICAT analysis for benzoate-induced proteomes, which complemented the 2-DE results. Phenylethylamine exposure induced beta-ketoacyl CoA thiolase (PhaD) and ring-opening enzyme (PhaL), both enzymes of the phenylacetate (pha) biodegradation pathway. Phenylalanine induced 4-hydroxyphenyl-pyruvate dioxygenase (Hpd) and homogentisate 1,2-dioxygenase (HmgA), key enzymes in the homogentisate degradation pathway. Alkyl hydroperoxide reductase (AphC) was induced under all aromatic compounds conditions. These results suggest that proteome analysis complements and supports predictive information obtained by genomic sequence analysis.

Mutagenicity of an aged gasworks soil during bioslurry treatment

PubMed Central

Lemieux, Christine L; Lynes, Krista D; White, Paul A; Lundstedt, Staffan; Öberg, Lars; Lambert, Iain B

2009-01-01

This study investigated changes in the mutagenic activity of organic fractions from soil contaminated with polycyclic aromatic hydrocarbons (PAHs) during pilot-scale bioslurry remediation. Slurry samples were previously analyzed for changes in PAH and polycyclic aromatic compound content, and this study examined the correspondence between the chemical and toxicological metrics. Nonpolar neutral and semipolar aromatic fractions of samples obtained on days 0, 3, 7, 24, and 29 of treatment were assayed for mutagenicity using the Salmonella mutation assay. Most samples elicited a significant positive response on Salmonella strains TA98, YG1041, and YG1042 with and without S9 metabolic activation; however, TA100 failed to detect mutagenicity in any sample. Changes in the mutagenic activity of the fractions across treatment time and metabolic activation conditions suggests a pattern of formation and transformation of mutagenic compounds that may include a wide range of PAH derivatives such as aromatic amines, oxygenated PAHs, and S-heterocyclic compounds. The prior chemical analyses documented the formation of oxygenated PAHs during the treatment (e.g., 4-oxapyrene-5-one), and the mutagenicity analyses showed high corresponding activity in the semipolar fraction with and without metabolic activation. However, it could not be verified that these specific compounds were the underlying cause of the observed changes in mutagenic activity. The results highlight the need for concurrent chemical and toxicological profiling of contaminated sites undergoing remediation to ensure elimination of priority contaminants as well as a reduction in toxicological hazard. Moreover, the results imply that remediation efficacy and utility be evaluated using both chemical and toxicological metrics. Environ. Mol. Mutagen. 2009. © 2009 Wiley-Liss, Inc. PMID:19274766

Genome sequence of the lignocellulose degrading fungus Phanerochaete chrysosporium strain RP78

Treesearch

Diego Martinez; Luis Larrondo; Nik Putnam; Maarten D. Sollewijn; Maarten D. Sollewijn Gelpke; Katherine Huang; Jarrod Chapman; Kevin G. Helfenbein; Preethi Ramaiya; J. Chris Detter; Frank Larimer; Pedro M. Coutinho; Bernard Henrissat; Randy Berka; Dan Cullen; Daniel Rokhsar

2004-01-01

White rot fungi efficiently degrade lignin, a complex aromatic polymer in wood that is among the most abundant natural materials on earth. These fungi use extracellular oxidative enzymes that are also able to transform related aromatic compounds found in explosive contaminants, pesticides and toxic waste. We have sequenced the 30-million base-pair genome of...

Polynuclear aromatic hydrocarbons in forest fire smoke

Treesearch

Charles K. McMahon; Skevos N. Tsoukalas

1978-01-01

The occurrence of polynuclear aromatic hydrocarbons (PAH) in the combustion products of carbonaceous fuels is a well known phenomenon. Several PAW are known to be carcinogenic in animals. Benzo[a]pyrene (BaP) is the most well-known and studied compound of those classified by the National Academy of Science (NAS) as strongly carcinogenic. Ambient BaP concentrations...

Genomic phenotyping by barcode sequencing broadly distinguishes between alkylating agents, oxidizing agents, and non-genotoxic agents, and reveals a role for aromatic amino acids in cellular recovery after quinone exposure.

PubMed

Svensson, J Peter; Quirós Pesudo, Laia; McRee, Siobhan K; Adeleye, Yeyejide; Carmichael, Paul; Samson, Leona D

2013-01-01

Toxicity screening of compounds provides a means to identify compounds harmful for human health and the environment. Here, we further develop the technique of genomic phenotyping to improve throughput while maintaining specificity. We exposed cells to eight different compounds that rely on different modes of action: four genotoxic alkylating (methyl methanesulfonate (MMS), N-Methyl-N-nitrosourea (MNU), N,N'-bis(2-chloroethyl)-N-nitroso-urea (BCNU), N-ethylnitrosourea (ENU)), two oxidizing (2-methylnaphthalene-1,4-dione (menadione, MEN), benzene-1,4-diol (hydroquinone, HYQ)), and two non-genotoxic (methyl carbamate (MC) and dimethyl sulfoxide (DMSO)) compounds. A library of S. cerevisiae 4,852 deletion strains, each identifiable by a unique genetic 'barcode', were grown in competition; at different time points the ratio between the strains was assessed by quantitative high throughput 'barcode' sequencing. The method was validated by comparison to previous genomic phenotyping studies and 90% of the strains identified as MMS-sensitive here were also identified as MMS-sensitive in a much lower throughput solid agar screen. The data provide profiles of proteins and pathways needed for recovery after both genotoxic and non-genotoxic compounds. In addition, a novel role for aromatic amino acids in the recovery after treatment with oxidizing agents was suggested. The role of aromatic acids was further validated; the quinone subgroup of oxidizing agents were extremely toxic in cells where tryptophan biosynthesis was compromised.

Genomic Phenotyping by Barcode Sequencing Broadly Distinguishes between Alkylating Agents, Oxidizing Agents, and Non-Genotoxic Agents, and Reveals a Role for Aromatic Amino Acids in Cellular Recovery after Quinone Exposure

PubMed Central

Svensson, J. Peter; Quirós Pesudo, Laia; McRee, Siobhan K.; Adeleye, Yeyejide; Carmichael, Paul; Samson, Leona D.

2013-01-01

Toxicity screening of compounds provides a means to identify compounds harmful for human health and the environment. Here, we further develop the technique of genomic phenotyping to improve throughput while maintaining specificity. We exposed cells to eight different compounds that rely on different modes of action: four genotoxic alkylating (methyl methanesulfonate (MMS), N-Methyl-N-nitrosourea (MNU), N,N′-bis(2-chloroethyl)-N-nitroso-urea (BCNU), N-ethylnitrosourea (ENU)), two oxidizing (2-methylnaphthalene-1,4-dione (menadione, MEN), benzene-1,4-diol (hydroquinone, HYQ)), and two non-genotoxic (methyl carbamate (MC) and dimethyl sulfoxide (DMSO)) compounds. A library of S. cerevisiae 4,852 deletion strains, each identifiable by a unique genetic ‘barcode’, were grown in competition; at different time points the ratio between the strains was assessed by quantitative high throughput ‘barcode’ sequencing. The method was validated by comparison to previous genomic phenotyping studies and 90% of the strains identified as MMS-sensitive here were also identified as MMS-sensitive in a much lower throughput solid agar screen. The data provide profiles of proteins and pathways needed for recovery after both genotoxic and non-genotoxic compounds. In addition, a novel role for aromatic amino acids in the recovery after treatment with oxidizing agents was suggested. The role of aromatic acids was further validated; the quinone subgroup of oxidizing agents were extremely toxic in cells where tryptophan biosynthesis was compromised. PMID:24040048

Production of Monomeric Aromatic Compounds from Oil Palm Empty Fruit Bunch Fiber Lignin by Chemical and Enzymatic Methods

PubMed Central

Tang, Pei-Ling; Hassan, Osman; Maskat, Mohamad Yusof; Badri, Khairiah

2015-01-01

In this study, oil palm empty fruit bunch (OPEFBF) was pretreated with alkali, and lignin was extracted for further degradation into lower molecular weight phenolic compounds using enzymes and chemical means. Efficiency of monomeric aromatic compounds production from OPEFBF lignin via chemical (nitrobenzene versus oxygen) and enzymatic [cutinase versus manganese peroxidase (MnP)] approaches was investigated. The effects of sodium hydroxide concentration (2, 5, and 10% wt.) and reaction time (30, 90, and 180 minutes) on the yield of aromatic compounds were studied. The results obtained indicated that nitrobenzene oxidation produced the highest yield (333.17 ± 49.44 ppm hydroxybenzoic acid, 5.67 ± 0.25 ppm p-hydroxybenzaldehyde, 25.57 ± 1.64 ppm vanillic acid, 168.68 ± 23.23 ppm vanillin, 75.44 ± 6.71 ppm syringic acid, 815.26 ± 41.77 ppm syringaldehyde, 15.21 ± 2.19 ppm p-coumaric acid, and 44.75 ± 3.40 ppm ferulic acid), among the tested methods. High sodium hydroxide concentration (10% wt.) was needed to promote efficient nitrobenzene oxidation. However, less severe oxidation condition was preferred to preserve the hydroxycinnamic acids (p-coumaric acid and ferulic acid). Cutinase-catalyzed hydrolysis was found to be more efficient than MnP-catalyzed oxidation in the production of aromatic compounds. By hydrolyzed 8% wt. of lignin with 0.625 mL cutinase g−1 lignin at pH 8 and 55°C for 24 hours, about 642.83 ± 14.45 ppm hydroxybenzoic acid, 70.19 ± 3.31 ppm syringaldehyde, 22.80 ± 1.04 ppm vanillin, 27.06 ± 1.20 ppm p-coumaric acid, and 50.19 ± 2.23 ppm ferulic acid were produced. PMID:26798644

Potential aromatic compounds as markers to differentiate between Tuber melanosporum and Tuber indicum truffles.

PubMed

Culleré, Laura; Ferreira, Vicente; Venturini, María E; Marco, Pedro; Blanco, Domingo

2013-11-01

The Tuber indicum (Chinese truffle) and Tuber melanosporum (Black truffle) species are morphologically very similar but their aromas are very different. The black truffle aroma is much more intense and complex, and it is consequently appreciated more gastronomically. This work tries to determine whether the differences between the aromatic compounds of both species are sufficiently significant so as to apply them to fraud detection. An olfactometric evaluation (GC-O) of T. indicum was carried out for the first time. Eight important odorants were identified. In order of aromatic significance, these were: 1-octen-3-one and 1-octen-3-ol, followed by two ethyl esters (ethyl isobutyrate and ethyl 2-methylbutyrate), 3-methyl-1-butanol, isopropyl acetate, and finally the two sulfides dimethyldisulfide (DMDS) and dimethylsulfide (DMS). A comparison of this aromatic profile with that of T. melanosporum revealed the following differences: T. indicum stood out for the significant aromatic contribution of 1-octen-3-one and 1-octen-3-ol (with modified frequencies (MF%) of 82% and 69%, respectively), while in the case of T. melanosporum both had modified frequencies of less than 30%. Ethyl isobutyrate, ethyl 2-methylbutyrate and isopropyl acetate were also significantly higher, while DMS and DMDS had low MF (30-40%) compared to T. melanosporum (>70%). The volatile profiles of both species were also studied by means of headspace solid-phase microextraction (HS-SPME-GC-MS). This showed that the family of C8 compounds (3-octanone, octanal, 1-octen-3-one, 3-octanol and 1-octen-3-ol) is present in T. indicum at much higher levels. The presence of 1-octen-3-ol was higher by a factor of about 100, while 1-octen-3-one was detected in T. indicum only (there was no chromatographic signal in T. melanosporum). As well as showing the greatest chromatographic differences, these two compounds were also the most powerful from the aromatic viewpoint in the T. indicum olfactometry. Therefore, either of the two chromatographic methods (GC-O or HS-SPME-GC-MS), together or separately, could be used as a screening technique to distinguish between T. indicum and T. melanosporum and thus avoid possible fraud. Copyright © 2013 Elsevier Ltd. All rights reserved.

Aromatic acids in a Eurasian Arctic ice core: a 2600-year proxy record of biomass burning

NASA Astrophysics Data System (ADS)

Grieman, Mackenzie M.; Aydin, Murat; Fritzsche, Diedrich; McConnell, Joseph R.; Opel, Thomas; Sigl, Michael; Saltzman, Eric S.

2017-04-01

Wildfires and their emissions have significant impacts on ecosystems, climate, atmospheric chemistry, and carbon cycling. Well-dated proxy records are needed to study the long-term climatic controls on biomass burning and the associated climate feedbacks. There is a particular lack of information about long-term biomass burning variations in Siberia, the largest forested area in the Northern Hemisphere. In this study we report analyses of aromatic acids (vanillic and para-hydroxybenzoic acids) over the past 2600 years in the Eurasian Arctic Akademii Nauk ice core. These compounds are aerosol-borne, semi-volatile organic compounds derived from lignin combustion. The analyses were made using ion chromatography with electrospray mass spectrometric detection. The levels of these aromatic acids ranged from below the detection limit (0.01 to 0.05 ppb; 1 ppb = 1000 ng L-1) to about 1 ppb, with roughly 30 % of the samples above the detection limit. In the preindustrial late Holocene, highly elevated aromatic acid levels are observed during three distinct periods (650-300 BCE, 340-660 CE, and 1460-1660 CE). The timing of the two most recent periods coincides with the episodic pulsing of ice-rafted debris in the North Atlantic known as Bond events and a weakened Asian monsoon, suggesting a link between fires and large-scale climate variability on millennial timescales. Aromatic acid levels also are elevated during the onset of the industrial period from 1780 to 1860 CE, but with a different ratio of vanillic and para-hydroxybenzoic acid than is observed during the preindustrial period. This study provides the first millennial-scale record of aromatic acids. This study clearly demonstrates that coherent aromatic acid signals are recorded in polar ice cores that can be used as proxies for past trends in biomass burning.

Enhancing muconic acid production from glucose and lignin-derived aromatic compounds via increased protocatechuate decarboxylase activity

DOE PAGES

Johnson, Christopher W.; Salvachua, Davinia; Khanna, Payal; ...

2016-04-22

The conversion of biomass-derived sugars and aromatic molecules to cis,cis-muconic acid (referred to hereafter as muconic acid or muconate) has been of recent interest owing to its facile conversion to adipic acid, an important commodity chemical. Metabolic routes to produce muconate from both sugars and many lignin-derived aromatic compounds require the use of a decarboxylase to convert protocatechuate (PCA, 3,4-dihydroxybenzoate) to catechol (1,2-dihydroxybenzene), two central aromatic intermediates in this pathway. Several studies have identified the PCA decarboxylase as a metabolic bottleneck, causing an accumulation of PCA that subsequently reduces muconate production. A recent study showed that activity of the PCAmore » decarboxylase is enhanced by co-expression of two genetically associated proteins, one of which likely produces a flavin-derived cofactor utilized by the decarboxylase. Using entirely genome-integrated gene expression, we have engineered Pseudomonas putida KT2440-derived strains to produce muconate from either aromatic molecules or sugars and demonstrate in both cases that co-expression of these decarboxylase associated proteins reduces PCA accumulation and enhances muconate production relative to strains expressing the PCA decarboxylase alone. In bioreactor experiments, co-expression increased the specific productivity (mg/g cells/h) of muconate from the aromatic lignin monomer p-coumarate by 50% and resulted in a titer of >15 g/L. In strains engineered to produce muconate from glucose, co-expression more than tripled the titer, yield, productivity, and specific productivity, with the best strain producing 4.92+/-0.48 g/L muconate. Furthermore, this study demonstrates that overcoming the PCA decarboxylase bottleneck can increase muconate yields from biomass-derived sugars and aromatic molecules in industrially relevant strains and cultivation conditions.« less

Effect of ZSM-5 acidity on aromatic product selectivity during upgrading of pine pyrolysis vapors

DOE PAGES

Engtrakul, Chaiwat; Mukarakate, Calvin; Starace, Anne K.; ...

2015-11-14

The impact of catalyst acidity on the selectivity of upgraded biomass pyrolysis products was studied by passing pine pyrolysis vapors over five ZSM-5 catalysts of varying acidity at 500 degrees C. The SiO 2-to-Al 2O 3 ratio (SAR) of the ZSM-5 zeolite was varied from 23 to 280 to control the acidity of the catalyst and the composition of upgraded products. The upgraded product stream was analyzed by GCMS. Additionally, catalysts were characterized using temperature programmed desorption, diffuse-reflectance FTIR spectroscopy, N 2 physisorption, and X-ray diffraction. The results showed that the biomass pyrolysis vapors were highly deoxygenated to form amore » slate of aromatic hydrocarbons over all of the tested ZSM-5 catalysts. As the overall acidity of the ZSM-5 increased the selectivity toward alkylated (substituted) aromatics (e.g., xylene, dimethyl-naphthalene, and methyl-anthracene) decreased while the selectivity toward unsubstituted aromatics (e.g., benzene, naphthalene, and anthracene) increased. Additionally, the selectivity toward polycyclic aromatic compounds (2-ring and 3-ring) increased as catalyst acidity increased, corresponding to a decrease in acid site spacing. The increased selectivity toward less substituted polycyclic aromatic compounds with increasing acidity is related to the relative rates of cyclization and alkylation reactions within the zeolite structure. As the acid site concentration increases and sites become closer to each other, the formation of additional cyclization products occurs at a greater rate than alkylated products. The ability to adjust product selectivity within 1-, 2-, and 3-ring aromatic families, as well as the degree of substitution, by varying ZSM-5 acidity could have significant benefits in terms creating a slate of upgraded biomass pyrolysis products to meet specific target market demands.« less

Polytetrafluoroethylene-jacketed stirrer modified with graphene oxide and polydopamine for the efficient extraction of polycyclic aromatic hydrocarbons.

PubMed

Zhang, Zinxin; Mwadini, Mwadini Ahmada; Chen, Zilin

2016-10-01

Steel stirrers jacketed with polytetrafluoroethylene can be regarded as an ideal substrate for stirrer bar sorptive extraction. However, it is still a great challenge to immobilize graphene onto a polytetrafluoroethylene stirrer due to the high chemical resistance of the surface of a polytetrafluoroethylene stirrer. We describe here a method to modify the surface of polytetrafluoroethylene stirrers with graphene. In this work, graphene was used as the sorbent due to its excellent adsorption capability for aromatic compounds, such as polycyclic aromatic compounds. Graphene was successfully immobilized onto polytetrafluoroethylene-stirrer by a bio-inspired polydopamine functionalization method. The graphene-modified polytetrafluoroethylene-stirrer shows good stability and tolerance to stirring, ultrasonication, strong acidic and basic solutions, and to organic solvents. The multilayer coating was characterized by scanning electronic microscopy and Fourier transform infrared spectroscopy. After the optimization of some experimental conditions, the graphene-modified polytetrafluoroethylene stirrer was used for the stirrer bar sorptive extraction of polycyclic aromatic hydrocarbons, in which the binding between the polycyclic aromatic hydrocarbons and the graphene layer was mainly based on π-π stacking and hydrophobic interactions. The graphene-modified polytetrafluoroethylene-stirrer-based stirrer bar sorptive extraction and high-performance liquid chromatography method was developed for the determination of polycyclic aromatic hydrocarbons with great extraction efficiency, with enrichment factors from 18 to 62. The method has low limits of detection of 1-5 pg/mL, wide linear range (5-100 and 10-200 pg/mL), good linearity (R ≥ 0.9957) and good reproducibility (RSD ≤ 6.45%). The proposed method has been applied to determine polycyclic aromatic hydrocarbons in real dust samples. Good recoveries were obtained, ranging from 88.53 to 109.43%. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Structural Enzymology of Iterative Aromatic Polyketide Synthases: A Critical Comparison with Fatty Acid Synthases.

PubMed

Tsai, Shiou-Chuan Sheryl

2018-06-20

Polyketides are a large family of structurally complex natural products including compounds with important bioactivities. Polyketides are biosynthesized by polyketide synthases (PKSs), multienzyme complexes derived evolutionarily from fatty acid synthases (FASs). The focus of this review is to critically compare the properties of FASs with iterative aromatic PKSs, including type II PKSs and fungal type I nonreducing PKSs whose chemical logic is distinct from that of modular PKSs. This review focuses on structural and enzymological studies that reveal both similarities and striking differences between FASs and aromatic PKSs. The potential application of FAS and aromatic PKS structures for bioengineering future drugs and biofuels is highlighted.

Optical spectra, electronic structure and aromaticity of benzannulated N-heterocyclic carbene and its analogues of the type C6H4(NR)2E: (E = Si, Ge, Sn, Pb).

PubMed

Aysin, Rinat R; Bukalov, Sergey S; Leites, Larissa A; Zabula, Alexander V

2017-07-11

A series of benzannulated N-heterocyclic compounds containing divalent 14 group atoms, C 6 H 4 (NR) 2 E II , E = C, Si, Ge, Sn, Pb, have been studied by various experimental (vibrational and UV-vis spectroscopy) and theoretical (NICS, ISE, ACID) techniques. The methods used confirm 10 π-electron delocalization (aromaticity) in these heterocycles, however, the aromaticity sequences estimated by the criteria based on different physical properties do not coincide.

Defining the role of a PACS technologist.

PubMed

Cabrera, Alfred

2002-01-01

As hospitals convert from conventional image processing to picture archiving and communication systems (PACS) technology, new job opportunities arose for PACS analysts, PACS system administrators, PACS operators, and PACS trainers. To support a PACS, these positions require education in computer information systems and work experience in information technology. At Texas Children's Hospital, new roles for radiologic technologists (RT) in supporting the operation of PACS were not recognized until after implementation of the filmless system. A new position entitled PACS technologis was created, but roles and responsibilities largely were undefined. The inadequate job description contributed to problems with appropriate utilization of the PACS technologist. The primary role of the technologist was nebulous, and the priority of tasks was undefined. There was an excessive volume of information and technology to be mastered. The role represented a new paradigm, so no template for the job description was available that encompassed the array of functions to be performed. The result was a "morph" of the RT and PACS analyst job descriptions that was contrived and unworkable. The role of the PACS technologist is vital to the operation of the radiology department that uses PACS. There is a well-established need for cross training of RTs in PACS. PACS technology is not taught in RT training programs. There are recurrent communications problems between RT and Information Technology (IT) personnel. The PACS technologist can participate in a number of activities that improve the overall level of proficiency in the imaging operation, such as specialized PACS training for RTs, collection and analysis of quality control data, and planning for installations of PACS acquisition modalities. RTs have acquired knowledge of medical terminology and human anatomy, imaging modalities, and workflow. These qualifications constitute a common basis for communication with other RTs, physicians, and other health care providers. In addition the appropriate candidate for PACS technologist should have computer software and hardware knowledge, interpersonal skills, oral and written communications skills, and analytical skills to troubleshoot issues. This report will describe the evolution of a more accurate job description for the PACS technologist, the relationship between the PACS technologist and the RT supervisor, and specific tasks are appropriate for the PACS technologist to perform.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ijam, M.J.; Qatami, S.Y.A.; Arif, S.F.

For several decades removal of aromatics from crude oil fractions (e.g. kerosene and lubricating oils) has been practiced in oil refining to produce fuels and lubricants of lower aromatic content and hence of improved quality. These aromatics are suitable raw materials for the manufacture of aromatic solvents, aromatic process oils, high octane gasoline, and as basic materials for making detergents, perfumes and dyes. Detailed study of molecular structure and substituent effects on the retention characteristics of aromatic hydrocarbons have been reported on alumina, silica and various chemically bonded silicas containing -C/sub 18/, -NH/sub 2/, -R(NH)/sub 2//sub 2/, -CN, RCN, RONmore » and phenyl-mercuric acetate for the compound class (ring-numbered) high performance liquid chromatography (2, 3, 8, 12, 24, 28). Previous work in this laboratory has demonstrated that individual normal and branched aliphatic hydrocarbons from kerosene and light gas oil were isolated and identified. This paper describes the extension of this work to cover the separation and identification of aromatic ring classes (mono-, di-, and tri-aromatics) in the gas oil fraction of Kuwait petroleum. Characterization and identification of the major components in the dinuclear aromatics is our primary objective in this study.« less

Cloning and expression profiling of the PacSnRK2 and PacPP2C gene families during fruit development, ABA treatment, and dehydration stress in sweet cherry.

PubMed

Shen, Xinjie; Guo, Xiao; Zhao, Di; Zhang, Qiang; Jiang, Yuzhuang; Wang, Yantao; Peng, Xiang; Wei, Yan; Zhai, Zefeng; Zhao, Wei; Li, Tianhong

2017-10-01

Plant SNF1-related protein kinase 2 (SnRK2) and protein phosphatase 2C (PP2C) family members are core components of the ABA signal transduction pathway. SnRK2 and PP2C proteins have been suggested to play crucial roles in fruit ripening and improving plant tolerance to drought stress, but supporting genetic information has been lacking in sweet cherry (Prunus avium L.). Here, we cloned six full-length SnRK2 genes and three full-length PP2C genes from sweet cherry cv. Hong Deng. Quantitative PCR analysis revealed that PacSnRK2.2, PacSnRK2.3, PacSnRK2.6, and PacPP2C1-3 were negatively regulated in fruits in response to exogenous ABA treatment, PacSnRK2.4 and PacSnRK2.5 were upregulated, and PacSnRK2.1 expression was not affected. The ABA treatment also significantly promoted the accumulation of anthocyanins in sweet cherry fruit. The expression of all PacSnRK2 and PacPP2C genes was induced by dehydration stress, which also promoted the accumulation of drought stress signaling molecules in the sweet cherry fruits, including ABA, soluble sugars, and anthocyanin. Furthermore, a yeast two-hybrid analysis demonstrated that PacPP2C1 interacts with all six PacSnRK2s, while PacPP2C3 does not interact with PacSnRK2.5. PacPP2C2 does not interact with PacSnRK2.1 or PacSnRK2.4. These results indicate that PacSnRK2s and PacPP2Cs may play a variety of roles in the sweet cherry ABA signaling pathway and the fruit response to drought stress. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Removal efficiency of polycyclic aromatic hydrocarbons and phthalate esters by surface flow wetland in Shunyi district, Beijing

NASA Astrophysics Data System (ADS)

Li, Binghua; Liu, Licai; Han, Li; Yang, Yong

2017-03-01

The surface flow wetland (SFW) system was located on Shunyi district, Beijing. It was built to treat industrial wastewater and domestic sewage, which were looked as its influent. Here sixteen polycyclic aromatic hydrocarbons (PAHs) and six phthalate esters (PAEs) were detected by gas chromatography-mass spectrometry (GC-MS).To determine treatment effect of SFW system, concentrations of targeted compounds in the influent were compared with those in the effluent. Results showed typical compounds of industrial wastewater were naphthalene (NAP), phenanthrene (PHE), dibutyl phthalate (DBP), di-(2-ethylhexyl) phthalate (DEHP), and their concentrations were ranged from 122.6 ng.L-1 to 760.6 ng.L-1. However typical compounds of domestic sewage were NAP, anthracene (ANT), PHE, DBP, diethyl phthalate (DEP), DEHP, and their concentrations were ranged from 280 ng.L-1 to 7998.1 ng.L-1. Typical compounds of effluent were NAP, PHE, DBP, DEHP, and their concentrations changed between 4.2 ng.L-1 and 1430.74 ng.L-1. The removal rate of those compounds were 10% ~ 99%, and nineteen compounds removal rate reached above 70%.Therefore, it can be concluded that SFW system had a strong effect on the removal of these compounds.

High-resolution mass spectrometry of nitrogenous compounds of the Colorado Green River formation oil shale.

NASA Technical Reports Server (NTRS)

Simoneit, B. R.; Schnoes, H. K.; Haug, P.; Burlingame, A. L.

1971-01-01

Basic nitrogenous compounds isolated from extracts of Green River Formation oil shale were analyzed. The major homologous constituents found were the compositional types - namely, quinolines, tetrahydrequinolines with minor amounts of pyridines and indoles series and traces of more aromatized nitrogen compounds. These results are correlated with nitrogen compounds isolated from Green River Formation retort oil and are a survey of the unaltered nitrogen compounds indigeneous to the shale.

Pyridine Group-Assisted Addition of Diazo-Compounds to Imines in the 3-CC Reaction of 2-Aminopyridines, Aldehydes, and Diazo-Compounds

PubMed Central

Gulevich, Anton V.; Helan, Victoria; Wink, Donald J.

2013-01-01

A novel three-component (3-CC) coupling reaction of 2-aminoazines, aromatic aldehydes and diazo-compounds producing polyfunctional β-amino-α-diazo-compounds has been developed. The reaction features an unprecedented heterocycle-assisted addition of a diazo-compound to an imine. The obtained diazoesters were efficiently converted into valuable heterocycles, as well as to β-amino acid derivatives. PMID:23373731

Effect of torrefaction on biomass structure and hydrocarbon production from fast pyrolysis

DOE PAGES

Neupane, Sneha; Adhikari, Sushil; Wang, Zhouhong; ...

2015-01-27

Torrefaction has been shown to improve the chemical composition of bio-oils produced from fast pyrolysis by lowering its oxygen content and enhancing the aromatic yield. A Py-GC/MS study was employed to investigate the effect of torrefaction temperatures (225, 250 and 275 °C) and residence times (15, 30 and 45 min) on product distribution from non-catalytic and H +ZSM-5 catalyzed pyrolysis of pinewood. During torrefaction, structural transformations in biomass constitutive polymers: hemicellulose, cellulose and lignin took place, which were evaluated using component analysis, solid state CP/MAS 13C NMR and XRD techniques. Torrefaction caused deacetylation and decomposition of hemicellulose, cleavage of arylmore » ether linkages and demethoxylation of lignin, degradation of cellulose and an overall increase in aromaticity of biomass, all of which affected the product yield from pyrolysis of torrefied biomass. For non-catalytic pyrolysis, selectivity of phenolic compounds increased with an increase in torrefaction severity while that of furan compounds decreased. In the case of catalytic pyrolysis, the sample torrefied at 225 °C-30 min and 250 °C-15 min resulted in a significant increase in aromatic hydrocarbon (HC) and also total carbon yield (approx. 1.6 times higher) as compared to catalytic pyrolysis of non-torrefied pine. Cleavage of aryl ether linkages and demethoxylation in lignin due to torrefaction caused increased yield of phenolic compounds, which in the presence of a catalyst were dehydrated to form aromatic HC.« less

Malaria parasite carbonic anhydrase: inhibition of aromatic/heterocyclic sulfonamides and its therapeutic potential

PubMed Central

Krungkrai, Sudaratana R; Krungkrai, Jerapan

2011-01-01

Plasmodium falciparum (P. falciparum) is responsible for the majority of life-threatening cases of human malaria, causing 1.5-2.7 million annual deaths. The global emergence of drug-resistant malaria parasites necessitates identification and characterization of novel drug targets and their potential inhibitors. We identified the carbonic anhydrase (CA) genes in P. falciparum. The pfCA gene encodes anα-carbonic anhydrase, a Zn2+-metalloenzme, possessing catalytic properties distinct from that of the human host CA enzyme. The amino acid sequence of the pfCA enzyme is different from the analogous protozoan and human enzymes. A library of aromatic/heterocyclic sulfonamides possessing a large diversity of scaffolds were found to be very good inhibitors for the malarial enzyme at moderate-low micromolar and submicromolar inhibitions. The structure of the groups substituting the aromatic-ureido- or aromatic-azomethine fragment of the molecule and the length of the parent sulfonamide were critical parameters for the inhibitory properties of the sulfonamides. One derivative, that is, 4- (3, 4-dichlorophenylureido)thioureido-benzenesulfonamide (compound 10) was the most effective in vitro Plasmodium falciparum CA inhibitor, and was also the most effective antimalarial compound on the in vitro P. falciparum growth inhibition. The compound 10 was also effective in vivo antimalarial agent in mice infected with Plasmodium berghei, an animal model of drug testing for human malaria infection. It is therefore concluded that the sulphonamide inhibitors targeting the parasite CA may have potential for the development of novel therapies against human malaria. PMID:23569766

Transition metal catalyzed manipulation of non-polar carbon–hydrogen bonds for synthetic purpose

PubMed Central

MURAI, Shinji

2011-01-01

The direct addition of ortho C–H bonds in various aromatic compounds such as ketones, esters, imines, imidates, nitriles, and aldehydes to olefins and acetylenes can be achieved with the aid of transition metal catalysts. The ruthenium catalyzed reaction is usually highly efficient and useful as a general synthetic method. The coordination to the metal center by a heteroatom in a directing group such as carbonyl and imino groups in aromatic compounds is the key step in this process. Mechanistically, the reductive elimination to form a C–C bond is the rate-determining step, while the C–H bond cleavage step is not. PMID:21558759

Luminescent Li-based metal-organic framework tailored for the selective detection of explosive nitroaromatic compounds: direct observation of interaction sites.

PubMed

Kim, Tae Kyung; Lee, Jae Hwa; Moon, Dohyun; Moon, Hoi Ri

2013-01-18

A luminescent lithium metal-organic framework (MOF) is constructed from the solvothermal reaction of Li(+) and a well-designed organic ligand, bis(4-carboxyphenyl)-N-methylamine (H(2)CPMA). A Li-based MOF can detect an explosive aromatic compound containing nitro groups as an explosophore, by showing a dramatic color change with concurrent luminescence quenching in the solid state. The detection sites are proven directly through single-crystal-to-single-crystal transformations, which show strong interactions between the aromatic rings of the electron-rich CPMA(2-) molecules and the electron-deficient nitrobenzene.

Hydrolates from lavender (Lavandula angustifolia)--their chemical composition as well as aromatic, antimicrobial and antioxidant properties.

PubMed

Prusinowska, Renata; Śmigielski, Krzysztof; Stobiecka, Agnieszka; Kunicka-Styczyńska, Alina

2016-01-01

It was shown that the method for obtaining hydrolates from lavender (Lavandula angustifolia) influences the content of active compounds and the aromatic, antimicrobial and antioxidant properties of the hydrolates. The content of volatile organic compounds ranged from 9.12 to 97.23 mg/100 mL of hydrolate. Lavender hydrolate variants showed low antimicrobial activity (from 0% to 0.05%). The radical scavenging activity of DPPH was from 3.6 ± 0.5% to 3.8 ± 0.6% and oxygen radical absorbance capacity (ORAC(FL)) results were from 0 to 266 μM Trolox equivalent, depending on the hydrolate variant.

Positron annihilation studies in solid substituted aromatic compounds

NASA Astrophysics Data System (ADS)

Oliveira, F. C.; Oliveira, A. M.; Donnici, C. L.; Machado, J. C.; Magalhães, W. F.; Windmöller, D.; Fulgêncio, F. H.; Souza, L. R.

2011-04-01

Positronium formation was investigated in benzene and naphthalene compounds with electron donating (sbnd NH2 and sbnd OH) and electron withdrawing (sbnd CN and sbnd NO2) substituents. The results exhibit an increase in the positronium formation yield whenever donating groups are bound to the ring and a decrease with withdrawing groups. These results can be attributed to the π-system electronic density variation in the aromatic ring. The amount of positronium obtained, I3 parameter, has been correlated with the Hammett (σ) and Brown-Okamoto (σp+) constants and adjusted through the modified Hammett equation, which employs the ratio I3/I3ϕ, yielding a satisfactory fit.

Mechanochemical synthesis and structural characterization of three novel cocrystals of dimethylglyoxime with N-heterocyclic aromatic compounds and acetamide

NASA Astrophysics Data System (ADS)

Abidi, Syed Sibte Asghar; Azim, Yasser; Gupta, Abhishek Kumar; Pradeep, Chullikkattil P.

2017-12-01

With an aim to explore the interactions of (RR'Cdbnd Nsbnd OH) oxime moiety of dimethylglyoxime (DMG) with pyridyl ring of N-heterocyclic aromatic compounds and acetamide, three novel cocrystals of dimethylglyoxime with acridine (ACR), 1,10-phenanthroline monohydrate (PT) and acetamide (ACT) are reported. These three cocrystals were obtained with a mechanochemical synthesis approach and were characterized by single crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), fourier transform-infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Additionally, Hirshfeld surface analysis is used to investigate the intermolecular interaction and the crystal packing of cocrystals.

Analysis of polycyclic aromatic hydrocarbons extracted from air particulate matter using a temperature programmable injector coupled to GC-C-IRMS.

PubMed

Mikolajczuk, Agnieszka; Przyk, Elzbieta Perez; Geypens, Benny; Berglund, Michael; Taylor, Philip

2010-03-01

Compound specific isotopic analysis (CSIA) can provide information about the origin of analysed compounds - in this case, polycyclic aromatic hydrocarbons (PAHs). In the study, PAHs were extracted from three dust samples: winter and summer filter dust and tunnel dust. The measurement was performed using the method validated in our laboratory using pure, solid compounds and EPA 610 reference assortment. CSIA required an appropriate clean-up method to avoid an unresolved complex in the gas chromatographic analysis usually found in the chromatography of PAHs. Extensive sample clean-up for this particular matrix was found to be necessary to obtain good gas chromatography-combustion-isotope ratio mass spectrometry analysis results. The sample purification method included two steps in which the sample is cleaned up and the aliphatic and aromatic hydrocarbons are separated. The concentration of PAHs in the measured samples was low; so a large volume injection technique (100 microl) was applied. The delta(VPDB)(13)C was measured with a final uncertainty smaller than 1 per thousand. Comparison of the delta(VPDB)(13)C signatures of PAHs extracted from different dust samples was feasible with this method and, doing so, significant differences were observed.

The Fermentative and Aromatic Ability of Kloeckera and Hanseniaspora Yeasts

NASA Astrophysics Data System (ADS)

Díaz-Montaño, Dulce M.; de Jesús Ramírez Córdova, J.

Spontaneous alcoholic fermentation from grape, agave and others musts into an alcoholic beverage is usually characterized by the presence of several non-Saccharomyces yeasts. These genera yeasts are dominant in the early stages of the alcoholic fermentation. However the genera Hanseniaspora and Kloeckera may survive at a significant level during fermentation and can influence the chemical composition of the beverage. Several strains belonging to the species Kloeckera api-culata and Hanseniaspora guilliermondii have been extensively studied in relation to the formation of some metabolic compounds affecting the bouquet of the final product. Indeed some apiculate yeast showed positive oenological properties and their use in the alcoholic fermentations has been suggested to enhance the aroma and flavor profiles. The non- Saccharomyces yeasts have the capability to produce and secrete enzymes in the medium, such as β -glucosidases, which release monoterpenes derived from their glycosylated form. These compounds contribute to the higher fruit-like characteristic of final product. This chapter reviews metabolic activity of Kloeckera and Hanseniaspora yeasts in several aspects: fermentative capability, aromatic compounds production and transformation of aromatic precursor present in the must, also covers the molecular methods for identifying of the yeast

Graphene stabilized ultra-small CuNi nanocomposite with high activity and recyclability toward catalysing the reduction of aromatic nitro-compounds.

PubMed

Fang, Hao; Wen, Ming; Chen, Hanxing; Wu, Qingsheng; Li, Weiying

2016-01-07

Nowadays, it is of great significance and a challenge to design a noble-metal-free catalyst with high activity and a long lifetime for the reduction of aromatic nitro-compounds. Here, a 2D structured nanocomposite catalyst with graphene supported CuNi alloy nanoparticles (NPs) is prepared, and is promising for meeting the requirements of green chemistry. In this graphene/CuNi nanocomposite, the ultra-small CuNi nanoparticles (∼2 nm) are evenly anchored on graphene sheets, which is not only a breakthrough in the structures, but also brings about an outstanding performance in activity and stability. Combined with a precise optimization of the alloy ratios, the reaction rate constant of graphene/Cu61Ni39 reached a high level of 0.13685 s(-1), with a desirable selectivity as high as 99% for various aromatic nitro-compounds. What's more, the catalyst exhibited a unprecedented long lifetime because it could be recycled over 25 times without obvious performance decay or even a morphology change. This work showed the promise and great potential of noble-metal-free catalysts in green chemistry.

A possible link between Balkan endemic nephropathy and the leaching of toxic organic compounds from Pliocene lignite by groundwater: Preliminary investigation

USGS Publications Warehouse

Orem, W.H.; Feder, G.L.; Finkelman, R.B.

1999-01-01

Balkan endemic nephropathy (BEN) is a fatal kidney disease that is known to occur only in clusters of villages in alluvial valleys of tributaries of the Danube River in Bulgaria, Romania, Yugoslavia, Bosnia, and Croatia. The confinement of this disease to a specific geographic area has led to speculation that an environmental factor may be involved in the etiology of BEN. Numerous environmental factors have been suggested as causative agents for producing BEN, including toxic metals in drinking water, metal deficiency in soils of BEN areas, and environmental mycotoxins to name a few. These hypotheses have either been disproved or have failed to conclusively demonstrate a connection to the etiology of BEN, or the clustering of BEN villages. In previous work, we observed a distinct geographic relationship between the distribution of Pliocene lignites in the Balkans and BEN villages. We hypothesized that the long-term consumption of well water containing toxic organic compounds derived from the leaching of nearby Pliocene lignites by groundwater was a primary factor in the etiology of BEN. In our current work, chemical analysis using 13C nuclear magnetic resonance (13CNMR) spectroscopy indicated a high degree of organic functionality in Pliocene lignite from the Balkans, and suggested that groundwater can readily leach organic matter from these coal beds. Semi-quantitative gas chromatography/mass spectroscopy analysis of solvent extracts of groundwater from shallow wells in BEN villages indicated the presence of potentially toxic aromatic compounds, such as napthalene, fluorene, phenanthrene, and pyrene at concentrations in the ppb range. Laboratory leaching of Balkan Pliocene lignites with distilled water yielded soluble organic matter (> 500 MW) containing large amounts of aromatic structures similar to the simple/discrete aromatic compounds detected in well water from BEN villages. These preliminary results are permissive of our hypothesis and suggest that further work on the possible relationship between the etiology of BEN and toxic aromatic substances leached from Pliocene lignites in well water is warranted.A distinct geographic relationship between the distribution of Pliocene lignites in the Balkans and villages where Balkan endemic nephropathy (BEN) occurs has been observed, indicating a possible link between BEN and the long-term consumption of well water containing toxic organic compounds derived from the leaching of nearby Pliocene lignites. Preliminary investigations by NMR spectroscopy, gas chromatography/mass spectroscopy and leaching experiments show a high degree of organic functionality in the Pliocene lignites, high-leachability by groundwater of organic matter from these beds, and the presence of toxic aromatic compounds.

Anomalous behavior of the magnetic hyperfine field at 140Ce impurities at La sites in LaMnSi2

NASA Astrophysics Data System (ADS)

Domienikan, C.; Bosch-Santos, B.; Cabrera-Pasca, G. A.; Saxena, R. N.; Carbonari, A. W.

2018-05-01

Magnetic hyperfine field has been measured in the orthorhombic intermetallic compound LaMnSi2 with perturbed angular correlation (PAC) spectroscopy using radioactive 140La(140Ce) nuclear probes. Magnetization measurements were also carried out in this compound with MPSM-SQUID magnetometer. Samples of LaMnSi2 compound were prepared by arc melting the component metals with high purity under argon atmosphere followed by annealing at 1000°C for 60 h under helium atmosphere and quenching in water. X-ray analysis confirmed the samples to be in a single phase with correct crystal structure expected for LaMnSi2 compound. The radioactive 140La (T1/2 = 40 h) nuclei were produced by direct irradiation of the sample with neutrons in the IEA-R1 nuclear research reactor at IPEN with a flux of ˜ 1013 n cm-2s-1 for about 3 - 4 min. The PAC measurements were carried out with a six BaF2 detector spectrometer at several temperatures between 10 K and 400 K. Temperature dependence of the hyperfine field, Bhf was found to be anomalous. A modified two-state model explained this anomalous behavior where the effective magnetic hyperfine field at 140Ce is believed to have two contributions, one from the unstable localized spins at Ce impurities and another from the magnetic Mn atoms of the host. The competition of these two contributions explains the anomalous behavior observed for the temperature dependence of the magnetic hyperfine field at 140Ce. The ferromagnetic transition temperature (TC) of LaMnSi2 was determined to be 400(1) K confirming the magnetic measurements.

Structure-Activity Relationships for Rates of Aromatic Amine Oxidation by Manganese Dioxide.

PubMed

Salter-Blanc, Alexandra J; Bylaska, Eric J; Lyon, Molly A; Ness, Stuart C; Tratnyek, Paul G

2016-05-17

New energetic compounds are designed to minimize their potential environmental impacts, which includes their transformation and the fate and effects of their transformation products. The nitro groups of energetic compounds are readily reduced to amines, and the resulting aromatic amines are subject to oxidation and coupling reactions. Manganese dioxide (MnO2) is a common environmental oxidant and model system for kinetic studies of aromatic amine oxidation. In this study, a training set of new and previously reported kinetic data for the oxidation of model and energetic-derived aromatic amines was assembled and subjected to correlation analysis against descriptor variables that ranged from general purpose [Hammett σ constants (σ(-)), pKas of the amines, and energies of the highest occupied molecular orbital (EHOMO)] to specific for the likely rate-limiting step [one-electron oxidation potentials (Eox)]. The selection of calculated descriptors (pKa, EHOMO, and Eox) was based on validation with experimental data. All of the correlations gave satisfactory quantitative structure-activity relationships (QSARs), but they improved with the specificity of the descriptor. The scope of correlation analysis was extended beyond MnO2 to include literature data on aromatic amine oxidation by other environmentally relevant oxidants (ozone, chlorine dioxide, and phosphate and carbonate radicals) by correlating relative rate constants (normalized to 4-chloroaniline) to EHOMO (calculated with a modest level of theory).

Three new constituents, latifolinal, latifolidin and cordicinol, from the fruits and leaves of Cordia latifolia.

PubMed

Siddiqui, Bina S; Perwaiz, Sobiya; Begum, Sabira; Ali, S Tariq

2010-01-01

Isolation and structure elucidation of three new natural constituents are reported. These include a new substituted furfuryl ester of stearic acid, latifolinal (1), and two aromatic compounds, latifolidin (2) and cordicinol (3). Compounds 1 and 2 were obtained from the dried fruits and compound 3 from the leaves of Cordia latifolia.

Organochlorines in surface soil at electronic-waste wire burning sites and metal contribution evaluated using quantitative X-ray speciation

NASA Astrophysics Data System (ADS)

Fujimori, Takashi; Takigami, Hidetaka; Takaoka, Masaki

2013-04-01

Heavy metals and toxic chlorinated aromatic compounds (aromatic-Cls) such as dioxins and polychlorinated biphenyls (PCBs) are found at high concentrations and persist in surface soil at wire burning sites (WBSs) in developing countries in which various wire cables are recycled to yield pure metals. Chlorine K-edge near-edge X-ray absorption fine structure (NEXAFS) is used to detect the specific chemical form of Cl and estimate its amount using a spectrum jump in the solid phase. Quantitative X-ray speciation of Cl was applied to study the mechanisms of aromatic-Cls formation in surface soil at WBSs in Southeast Asia. Relationships between aromatic-Cls and chlorides of heavy metals were evaluated because heavy metals are promoters of the thermochemical solid-phase formation of aromatic-Cls.

Air-water partition coefficients for a suite of polycyclic aromatic and other C10 through C20 unsaturated hydrocarbons.

PubMed

Rayne, Sierra; Forest, Kaya

2016-09-18

The air-water partition coefficients (Kaw) for 86 large polycyclic aromatic hydrocarbons and their unsaturated relatives were estimated using high-level G4(MP2) gas and aqueous phase calculations with the SMD, IEFPCM-UFF, and CPCM solvation models. An extensive method validation effort was undertaken which involved confirming that, via comparisons to experimental enthalpies of formation, gas-phase energies at the G4(MP2) level for the compounds of interest were at or near thermochemical accuracy. Investigations of the three solvation models using a range of neutral and ionic compounds suggested that while no clear preferential solvation model could be chosen in advance for accurate Kaw estimates of the target compounds, the employment of increasingly higher levels of theory would result in lower Kaw errors. Subsequent calculations on the polycyclic aromatic and unsaturated hydrocarbons at the G4(MP2) level revealed excellent agreement for the IEFPCM-UFF and CPCM models against limited available experimental data. The IEFPCM-UFF-G4(MP2) and CPCM-G4(MP2) solvation energy calculation approaches are anticipated to give Kaw estimates within typical experimental ranges, each having general Kaw errors of less than 0.5 log10 units. When applied to other large organic compounds, the method should allow development of a broad and reliable Kaw database for multimedia environmental modeling efforts on various contaminants.