Volatiles from the fungal microbiome of the marine sponge Callyspongia cf. flammea.

PubMed

Barra, Lena; Barac, Paul; König, Gabriele M; Crüsemann, Max; Dickschat, Jeroen S

2017-09-13

The volatiles emitted by five fungal strains previously isolated from the marine sponge Callyspongia cf. flammea were captured with a closed-loop stripping apparatus (CLSA) and analyzed by GC-MS. Besides several widespread compounds, a series of metabolites with interesting bioactivities were found, including the quorum sensing inhibitor protoanemonin, the fungal phytotoxin 3,4-dimethylpentan-4-olide, and the insect attractant 1,2,4-trimethoxybenzene. In addition, the aromatic polyketides isotorquatone and chartabomone that are both known from Eucalyptus and a new O-desmethyl derivative were identified. The biosynthesis of isotorquatone was studied by feeding experiments with isotopically labeled precursors and its absolute configuration was determined by enantioselective synthesis of a reference compound. Bioactivity testings showed algicidal activity for some of the identified compounds, suggesting a potential ecological function in sponge defence.

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.

De novo transcriptome assembly and identification of the gene conferring a "pandan-like" aroma in coconut (Cocos nucifera L.).

PubMed

Saensuk, Chatree; Wanchana, Samart; Choowongkomon, Kiattawee; Wongpornchai, Sugunya; Kraithong, Tippaya; Imsabai, Wachiraya; Chaichoompu, Ekawat; Ruanjaichon, Vinitchan; Toojinda, Theerayut; Vanavichit, Apichart; Arikit, Siwaret

2016-11-01

Thailand's aromatic coconut (Cocos nucifera L.) is a special type of green dwarf coconut, the liquid endosperm of which is characterized by a pleasant "pandan-like" aroma due to the presence of 2-acetyl-1-pyrroline (2AP). The aim of this study was to perform a de novo assembly of transriptome from C. nucifera endosperm and to identify the gene responsible for 2AP biosynthesis. CnAMADH2 was identified as an ortholog of the rice aromatic gene and a G-to-C substitution found in exon 14 was associated with 2AP content in the aromatic green dwarf coconut accessions. The base substitution caused an amino-acid change, alanine-to-proline, at position 442 (P442A). The presence of P at this position might alter the steric conformation at the loop region and subsequently result in an unstabilized dimer conformation that could lower AMADH enzyme activity. Among AMADH/BADH protein sequences in different plant species, the P442A mutation was found exclusively in aromatic coconut. The PCR marker developed based on this sequence variation can perfectly detect the aromatic and non-aromatic alleles of the gene. This study confirms the hypothesis that plants may share a mechanism of 2AP biosynthesis. This is the first identification of the gene associated with 2AP biosynthesis in a tree plant. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Increasing Signal Specificity of the TOL Network of Pseudomonas putida mt-2 by Rewiring the Connectivity of the Master Regulator XylR

PubMed Central

de las Heras, Aitor; Fraile, Sofia; de Lorenzo, Victor

2012-01-01

Prokaryotic transcription factors (TFs) that bind small xenobiotic molecules (e.g., TFs that drive genes that respond to environmental pollutants) often display a promiscuous effector profile for analogs of the bona fide chemical signals. XylR, the master TF for expression of the m-xylene biodegradation operons encoded in the TOL plasmid pWW0 of Pseudomonas putida, responds not only to the aromatic compound but also, albeit to a lesser extent, to many other aromatic compounds, such as 3-methylbenzylalcohol (3MBA). We have examined whether such a relaxed regulatory scenario can be reshaped into a high-capacity/high-specificity regime by changing the connectivity of this effector-sensing TF within the rest of the circuit rather than modifying XylR structure itself. To this end, the natural negative feedback loop that operates on xylR transcription was modified with a translational attenuator that brings down the response to 3MBA while maintaining the transcriptional output induced by m-xylene (as measured with a luxCDABE reporter system). XylR expression was then subject to a positive feedback loop in which the TF was transcribed from its own target promoters, each known to hold different input/output transfer functions. In the first case (xylR under the strong promoter of the upper TOL operon, Pu), the reporter system displayed an increased transcriptional capacity in the resulting network for both the optimal and the suboptimal XylR effectors. In contrast, when xylR was expressed under the weaker Ps promoter, the resulting circuit unmistakably discriminated m-xylene from 3MBA. The non-natural connectivity engineered in the network resulted both in a higher promoter activity and also in a much-increased signal-to-background ratio. These results indicate that the working regimes of given genetic circuits can be dramatically altered through simple changes in the way upstream transcription factors are self-regulated by positive or negative feedback loops. PMID:23071444

Tracking changes in composition and amount of dissolved organic matter throughout drinking water treatment plants by comprehensive two-dimensional gas chromatography-quadrupole mass spectrometry.

PubMed

Li, Chunmei; Wang, Donghong; Xu, Xiong; Xu, Meijia; Wang, Zijian; Xiao, Ruiyang

2017-12-31

Dissolved organic matter (DOM) can affect the performance of water treatment processes and produce undesirable disinfection by-products during disinfection. Several studies have been undertaken on the structural characterization of DOM, but its fate during drinking water treatment processes is still not fully understood. In this work, the nontargeted screening method of comprehensive two-dimensional gas chromatography-quadrupole mass spectrometry (GC×GC-qMS) was used to reveal the detailed changes of different chemical classes of compounds in DOM during conventional and advanced drinking water treatment processes at three drinking water treatment plants in China. The results showed that when the dissolved organic carbon removal was low, shifts in the DOM composition could not be detected with the specific ultraviolet absorbance at 254nm, but the changes were clear in the three-dimensional fluorescence excitation-emission matrix or GC×GC-qMS analyses. Coagulation-sedimentation processes selectively removed 37-59% of the nitrogenous compounds, alcohols and aromatic hydrocarbons but increased the concentrations of halogen-containing compounds by 17-26% because of the contact time with chlorine in this step. Filtration was less efficient at removing DOM but preferentially removed 21-60% of the acids. However, other organic matter would be released from the filter (e.g., nitrogenous compounds, acids, and aromatic hydrocarbons). Biological activated carbon (BAC) treatment removed most of the compounds produced from ozonation, particularly ketones, alcohols, halogen-containing compounds and acids. However, it should be noted that certain highly polar or high molecular weight compounds not identified in this study might be released from the BAC bed. After the whole treatment processes, the concentrations of nitrogenous compounds, alcohols, alkenes, aromatic hydrocarbons and ketones were decreased more by the advanced treatment processes than by the conventional treatment processes. Alcohol and ketone removals were probably related to the reduction in protein-like materials. Alkane removal was probably related to the reduction in fulvic acid-like and humic acid-like materials. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

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.

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

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.

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

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.

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.

Photochemical processes on Titan: Irradiation of mixtures of gases that simulate Titan's atmosphere

NASA Astrophysics Data System (ADS)

Tran, Buu N.; Joseph, Jeffrey C.; Force, Michael; Briggs, Robert G.; Vuitton, Veronique; Ferris, James P.

2005-09-01

Photochemical reaction pathways in Titan's atmosphere were investigated by irradiation of the individual components and the mixture containing nitrogen, methane, hydrogen, acetylene, ethylene, and cyanoacetylene. The quantum yields for the loss of the reactants and the formation of products were determined. Photolysis of ethylene yields mainly saturated compounds (ethane, propane, and butane) while photolysis of acetylene yields the same saturated compounds as well as ethylene and diacetylene. Irradiation of cyanoacetylene yields mainly hydrogen cyanide and small amounts of acetonitrile. When an amount of methane corresponding to its mixing ratio on Titan was added to these mixtures the quantum yields for the loss of reactants decreased and the quantum yields for hydrocarbon formation increased indicative of a hydrogen atom abstraction from methane by the photochemically generated radicals. GC/MS analysis of the products formed by irradiation of mixtures of all these gases generated over 120 compounds which were mainly aliphatic hydrocarbons containing double and triple bonds along with much smaller amounts of aromatic compounds like benzene, toluene and phenylacetylene. The reaction pathways were investigated by the use of 13C acetylene in these gas mixtures. No polycyclic aromatic compounds were detected. Vapor pressures of these compounds under conditions present in Titan's atmosphere were calculated. The low molecular weight compounds likely to be present in the atmosphere and aerosols of Titan as a result of photochemical processes are proposed.

A MIXTURE OF DIOXINS, FURANS, AND NON-ORTHO PCBS BASED UPON CONCENSUS TOXIC EQUIVLENCY FACTORS PRODUCES DIOXIN-LIKE REPRODUCTIVE EFFECTS

EPA Science Inventory

2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD; dioxin) and related polyhalogenated aromatic hydrocarbons (PHAHs) alter the reproductive development of laboratory animals. Therefore, we exposed animals to a mixture of dioxin and dioxin-like compounds including TCDD, 1,2,3,7,8-pentachl...

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

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

Emission of Volatile Compounds from Apple Plants Infested with Pandemis heparana Larvae, Antennal Response of Conspecific Adults, and Preliminary Field Trial.

PubMed

Giacomuzzi, Valentino; Cappellin, Luca; Khomenko, Iuliia; Biasioli, Franco; Schütz, Stefan; Tasin, Marco; Knight, Alan L; Angeli, Sergio

2016-12-01

This study investigated the volatile emission from apple (Malus x domestica Borkh., cv. Golden Delicious) foliage that was either intact, mechanically-damaged, or exposed to larval feeding by Pandemis heparana (Denis and Schiffermüller) (Lepidoptera: Tortricidae). Volatiles were collected by closed-loop-stripping-analysis and characterized by gas chromatography-mass spectrometry in three time periods: after 1 h and again 24 and 48 h later. Volatiles for all treatments also were monitored continuously over a 72-h period by the use of proton transfer reaction - time of flight-mass spectrometry (PTR-ToF-MS). In addition, the volatile samples were analyzed by gas chromatography-electroantennographic detection (GC-EAD) using male and female antennae of P. heparana. Twelve compounds were detected from intact foliage compared with 23 from mechanically-damaged, and 30 from P. heparana-infested foliage. Interestingly, six compounds were released only by P. heparana-infested foliage. The emission dynamics of many compounds measured by PTR-ToF-MS showed striking differences according to the timing of herbivory and the circadian cycle. For example, the emission of green leaf volatiles began shortly after the start of herbivory, and increased over time independently from the light-dark cycle. Conversely, the emission of terpenes and aromatic compounds showed a several-hour delay in response to herbivory, and followed a diurnal rhythm. Methanol was the only identified volatile showing a nocturnal rhythm. Consistent GC-EAD responses were found for sixteen compounds, including five aromatic ones. A field trial in Sweden demonstrated that benzyl alcohol, 2-phenylethanol, phenylacetonitrile, and indole lures placed in traps were not attractive to Pandemis spp. adults, but 2-phenylethanol and phenylacetonitrile when used in combination with acetic acid were attractive to both sexes.

Propensities of Aromatic Amino Acids versus Leucine and Proline to Induce Residual Structure in the Denatured State Ensemble of Iso-1-cytochrome c

PubMed Central

Finnegan, Michaela L.; Bowler, Bruce E.

2010-01-01

Histidine-heme loop formation in the denatured state of a protein is a sensitive means to probe for residual structure under unfolding conditions. In this study, we use a host-guest approach to investigate the relative tendencies of different amino acids to promote residual structure under denaturing conditions. The host for this work is a 6 amino acid insert of five alanines followed by a lysine engineered immediately following a unique histidine near the N-terminus of yeast iso-1-cytochrome c. We substitute the 4th alanine in this sequence, HAAAXAK, with X = Trp, Phe, Tyr and Leu. The effects of proline are tested with substitutions at positions 1 and 5 in the insert, HPAAAAK and HAAAAPK, respectively. Thermodynamic studies on His-heme loop formation in 3 M guanidine hydrochloride reveal significant stabilization of residual structure by aromatic amino acids, particularly, Trp and Phe, and minimal stabilization of residual structure by Leu. Prolines disfavor His-heme loop formation slightly, presumably due to enhanced chain stiffness. Kinetic studies reveal that much of the change in His-heme loop stability for the aromatic amino acids is caused by a slowing of the rate of His-heme loop breakage, indicating that residual structure is preferentially stabilized in the closed-loop form of the denatured state. PMID:20850458

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.

Phenylpropanoid, sapnol A, lignan and neolignan sophorosides, saposides A and B, isolated from Canadian sugar maple sap.

PubMed

Yoshikawa, Kazuko; Tani, Sakiko; Baba, Chihiro; Hashimoto, Toshihiro

2013-08-12

One new phenolic compound, sapnol A (1), and two new aromatic sophorosides, named saposides A (2) and B (3) were isolated from sugar maple sap. In addition, seven known phenolic compounds 4-10 were isolated. These structures were determined on the basis of NMR experiments as well as chemical evidence. Furthermore, all the isolated compounds 1-10 were tested for antioxidative activity by the superoxide dismutase (SOD)-like assay.

New analytical technique for establishing the quality of Soil Organic Matter affected by a wildfire. A first approach using Fourier transform ion cyclotron resonance mass spectrometry

NASA Astrophysics Data System (ADS)

Jiménez-Morillo, Nicasio T.; González-Pérez, José A.; Waggoner, Derek C.; Almendros, Gonzalo; González-Vila, Francisco J.; Hatcher, Patrick G.

2016-04-01

Introduction: Fire is one of the most important modulator factors of the environment and the forest. It is able to induce chemical and biological shifts and these, in turn, can alter the physical properties of soil. Generally, fire affects the most reactive fraction, soil organic matter (SOM) (González-Pérez et al., 2004) resulting in changes to several soil properties and functions. To study changes in SOM following a wildfire, researchers can count on several traditional as well as new analytical techniques. One of the most recently employed techniques is Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). This new powerful ultra-high resolution mass spectral technique, together with graphic interpretation tools such as van Krevelen diagrams (Kim et al, 2003), may be used to shed light on alterations caused by the burning of SOM. The objective of this research is to study fire impacts on SOM, using a sandy soil collected under a Cork oak (Quercus suber) in Doñana National Park, Southwest Spain. that was affected by a wildfire in August 2012. Methods: The impact of fire on SOM was studied in various different sieve fractions (coarse, 1-2 mm, and fine, <0.05 mm) collected in a burned area and an adjacent unburned control site with the same physiographic conditions. Alkaline extracts of SOM from each soil sample were examined using a Bruker Daltonics 12 Tesla Apex Qe FT-ICR-MS equipped with an Apollo II ESI ion source (operating in negative ion mode). The ESI voltages were optimized for each sample, and all spectra were internally calibrated following the procedure of (Sleighter and Hatcher, 2007), after which, peaks were assigned unique molecular formulas using a MatLab script written in house by Dr. Wassim Obeid of Old Dominion University. Results: The van Krevelen diagrams together with the relative intensity of each chemical compound, both obtained by FT-ICR-MS, allowed us to assess SOM quality for each sample and size fractions. The chemical compounds were grouped into the 7 main families; condensed aromatic compounds, unspecific aromatics, tannins, lignin, lipids, protein and carbohydrate derived. The unburnt SOM in the coarse fraction was mainly composed of compounds with a high intensity in the tannin-like, lignin-like and carbohydrate-like regions of the van Krevelen diagram, whereas the SOM in the fine fraction showed a high intensity in the lipid-like and protein-like regions. These results suggest that the SOM in the coarse fraction was less altered than that of the fine fraction; the latter believed to be subjected to higher microbial activity. We suggest that the observed changes occurs via a methylation process, producing a SOM that is highly humified (Jiménez-Morillo et al., 2014). The SOM in the coarse fraction affected by fire, showed a high relative intensity of chemical compounds in the carbohydrate-like and lignin-like regions, indicating the input of fresh organic matter. The presence of molecular formulas which plot in the aromatic and condensed aromatics regions also indicates that this fraction may have contributions from a second, more recalcitrant, organic carbon pool. The appearance of aromatic and condensed aromatic compounds could suggest that, in this fraction the fire induced condensation processes. In the burnt fine fraction, two different SOM sources of alteration could be identified; i) from microbial origin with high relative intensity of lipid-like and protein-like compounds and ii) fire origin with large amounts of condensed aromatic compounds and a high contribution from the carbohydrate-like compounds region. We suggest that these results indicate both, condensation processes yielding black carbon like materials and additions from the coarse fraction during fire mediated distillation process. Acknowledgements: This study is part of the results of the GEOFIRE Project (CGL2012-38655-C04-01) funded by the Spanish Ministry for Economy and Competitiveness. N.T Jiménez-Morillo is funded by a FPI research grant and EEBB 2015 research grant (BES-2013-062573 and EEBB-I-15-09334 respectively). In addition, we thank the large number of individuals in the Hatcher research group who contributed indirectly to the work presented here. References: González-Pérez JA, González-Vila FJ, Almendros G, Knicker H. 2004. The effect of fire on soil organic matter - a review. Environment International 30, 855-870. DOI:10.1016/j.envint.2004.02.003. Jiménez-Morillo NT, González-Pérez JA, Jordán A, Zavala LM, de la Rosa JM, Jiménez-González MA, González-Vila FJ. 2014. Organic matter fractions controlling soil water repellency in sandy soils from the Doñana National Park (Southwestern Spain). Land Degradation & Development. DOI: 10.1002/ldr.2314. Kim S, Kramer RW, and Hatcher PG. 2003. An informative graphical method for analysis of ultrahigh-resolution broadband mass spectra of natural organic matter - the van Krevelen diagram. Analytical Chemistry, 75: 5336-5344. DOI: 10.1021/ac034415p Sleighter RL, Hatcher PG. 2007. The application of electrospray ionization coupled to ultrahigh resolution mass spectrometry for the molecular characterization of natural organic matter. Journal of Mass Spectrometry. 2007; 42: 559-574. DOI: 10.1002/jms.1221

A TIME-TRENDS STUDY OF THE OCCURRENCES AND LEVELS OF CDDS, CDFS AND DIOXIN-LIKE PCBS IN SEDIMENT CORES FROM 11 GEOGRAPHICALLY DISTRIBUTED LAKES IN THE U.S.

EPA Science Inventory

Polychlorinated dibenzo-p-dioxins (CDDs), polychlorinated dibenzofurans (CDFs) and certain non- and mono-ortho substituted polychlorinated biphenyls (cp-PCBs) are a general class of chlorinated aromatic compounds that are considered as dioxin-like. Because these chemicals are hi...

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.

Selectivity of hexaphenylbenzene-based hydrocarbon stationary phase with propeller-like conformation for aromatic and aliphatic isomers.

PubMed

Yang, Yinhui; Chang, Zhengfeng; Yang, Xiaohong; Qi, Meiling; Wang, Jinliang

2018-08-03

Herein we report a propeller-like hexaphenylbenzene-based hydrocarbon material (denoted as BT) as the stationary phase for capillary gas chromatography (GC). The statically-coated BT capillary column showed a high column efficiency of 4340 plates m -1 and weak polarity. Owing to its unique conformation, π-electron toroidal delocalization and intrinsic microporosity, the BT stationary phase exhibited interesting selectivity for aromatic compounds over alkanes. Compared with the graphene (G) column, the BT column showed much prolonged retention and high selectivity for aromatic isomers, especially methylnaphthalenes, dimethylnaphthalenes and phenanthrene/anthracene, mainly because of its propeller-like conformation with rich intercalation effects. Moreover, it exhibited good column repeatability (intra-day, inter-day) and reproducibility (between-column) with RSD values on the retention times less than 0.08% for intra-day, 0.32% for inter-day and 3.8% for between-column, respectively. Also, it showed good potential for determination of minor isomer impurities in real samples. To the best of our knowledge, this work presents the first example of employing an neat aromatic hydrocarbon material as the GC stationary phase with high selectivity for analytes of a wide ranging polarity. Copyright © 2018 Elsevier B.V. All rights reserved.

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.

Electricity generation from food wastes and characteristics of organic matters in microbial fuel cell.

PubMed

Li, Hui; Tian, Yu; Zuo, Wei; Zhang, Jun; Pan, Xiaoyue; Li, Lipin; Su, Xinying

2016-04-01

The microbial fuel cell (MFC) was evaluated as an alternative way to recover electricity from canteen based food waste. Characteristics of the organics in food waste before and after the MFC treatment were analyzed to investigate how the organic matters were biodegraded and transformed during the MFC treatment. A maximum power density of 5.6W/m(3) and an average output voltage of 0.51V were obtained. During the MFC operation, the hydrophilic and acidic fractions were more readily degraded, compared to the neutral fractions. Additionally, aromatic compounds in the hydrophilic fraction were more preferentially removed than non-aromatic compounds. The MFC could easily remove the tryptophan protein-like substances in all fractions and aromatic proteins in hydrophilic and hydrophobic neutral fractions. Additionally, the hydrophobic amide-1 proteins and aliphatic components were readily hydrolyzed and biodegraded in the MFC. These findings may facilitate the pretreatment and posttreatment choices for MFC system fed with food waste. Copyright © 2016 Elsevier Ltd. All rights reserved.

A general strategy for synthesis of cyclophane-braced peptide macrocycles via palladium-catalysed intramolecular sp3 C-H arylation

NASA Astrophysics Data System (ADS)

Zhang, Xuekai; Lu, Gang; Sun, Meng; Mahankali, Madhu; Ma, Yanfei; Zhang, Mingming; Hua, Wangde; Hu, Yuting; Wang, Qingbing; Chen, Jinghuo; He, Gang; Qi, Xiangbing; Shen, Weijun; Liu, Peng; Chen, Gong

2018-05-01

New methods capable of effecting cyclization, and forming novel three-dimensional structures while maintaining favourable physicochemical properties are needed to facilitate the development of cyclic peptide-based drugs that can engage challenging biological targets, such as protein-protein interactions. Here, we report a highly efficient and generally applicable strategy for constructing new types of peptide macrocycles using palladium-catalysed intramolecular C(sp3)-H arylation reactions. Easily accessible linear peptide precursors of simple and versatile design can be selectively cyclized at the side chains of either aromatic or modified non-aromatic amino acid units to form various cyclophane-braced peptide cycles. This strategy provides a powerful tool to address the long-standing challenge of size- and composition-dependence in peptide macrocyclization, and generates novel peptide macrocycles with uniquely buttressed backbones and distinct loop-type three-dimensional structures. Preliminary cell proliferation screening of the pilot library revealed a potent lead compound with selective cytotoxicity toward proliferative Myc-dependent cancer cell lines.

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

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.

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.

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.

Light fluorous-tagged traceless one-pot synthesis of benzimidazoles facilitated by microwave irradiation.

PubMed

Tseng, Chih-Chung; Tasi, Cheng-Hsun; Sun, Chung-Ming

2012-06-01

A novel protocol for rapid assemble of benzimidazole framework has been demonstrated. This method incorporated with light fluorous-tag provides a convenient method for diversification of benzimidazoles and for easy purification via fluorous solid-phase extraction (F-SPE) in a parallel manner. The key transformation of this study involves in situ reduction of aromatic nitro compound, amide formation, cyclization and aromatization promoted by microwave irradiation in a one-pot fashion. The strategy is envisaged to be applied for the establishment of drug-like small molecule libraries for high throughput screening.

Synthesis and serotonergic activity of substituted 2, N-benzylcarboxamido-5-(2-ethyl-1-dioxoimidazolidinyl)-N, N-dimethyltryptamine derivatives: novel antagonists for the vascular 5-HT(1B)-like receptor.

PubMed

Moloney, G P; Martin, G R; Mathews, N; Milne, A; Hobbs, H; Dodsworth, S; Sang, P Y; Knight, C; Williams, M; Maxwell, M; Glen, R C

1999-07-15

The synthesis and vascular 5-HT(1B)-like receptor activity of a novel series of substituted 2, N-benzylcarboxamido-5-(2-ethyl-1-dioxoimidazolidinyl)-N, N-dimethyltryptamine derivatives are described. Modifications to the 5-ethylene-linked heterocycle and to substituents on the 2-benzylamide side chain have been explored. Several compounds were identified which exhibited affinity at the vascular 5-HT(1B)-like receptor of pK(B) > 7.0, up to 100-fold selectivity over alpha(1)-adrenoceptor affinity and 5-HT(2A) receptor affinity, and which exhibited a favorable pharmacokinetic profile. N-Benzyl-3-[2-(dimethylamino)ethyl]-5-[2-(4,4-dimethyl-2, 5-dioxo-1-imidazolidinyl)ethyl]-1H-indole-2-carboxamide (23) was identified as a highly potent, silent (as judged by the inability of angiotensin II to unmask 5-HT(1B)-like receptor-mediated agonist activity in the rabbit femoral artery), and competitive vascular 5-HT(1B)-like receptor antagonist with a plasma elimination half-life of approximately 4 h in dog plasma and with good oral bioavailability. The selectivity of compounds from this series for the vascular 5-HT(1B)-like receptors over other receptor subtypes is discussed as well as a proposed mode of binding to the receptor pharmacophore. It has been proposed that the aromatic ring of the 2, N-benzylcarboxamide group can occupy an aromatic binding site rather than the indole ring. The resulting conformation allows an amine-binding site to be occupied by the ethylamine nitrogen and a hydrogen-bonding site to be occupied by one of the hydantoin carbonyls. The electronic nature of the 2,N-benzylcarboxamide aromatic group as well as the size of substituents on this aromatic group is crucial for producing potent and selective antagonists. The structural requirement on the 3-ethylamine side chain incorporating the protonatable nitrogen is achieved by the bulky 2, N-benzylcarboxamide group and its close proximity to the 3-side chain.

Biomedical Applications Of Aromatic Azo Compounds: From Chromophore To Pharmacophore.

PubMed

Ali, Yousaf; Hamid, Shafida Abd; Rashid, Umer

2018-05-23

Azo dyes are widely used in textile, fiber, cosmetic, leather, paint and printing industries. Besides their characteristic coloring function, biological properties of certain azo compounds including antibacterial, antiviral, antifungal and cytotoxic are also reported. Azo compounds can be used as drug carriers, either by acting as a 'cargo' that entrap therapeutic agents or by prodrug approach. The drug is released by internal or external stimuli in the region of interest, as observed in colon-targeted drug delivery. Besides drug-like and drug carrier properties, a number of azo dyes are used in cellular staining to visualize cellular components and metabolic processes. However, the biological significance of azo compounds, especially in cancer chemotherapy, is still in its infancy. This may be linked to early findings that declared azo compounds as one of the possible causes of cancer and mutagenesis. Currently, researchers are screening the aromatic azo compounds for their potential biomedical use, including cancer diagnosis and therapy. The medical applications of azo compounds, particularly in cancer research are discussed. The biomedical significance of cis-trans interchange and negative implications of azo compounds are also highlighted in brief. This review may provide the researchers a platform in the quest of more potent therapeutic agents of this class. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

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.

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).

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.

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.

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.

Bromination of Aromatic Compounds by Residual Bromide in Sodium Chloride Matrix Modifier Salt During Heated Headspace GC/MS Analysis

EPA Science Inventory

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 rea...

A deeper analysis of the epitope/paratope of PLY-5, a mouse monoclonal antibody which recognises the conserved undecapeptide tryptophan-rich loop (ECTGLAWEWWR) of bacterial cholesterol-dependent cytolysins.

PubMed

González-Menéndez, Pedro; García-Ocaña, Marcos; de los Toyos, Juan R

2013-01-04

A previous study showed that the minimal epitope recognised by the PLY-5 mAb in the conserved undecapeptide Trp-rich loop of bacterial CDCs should consist of WEWWRT (Jacobs et al., 1999) [5]. Now, through immunoscreening of amino acid substitution analogues, it is concluded that the second Trp and the Arg residues are essential in the PLY-5 epitope. The E residue is an auxiliary epitope contributor. Antibody modelling and docking simulations provided support for these findings. For recognition by the antibody, the Trp-rich loop flipped out, mimicking the mechanism of membrane insertion. The displaced second Trp was seen to establish aromatic stacking interactions with aromatic residues of the antibody paratope and the notably extruded guanidium tip of the arginine residue mediated electrostatic interactions with well-exposed carboxylic groups of glutamic residues on the surface of the paratope. Thus, the epitope/paratope interaction is mainly mediated by aromatic and by ionic interactions. Copyright © 2012 Elsevier Inc. 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.

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

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.

Source and Biological Response of Biochar Organic Compounds Released into Water; Relationships with Bio-Oil Composition and Carbonization Degree.

PubMed

Ghidotti, Michele; Fabbri, Daniele; Mašek, Ondřej; Mackay, Colin Logan; Montalti, Marco; Hornung, Andreas

2017-06-06

Water-soluble organic compounds (WSOCs) were extracted from corn stalk biochar produced at increasing pyrolysis temperatures (350-650 °C) and from the corresponding vapors, collected as bio-oil. WSOCs were characterized by gas chromatography (semivolatile fraction), negative electron spray ionization high resolution mass spectrometry (hydrophilic fraction) and fluorescence spectroscopy. The pattern of semivolatile WSOCs in bio-oil was dominated by aromatic products from lignocellulose, while in biochar was featured by saturated carboxylic acids from hemi/cellulose and lipids with concentrations decreasing with decreasing H/C ratios. Hydrophilic species in poorly carbonized biochar resembled those in bio-oil, but the increasing charring intensity caused a marked reduction in the molecular complexity and degree of aromaticity. Differences in the fluorescence spectra were attributed to the predominance of fulvic acid-like structures in biochar and lignin-like moieties in bio-oil. The divergence between pyrolysis vapors and biochar in the distribution of WSOCs with increasing carbonization was explained by the hydrophobic carbonaceous matrix acting like a filter favoring the release into water of carboxylic and fulvic acid-like components. The formation of these structures was confirmed in biochar produced by pilot plant pyrolysis units. Biochar affected differently shoot and root length of cress seedlings in germination tests highlighting its complex role on plant growth.

Adsorptive behavior and solid-phase microextraction of bare stainless steel sample loop in high performance liquid chromatography.

PubMed

Zhang, Wenpeng; Zhang, Zixin; Meng, Jiawei; Zhou, Wei; Chen, Zilin

2014-10-24

In this work, we interestingly happened to observe the adsorption of stainless steel sample loop of HPLC. The adsorptive behaviors of the stainless steel loop toward different kinds of compounds were studied, including polycyclic aromatic hydrocarbons (PAHs), halogeno benzenes, aniline derivatives, benzoic acid derivatives, phenols, benzoic acid ethyl ester, benzaldehyde, 1-phenyl-ethanone and phenethyl alcohol. The adsorptive mechanism was probably related to hydrophobic interaction, electron-rich element-metal interaction and hydrogen bond. Universal adsorption of stainless steels was also testified. Inspired by its strong adsorptive capability, bare stainless steel loop was developed as a modification-free in-tube device for solid-phase microextraction (SPME), which served as both the substrate and sorbent and possessed ultra-high strength and stability. Great extraction efficiency toward PAHs was obtained by stainless steel loop without any modification, with enrichment factors of 651-834. By connecting the stainless steel loop onto a six-port valve, an online SPME-HPLC system was set up and an SPME-HPLC method has been validated for determination of PAHs. The method has exceptionally low limits of detection of 0.2-2pg/mL, which is significantly lower than that of reported methods with different kinds of sorbents. Wide linear range (0.5-500 and 2-1000pg/mL), good linearity (R(2)≥0.9987) and good reproducibility (RSD≤2.9%) were also obtained. The proposed method has been applied to determine PAHs in environmental samples. Good recoveries were obtained, ranging from 88.5% to 93.8%. Copyright © 2014 Elsevier B.V. All rights reserved.

Yellow phosphorus process to convert toxic chemicals to non-toxic products

DOEpatents

Chang, S.G.

1994-07-26

The present invention relates to a process for generating reactive species for destroying toxic chemicals. This process first contacts air or oxygen with aqueous emulsions of molten yellow phosphorus. This contact results in rapid production of abundant reactive species such as O, O[sub 3], PO, PO[sub 2], etc. A gaseous or liquid aqueous solution organic or inorganic chemicals is next contacted by these reactive species to reduce the concentration of toxic chemical and result in a non-toxic product. The final oxidation product of yellow phosphorus is phosphoric acid of a quality which can be recovered for commercial use. A process is developed such that the byproduct, phosphoric acid, is obtained without contamination of toxic species in liquids treated. A gas stream containing ozone without contamination of phosphorus containing species is also obtained in a simple and cost-effective manner. This process is demonstrated to be effective for destroying many types of toxic organic, or inorganic, compounds, including polychlorinated biphenyls (PCB), aromatic chlorides, amines, alcohols, acids, nitro aromatics, aliphatic chlorides, polynuclear aromatic compounds (PAH), dyes, pesticides, sulfides, hydroxyamines, ureas, dithionates and the like. 20 figs.

Yellow phosphorus process to convert toxic chemicals to non-toxic products

DOEpatents

Chang, Shih-Ger

1994-01-01

The present invention relates to a process for generating reactive species for destroying toxic chemicals. This process first contacts air or oxygen with aqueous emulsions of molten yellow phosphorus. This contact results in rapid production of abundant reactive species such as O, O.sub.3, PO, PO.sub.2, etc. A gaseous or liquid aqueous solution organic or inorganic chemicals is next contacted by these reactive species to reduce the concentration of toxic chemical and result in a non-toxic product. The final oxidation product of yellow phosphorus is phosphoric acid of a quality which can be recovered for commercial use. A process is developed such that the byproduct, phosphoric acid, is obtained without contamination of toxic species in liquids treated. A gas stream containing ozone without contamination of phosphorus containing species is also obtained in a simple and cost-effective manner. This process is demonstrated to be effective for destroying many types of toxic organic, or inorganic, compounds, including polychlorinated biphenyls (PCB), aromatic chlorides, amines, alcohols, acids, nitro aromatics, aliphatic chlorides, polynuclear aromatic compounds (PAH), dyes, pesticides, sulfides, hydroxyamines, ureas, dithionates and the like.

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.

[High-performance liquid-liquid chromatography in beverage analysis].

PubMed

Bricout, J; Koziet, Y; de Carpentrie, B

1978-01-01

Liquid liquid chromatography was performed with columns packed with stationary phases chemically bonded to silica microparticules. These columns show a high efficiency and are used very easily. Flavouring compounds like aromatic aldehydes which have a low volatility were analyzed in brandy using a polar phase alkylnitrile. Sapid substances like amarogentin in Gentiana lutea or glyryrrhizin in Glycyrrhiza glabra were determined by reversed phase chromatography. Finally ionizable substances like synthetic dyes can be analyzed by paired ion chromatography witha non polar stationary phase.

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.

Geogenic organic contaminants in the low-rank coal-bearing Carrizo-Wilcox aquifer of East Texas, USA

NASA Astrophysics Data System (ADS)

Chakraborty, Jayeeta; Varonka, Matthew; Orem, William; Finkelman, Robert B.; Manton, William

2017-06-01

The organic composition of groundwater along the Carrizo-Wilcox aquifer in East Texas (USA), sampled from rural wells in May and September 2015, was examined as part of a larger study of the potential health and environmental effects of organic compounds derived from low-rank coals. The quality of water from the low-rank coal-bearing Carrizo-Wilcox aquifer is a potential environmental concern and no detailed studies of the organic compounds in this aquifer have been published. Organic compounds identified in the water samples included: aliphatics and their fatty acid derivatives, phenols, biphenyls, N-, O-, and S-containing heterocyclic compounds, polycyclic aromatic hydrocarbons (PAHs), aromatic amines, and phthalates. Many of the identified organic compounds (aliphatics, phenols, heterocyclic compounds, PAHs) are geogenic and originated from groundwater leaching of young and unmetamorphosed low-rank coals. Estimated concentrations of individual compounds ranged from about 3.9 to 0.01 μg/L. In many rural areas in East Texas, coal strata provide aquifers for drinking water wells. Organic compounds observed in groundwater are likely to be present in drinking water supplied from wells that penetrate the coal. Some of the organic compounds identified in the water samples are potentially toxic to humans, but at the estimated levels in these samples, the compounds are unlikely to cause acute health problems. The human health effects of low-level chronic exposure to coal-derived organic compounds in drinking water in East Texas are currently unknown, and continuing studies will evaluate possible toxicity.

Structure-Activity Relationships for Rates of Aromatic Amine Oxidation by Manganese Dioxide

DOE PAGES

Salter-Blanc, Alexandra J.; Bylaska, Eric J.; Lyon, Molly A.; ...

2016-04-13

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 (MnO 2) is a common environmental oxidant and model system for kinetic studies of aromatic amine oxidation. Here 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 [Hammettmore » $$\\sigma$$ constants ($$\\sigma^-$$), pK as of the amines, and energies of the highest occupied molecular orbital (E HOMO)] to specific for the likely rate-limiting step [one-electron oxidation potentials (E ox)]. The selection of calculated descriptors (pK a), E HOMO, and E ox) 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 MnO 2 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 E HOMO (calculated with a modest level of theory).« less

Structure-Activity Relationships for Rates of Aromatic Amine Oxidation by Manganese Dioxide

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

Salter-Blanc, Alexandra J.; Bylaska, Eric J.; Lyon, Molly A.

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 (MnO 2) is a common environmental oxidant and model system for kinetic studies of aromatic amine oxidation. Here 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 [Hammettmore » $$\\sigma$$ constants ($$\\sigma^-$$), pK as of the amines, and energies of the highest occupied molecular orbital (E HOMO)] to specific for the likely rate-limiting step [one-electron oxidation potentials (E ox)]. The selection of calculated descriptors (pK a), E HOMO, and E ox) 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 MnO 2 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 E HOMO (calculated with a modest level of theory).« less

Fast detection of narcotics by single photon ionization mass spectrometry and laser ion mobility spectrometry

NASA Astrophysics Data System (ADS)

Laudien, Robert; Schultze, Rainer; Wieser, Jochen

2010-10-01

In this contribution two analytical devices for the fast detection of security-relevant substances like narcotics and explosives are presented. One system is based on an ion trap mass spectrometer (ITMS) with single photon ionization (SPI). This soft ionization technique, unlike electron impact ionization (EI), reduces unwanted fragment ions in the mass spectra allowing the clear determination of characteristic (usually molecular) ions. Their enrichment in the ion trap and identification by tandem MS investigations (MS/MS) enables the detection of the target substances in complex matrices at low concentrations without time-consuming sample preparation. For SPI an electron beam pumped excimer light source of own fabrication (E-Lux) is used. The SPI-ITMS system was characterized by the analytical study of different drugs like cannabis, heroin, cocaine, amphetamines, and some precursors. Additionally, it was successfully tested on-site in a closed illegal drug laboratory, where low quantities of MDMA could be directly detected in samples from floors, walls and lab equipments. The second analytical system is based on an ion mobility (IM) spectrometer with resonant multiphoton ionization (REMPI). With the frequency quadrupled Nd:YAG laser (266 nm), used for ionization, a selective and sensitive detection of aromatic compounds is possible. By application of suited aromatic dopants, in addition, also non-aromatic polar compounds are accessible by ion molecule reactions like proton transfer or complex formation. Selected drug precursors could be successfully detected with this device as well, qualifying it to a lower-priced alternative or useful supplement of the SPI-ITMS system for security analysis.

Fullerene-like chemistry at the interior carbon atoms of an alkene-centered C26H12 geodesic polyarene.

PubMed

Bronstein, Hindy E; Scott, Lawrence T

2008-01-04

The title compound (1) undergoes 1,2-addition reactions of both electrophilic and nucleophilic reagents preferentially at the "interior" carbon atoms of the central 6:6-bond to give fullerene-type adducts 2, 3, 4, and 5. Such fullerene-like chemistry is unprecedented for a topologically 2-dimensional polycyclic aromatic hydrocarbon and qualifies this geodesic polyarene as a "bridge" between the old flat world of polycyclic aromatic hydrocarbons (PAHs) and the new round world of fullerenes. The relief of pyramidalization strain, as in the addition reactions of fullerenes, presumably contributes to the atypical mode of reactivity seen in 1. Molecular orbital calculations, however, reveal features of the nonalternant pi system in 1 that may also play an important role. Thus, the fullerene-like chemistry of 1 may be driven by two or more factors, the relative importances of which are difficult to discern.

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.

Health risk assessment and personal exposure to Volatile Organic Compounds (VOCs) in metro carriages - A case study in Shanghai, China.

PubMed

Gong, Yu; Wei, Yijie; Cheng, Jinghui; Jiang, Tianyao; Chen, Ling; Xu, Bin

2017-01-01

Air pollution in transportation cabins has recently become a public concern. However, few studies assessed the exposure levels of suspected air pollutants including Volatile Organic Compounds (VOCs). This paper studied the exposure levels of in-carriage VOCs (benzene, toluene, ethylbenzene, xylene, styrene, formaldehyde, acetaldehyde, acetone and acrolein) in Shanghai, China and estimated the health risk in different conditions. The results indicated that VOCs concentrations in metro carriages varied from different train models, due to the difference in carriage size and ventilation system. The concentrations of aromatic VOCs in old metro carriage were 1-2 times higher than the new ones, as better paintings were used in new trains. Poor air circulation and ventilation in the underground track was likely to be the cause of higher VOCs levels (~10%) than the above-ground track. Lower aromatic compounds levels and higher carbonyls levels were observed in metro carriages at suburban areas than those at urban areas, likely due to less aromatic emission sources and more carbonyls emission sources in suburban areas. Acetone and acrolein were found to increase from 7.71 to 26.28μg/m 3 with number of commuters increasing from 40 to 200 in the carriages. According to the acceptable level proposed by the World Health Organization (1×10 -6 -1×10 -5 ), the life carcinogenic risk of commuters by subway (8.5×10 -6 -4.8×10 -5 ) was little above the acceptable level in Shanghai. Further application of our findings is possible to act as a reference in facilitating regulations for metro systems in other cities around world, so that in-carriage air quality might be improved. Copyright © 2016 Elsevier B.V. All rights reserved.

Organic superalkalis with closed-shell structure and aromaticity

NASA Astrophysics Data System (ADS)

Srivastava, Ambrish Kumar

2018-06-01

Benzene (C6H6) and polycyclic hydrocarbons such as naphthalene (C10H8), anthracene (C14H10) and coronene (C24H12) are well known aromatic organic compounds. We study the substitution of Li replacing all H-atoms in these hydrocarbons using density functional method. The vertical ionisation energy of such lithiated species, i.e. C6Li6, C10Li8, C14Li10 and C24Li12 ranges 4.24-4.50 eV, which is lower than the ionisation energy (IE) of Li atom. Thus, these species may behave as superalkalis due to their lower IE than alkali metal. However, these lithiated species possess planar and closed-shell structure, unlike typical superalkalis. Furthermore, all Li-substituted species are aromatic although their degree of aromaticity is reduced as compared to corresponding hydrocarbon analogues. We have further explored the structure of C6Li6 as star-like, unlike its inorganic analogue B3N3Li6, which appears as fan-like structure. We have also demonstrated that the interaction of C6Li6 with a superhalogen (such as BF4) is similar to that of a typical superalkali (such as OLi3). This may further suggest that the proposed lithiated species may form a new class of closed-shell organic superalkalis with aromaticity.

Molecular characterization of primary humic-like substances in fine smoke particles by thermochemolysis-gas chromatography-mass spectrometry

NASA Astrophysics Data System (ADS)

Fan, Xingjun; Wei, Siye; Zhu, Mengbo; Song, Jianzhong; Peng, Ping'an

2018-05-01

In this study, the molecular structures of primary humic-like substances (HULIS) in fine smoke particles emitted from the combustion of biomass materials (including rice straw, corn straw, and pine branches) and coal, and atmospheric HULIS were determined by off-line tetramethylammonium hydroxide thermochemolysis coupled with gas chromatography and mass spectrometry (TMAH-GC/MS). A total of 89 pyrolysates were identified by the thermochemolysis of primary and atmospheric HULIS. The main groups were polysaccharide derivatives, N-containing compounds, lignin derivatives, aromatic acid methyl ester, aliphatic acid methyl ester, and diterpenoid derivatives. Both the type and distribution of pyrolysates among primary HULIS were comparable to those in atmospheric HULIS. This indicates that primary HULIS from combustion processes are important contributors to atmospheric HULIS. Some distinct differences were also observed. The aromatic compounds, including lignin derivatives and aromatic acid methyl ester, were the major pyrolysates (53.0%-84.9%) in all HULIS fractions, suggesting that primary HULIS significantly contributed aromatic structures to atmospheric HULIS. In addition, primary HULIS from biomass burning (BB) contained a relatively high abundance of lignin and polysaccharide derivatives, which is consistent with the large amounts of lignin and cellulose structures contained in biomass materials. Aliphatic acid methyl ester and benzyl methyl ether were prominent pyrolysates in atmospheric HULIS. Moreover, some molecular markers of specific sources were obtained from the thermochemolysis of primary and atmospheric HULIS. For example, polysaccharide derivatives, pyridine and pyrrole derivatives, and lignin derivatives can be used as tracers of fresh HULIS emitted from BB. Diterpenoid derivatives are important markers of HULIS from pine wood combustion sources. Finally, the differences in pyrolysate types and the distributions between primary and atmospheric HULIS suggested that the primary HULIS would undergo many atmospheric processes to reconstruct the macromolecular organic matter in atmospheric aerosols.

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.

Emissions databases for polycyclic aromatic compounds in the Canadian Athabasca oil sands region - development using current knowledge and evaluation with passive sampling and air dispersion modelling data

NASA Astrophysics Data System (ADS)

Qiu, Xin; Cheng, Irene; Yang, Fuquan; Horb, Erin; Zhang, Leiming; Harner, Tom

2018-03-01

Two speciated and spatially resolved emissions databases for polycyclic aromatic compounds (PACs) in the Athabasca oil sands region (AOSR) were developed. The first database was derived from volatile organic compound (VOC) emissions data provided by the Cumulative Environmental Management Association (CEMA) and the second database was derived from additional data collected within the Joint Canada-Alberta Oil Sands Monitoring (JOSM) program. CALPUFF modelling results for atmospheric polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs, and dibenzothiophenes (DBTs), obtained using each of the emissions databases, are presented and compared with measurements from a passive air monitoring network. The JOSM-derived emissions resulted in better model-measurement agreement in the total PAH concentrations and for most PAH species concentrations compared to results using CEMA-derived emissions. At local sites near oil sands mines, the percent error of the model compared to observations decreased from 30 % using the CEMA-derived emissions to 17 % using the JOSM-derived emissions. The improvement at local sites was likely attributed to the inclusion of updated tailings pond emissions estimated from JOSM activities. In either the CEMA-derived or JOSM-derived emissions scenario, the model underestimated PAH concentrations by a factor of 3 at remote locations. Potential reasons for the disagreement include forest fire emissions, re-emissions of previously deposited PAHs, and long-range transport not considered in the model. Alkylated PAH and DBT concentrations were also significantly underestimated. The CALPUFF model is expected to predict higher concentrations because of the limited chemistry and deposition modelling. Thus the model underestimation of PACs is likely due to gaps in the emissions database for these compounds and uncertainties in the methodology for estimating the emissions. Future work is required that focuses on improving the PAC emissions estimation and speciation methodologies and reducing the uncertainties in VOC emissions which are subsequently used in PAC emissions estimation.

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

Detection of Aryl Hydrocarbon Receptor Activation by Some Chemicals in Food Using a Reporter Gene Assay

PubMed Central

Amakura, Yoshiaki; Tsutsumi, Tomoaki; Yoshimura, Morio; Nakamura, Masafumi; Handa, Hiroshi; Matsuda, Rieko; Teshima, Reiko; Watanabe, Takahiro

2016-01-01

The purpose of this study was to examine whether a simple bioassay used for the detection of dioxins (DXNs) could be applied to detect trace amounts of harmful DXN-like substances in food products. To identify substances with possible DXN-like activity, we assessed the ability of various compounds in the environment to bind the aryl hydrocarbon receptor (AhR) that binds specifically to DXNs. The compounds tested included 19 polycyclic aromatic hydrocarbons (PAHs), 20 PAH derivatives (nitrated, halogenated, and aminated derivatives), 23 pesticides, six amino acids, and eight amino acid metabolites. The AhR binding activities (AhR activity) of these compounds were measured using the chemical activated luciferase gene expression (CALUX) reporter gene assay system. The majority of the PAHs exhibited marked AhR activity that increased in a concentration-dependent manner. Furthermore, there was a positive link between AhR activity and the number of aromatic rings in the PAH derivatives. Conversely, there appeared to be a negative correlation between AhR activity and the number of chlorine residues present on halogenated PAH derivatives. However, there was no correlation between AhR activity and the number and position of substituents among nitrated and aminated derivatives. Among the pesticides tested, the indole-type compounds carbendazim and thiabendazole showed high levels of activity. Similarly, the indole compound tryptamine was the only amino acid metabolite to induce AhR activity. The results are useful in understanding the identification and characterization of AhR ligands in the CALUX assay. PMID:28231110

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.

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

Inhibition of Influenza H7 Hemagglutinin-Mediated Entry

PubMed Central

Antanasijevic, Aleksandar; Cheng, Han; Wardrop, Duncan J.; Rong, Lijun; Caffrey, Michael

2013-01-01

The recent outbreak of H7N9 influenza in China is of high concern to public health. H7 hemagglutinin (HA) plays a critical role in influenza entry and thus HA presents an attractive target for antivirals. Previous studies have suggested that the small molecule tert-butyl hydroquinone (TBHQ) inhibits the entry of influenza H3 HA by binding to the stem loop of HA and stabilizing the neutral pH conformation of HA, thereby disrupting the membrane fusion step. Based on amino acid sequence, structure and immunogenicity, H7 is a related Group 2 HA. In this work we show, using a pseudovirus entry assay, that TBHQ inhibits H7 HA-mediated entry, as well as H3 HA-mediated entry, with an IC50∼6 µM. Using NMR, we show that TBHQ binds to the H7 stem loop region. STD NMR experiments indicate that the aromatic ring of TBHQ makes extensive contact with the H7 HA surface. Limited proteolysis experiments indicate that TBHQ inhibits influenza entry by stabilizing the H7 HA neutral pH conformation. Together, this work suggests that the stem loop region of H7 HA is an attractive target for therapeutic intervention and that TBHQ, which is a widely used food preservative, is a promising lead compound. PMID:24194835

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

Polycyclic aromatic hydrocarbons in oysters and sediments from the Yatsushiro Sea, Japan: comparison of potential risks among PAHs, dioxins and dioxin-like compounds in benthic organisms.

PubMed

Nakata, Haruhiko; Uehara, Kiriko; Goto, Yuta; Fukumura, Miki; Shimasaki, Hideyuki; Takikawa, Kiyoshi; Miyawaki, Takashi

2014-01-01

Polycyclic aromatic hydrocarbons (PAHs) were analyzed in oysters collected from 18 stations in the Yatsushiro Sea, western Japan. PAHs were detected in all samples analyzed, and the highest concentration (mean 230 ng/g wet weight) was found in oysters from Tanoura Bay. The high molecular weight PAHs to low molecular weight PAHs ratios in oysters from Tanoura Bay were higher than at other stations. Sediment samples collected from 42 stations in Tanoura Bay were analyzed for PAHs to understand their concentrations and distribution. Higher concentrations were found in sediment samples at two stations in the southern inner bay (mean 30,200 ng/g dry weight), which were approximately two orders of magnitude higher than at a reference site. These observations strongly suggest severe contamination and significant sources of PAHs in Tanoura Bay. Dioxins and dioxin-like compounds (PCDFs, and non- and mono-ortho coplanar PCBs) were analyzed in sediments from eight stations in Tanoura Bay. The concentrations were comparable to, or lower than, at the reference sites, suggesting that there are no specific sources of these compounds in this bay. PAH, dioxins and dioxin-like compounds DR-CALUX relative potencies (REP) were applied to the sediment concentrations to evaluate the potential for toxicological effects on benthic organisms. PAHs made the highest contribution to the total REP concentration, supplying 99% of the total REP, followed by PCDDs (0.18%), PCDFs (0.04%), and PCBs (<0.001%). In this area, PAHs appear to be the most important Ah receptor binding chemicals for potential toxicity to benthic species. © 2013 Published by Elsevier Inc.

Bioremediation of PAH-contamined soils: Consequences on formation and degradation of polar-polycyclic aromatic compounds and microbial community abundance.

PubMed

Biache, Coralie; Ouali, Salma; Cébron, Aurélie; Lorgeoux, Catherine; Colombano, Stéfan; Faure, Pierre

2017-05-05

A bioslurry batch experiment was carried out over five months on three polycyclic aromatic compound (PAC) contaminated soils to study the PAC (PAH and polar-PAC) behavior during soil incubation and to evaluate the impact of PAC contamination on the abundance of microbial communities and functional PAH-degrading populations. Organic matter characteristics and reactivity, assessed through solvent extractable organic matter and PAC contents, and soil organic matter mineralization were monitored during 5 months. Total bacteria and fungi, and PAH-ring hydroxylating dioxygenase genes were quantified. Results showed that PAHs and polar-PACs were degraded with different degradation dynamics. Differences in degradation rates were observed among the three soils depending on PAH distribution and availability. Overall, low molecular weight compounds were preferentially degraded. Degradation selectivity between isomers and structurally similar compounds was observed which could be used to check the efficiency of bioremediation processes. Bacterial communities were dominant over fungi and were most likely responsible for PAC degradation. Abundance of PAH-degrading bacteria increased during incubations, but their proportion in the bacterial communities tended to decrease. The accumulation of some oxygenated-PACs during the bioslurry experiment underlines the necessity to monitor these compounds during application of remediation treatment on PAH contaminated soils. Copyright © 2017 Elsevier B.V. All rights reserved.

Geogenic organic contaminants in the low-rank coal-bearing Carrizo-Wilcox aquifer of East Texas, USA

USGS Publications Warehouse

Chakraborty, Jayeeta; Varonka, Matthew S.; Orem, William H.; Finkelman, Robert B.; Manton, William

2017-01-01

The organic composition of groundwater along the Carrizo-Wilcox aquifer in East Texas (USA), sampled from rural wells in May and September 2015, was examined as part of a larger study of the potential health and environmental effects of organic compounds derived from low-rank coals. The quality of water from the low-rank coal-bearing Carrizo-Wilcox aquifer is a potential environmental concern and no detailed studies of the organic compounds in this aquifer have been published. Organic compounds identified in the water samples included: aliphatics and their fatty acid derivatives, phenols, biphenyls, N-, O-, and S-containing heterocyclic compounds, polycyclic aromatic hydrocarbons (PAHs), aromatic amines, and phthalates. Many of the identified organic compounds (aliphatics, phenols, heterocyclic compounds, PAHs) are geogenic and originated from groundwater leaching of young and unmetamorphosed low-rank coals. Estimated concentrations of individual compounds ranged from about 3.9 to 0.01 μg/L. In many rural areas in East Texas, coal strata provide aquifers for drinking water wells. Organic compounds observed in groundwater are likely to be present in drinking water supplied from wells that penetrate the coal. Some of the organic compounds identified in the water samples are potentially toxic to humans, but at the estimated levels in these samples, the compounds are unlikely to cause acute health problems. The human health effects of low-level chronic exposure to coal-derived organic compounds in drinking water in East Texas are currently unknown, and continuing studies will evaluate possible toxicity.

The distribution and sources of polycyclic aromatic hydrocarbons in shallow groundwater from an alluvial-diluvial fan of the Hutuo River in North China

NASA Astrophysics Data System (ADS)

Wang, Jincui; Zhao, Yongsheng; Sun, Jichao; Zhang, Ying; Liu, Chunyan

2018-06-01

This paper has investigated the concentration and distribution of polycyclic aromatic hydrocarbons in shallow groundwater from an alluvial-diluvial fan of the Hutuo River in North China. Results show that the concentration levels of 16 priority polycyclic aromatic hydrocarbons range from 0 to 92.06 ng/L, do not conform to drinking water quality standards in China (GB 5749- 2006). However, the concentration figures of priority polycyclic aromatic hydrocarbons are much lower than that of other studies conducted elsewhere in China. In addition, highly-concentrated polycyclic aromatic hydrocarbons (50-92 ng/L) are fragmentarily distributed. The composition of polycyclic aromatic hydrocarbons from this study indicates that low molecular polycyclic aromatic hydrocarbons are predominant in groundwater samples, medium molecular compounds occur at low concentrations, and high molecular hydrocarbons are not detected. The polycyclic aromatic hydrocarbon composition in groundwater samples is basically the same as that of gaseous samples in the atmosphere in this study. Therefore, the atmospheric input is assumed to be an important source of polycyclic aromatic hydrocarbons, no less than wastewater discharge, adhesion on suspended solids, and surface water leakage. Ratios of specific polycyclic aromatic hydrocarbons demonstrate that they mainly originate from wood or coal combustion as well as natural gas and partially from petroleum according to the result of principal component analysis. On the whole, conclusions are drawn that the contamination sources of these polycyclic aromatic hydrocarbons are likely petrogenic and pyrolytic inputs. Future investigations by sampling topsoil, vadose soil, and the atmosphere can further verify aforementioned conclusions.

Analgesic-Like Activity of Essential Oil Constituents: An Update

PubMed Central

de Cássia da Silveira e Sá, Rita; Lima, Tamires Cardoso; da Nóbrega, Flávio Rogério; de Brito, Anna Emmanuela Medeiros

2017-01-01

The constituents of essential oils are widely found in foods and aromatic plants giving characteristic odor and flavor. However, pharmacological studies evidence its therapeutic potential for the treatment of several diseases and promising use as compounds with analgesic-like action. Considering that pain affects a significant part of the world population and the need for the development of new analgesics, this review reports on the current studies of essential oils’ chemical constituents with analgesic-like activity, including a description of their mechanisms of action and chemical aspects. PMID:29232831

Content of polyphenol compound in mangrove and macroalga extracts

NASA Astrophysics Data System (ADS)

Takarina, N. D.; Patria, M. P.

2017-07-01

Polyphenol or phenolic are compounds containing one or more hydroxyl group of the aromatic ring [1]. These compounds have some activities like antibacterial, antiseptic, and antioxidants. Natural resources like mangrove and macroalga were known containing these compounds. The purpose of the research was to investigate polyphenol content in mangrove and macroalga. Materials used in this research were mangrove (Avicennia sp.) leaves and the whole part of macroalga (Caulerpa racemosa). Samples were dried for 5 days then macerated in order to get an extract. Maceration were done using methanol for 48 hours (first) and 24 hours (second) continously. Polyphenol content was determined using phytochemical screening on both extracts. The quantitative test was carried out to determine catechin and tannin as polyphenol compound. The result showed that catechin was observed in both extracts while tannin in mangrove extract only. According to quantitative test, mangrove has a higher content of catechin and tannin which were 12.37-13.44 % compared to macroalga which was 2.57-4.58 %. Those indicated that both materials can be the source of polyphenol compound with higher content on mangrove. Moreover, according to this result, these resources can be utilized for advanced studies and human needs like medical drug.

Creosote released from railway-ties recycled and the sanitary risks.

PubMed

Zicari, Giuseppe; Allegro, Giuseppe; Russo, Domenico; Rivetti, Daniela; Soardo, Vincenzo; Cerrato, Elena

2013-01-01

Through the history of railways, wooden crossties impregnated with potentially hazardous creosote tar, have been used for years. There are six major classes of compounds in the creosote: aromatic hydrocarbons; tar acids/phenolics; tar bases/nitrogen-containing heterocycles; aromatic amines; sulfur-containing heterocycles; and oxygen-containing heterocycles. The creosote molecules applied in railway crossties can be released in the environment and they can bioaccumulate in animals and vegetables. Some constituents (benzo(a)pyrene and phenolics like benzene) are considered as being carcinogenic which renders the entire complex of creosote to be classified as potentially carcinogenic. After several decades of use the railway-ties are been recycled for varies uses like fences, stakes for agriculture and fruit production or bank protection. In this paper are examined some environmental and sanitary risks from wood impregnated with creosote reported in the literature.

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

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.

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.

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.

Metabolic Engineering of the Shikimate Pathway for Production of Aromatics and Derived Compounds—Present and Future Strain Construction Strategies

PubMed Central

Averesch, Nils J. H.; Krömer, Jens O.

2018-01-01

The aromatic nature of shikimate pathway intermediates gives rise to a wealth of potential bio-replacements for commonly fossil fuel-derived aromatics, as well as naturally produced secondary metabolites. Through metabolic engineering, the abundance of certain intermediates may be increased, while draining flux from other branches off the pathway. Often targets for genetic engineering lie beyond the shikimate pathway, altering flux deep in central metabolism. This has been extensively used to develop microbial production systems for a variety of compounds valuable in chemical industry, including aromatic and non-aromatic acids like muconic acid, para-hydroxybenzoic acid, and para-coumaric acid, as well as aminobenzoic acids and aromatic α-amino acids. Further, many natural products and secondary metabolites that are valuable in food- and pharma-industry are formed outgoing from shikimate pathway intermediates. (Re)construction of such routes has been shown by de novo production of resveratrol, reticuline, opioids, and vanillin. In this review, strain construction strategies are compared across organisms and put into perspective with requirements by industry for commercial viability. Focus is put on enhancing flux to and through shikimate pathway, and engineering strategies are assessed in order to provide a guideline for future optimizations. PMID:29632862

Evaluating Activated Carbon Adsorption of Dissolved Organic Matter and Micropollutants Using Fluorescence Spectroscopy.

PubMed

Shimabuku, Kyle K; Kennedy, Anthony M; Mulhern, Riley E; Summers, R Scott

2017-03-07

Dissolved organic matter (DOM) negatively impacts granular activated carbon (GAC) adsorption of micropollutants and is a disinfection byproduct precursor. DOM from surface waters, wastewater effluent, and 1 kDa size fractions were adsorbed by GAC and characterized using fluorescence spectroscopy, UV-absorption, and size exclusion chromatography (SEC). Fluorescing DOM was preferentially adsorbed relative to UV-absorbing DOM. Humic-like fluorescence (peaks A and C) was selectively adsorbed relative to polyphenol-like fluorescence (peaks T and B) potentially due to size exclusion effects. In the surface waters and size fractions, peak C was preferentially removed relative to peak A, whereas the reverse was found in wastewater effluent, indicating that humic-like fluorescence is associated with different compounds depending on DOM source. Based on specific UV-absorption (SUVA), aromatic DOM was preferentially adsorbed. The fluorescence index (FI), if interpreted as an indicator of aromaticity, indicated the opposite but exhibited a strong relationship with average molecular weight, suggesting that FI might be a better indicator of DOM size than aromaticity. The influence of DOM intermolecular interactions on adsorption were minimal based on SEC analysis. Fluorescence parameters captured the impact of DOM size on the fouling of 2-methylisoborneol and warfarin adsorption and correlated with direct competition and pore blockage indicators.

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

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.

Discovery of biaryl-4-carbonitriles as antihyperglycemic agents that may act through AMPK-p38 MAPK pathway.

PubMed

Goel, Atul; Nag, Pankaj; Rahuja, Neha; Srivastava, Rohit; Chaurasia, Sumit; Gautam, Sudeep; Chandra, Sharat; Siddiqi, Mohammad Imran; Srivastava, Arvind K

2014-08-25

A series of functionalized biaryl-4-carbonitriles was synthesized in three steps and evaluated for PTP-1B inhibitory activity. Among the synthesized compounds, four biaryls 6a-d showed inhibition (IC50 58-75 μM) against in vitro PTP-1B assay possibly due to interaction with amino acid residues Lys120, Tyr46 through hydrogen bonding and aromatic-aromatic interactions, respectively. Two biaryl-4-carbonitriles 6b and 6c showed improved glucose tolerance, fasting as well as postprandial blood glucose, serum total triglycerides, and increased high-density lipoprotein-cholesterol in SLM, STZ, STZ-S and C57BL/KsJ-db/db animal models. The bioanalysis of 4'-bromo-2,3-dimethyl-5-(piperidin-1-yl)biphenyl-4-carbonitrile (6b) revealed that like insulin, it increased 2-deoxyglucose uptake in skeletal muscle cells (L6 and C2C12 myotubes). The compound 6b significantly up-regulated the genes related to the insulin signaling pathways like AMPK, MAPK including glucose transporter-4 (GLUT-4) gene in muscle tissue of C57BL/KsJ-db/db mice. Furthermore, it was observed that the compound 6b up-regulated PPARα, UCP2 and HNF4α, which are key regulator of glucose, lipid, and fatty acid metabolism. Western blot analysis of the compound 6b showed that it significantly increased the phosphorylation of AMPK and p38 MAPK and ameliorated glucose uptake in C57BL/KsJ-db/db mice through the AMPK-p38 MAPK pathway. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

Shift in the chemical composition of dissolved organic matter in the Congo River network

NASA Astrophysics Data System (ADS)

Lambert, Thibault; Bouillon, Steven; Darchambeau, François; Massicotte, Philippe; Borges, Alberto V.

2016-09-01

The processing of terrestrially derived dissolved organic matter (DOM) during downstream transport in fluvial networks is poorly understood. Here, we report a dataset of dissolved organic carbon (DOC) concentrations and DOM composition (stable carbon isotope ratios, absorption and fluorescence properties) acquired along a 1700 km transect in the middle reach of the Congo River basin. Samples were collected in the mainstem and its tributaries during high-water (HW) and falling-water (FW) periods. DOC concentrations and DOM composition along the mainstem were found to differ between the two periods because of a reduced lateral mixing between the central water masses of the Congo River and DOM-rich waters from tributaries and also likely because of a greater photodegradation during FW as water residence time (WRT) increased. Although the Cuvette Centrale wetland (one of the world's largest flooded forests) continuously releases highly aromatic DOM in streams and rivers of the Congo Basin, the downstream transport of DOM was found to result in an along-stream gradient from aromatic to aliphatic compounds. The characterization of DOM through parallel factor analysis (PARAFAC) suggests that this transition results from (1) the losses of aromatic compounds by photodegradation and (2) the production of aliphatic compounds by biological reworking of terrestrial DOM. Finally, this study highlights the critical importance of the river-floodplain connectivity in tropical rivers in controlling DOM biogeochemistry at a large spatial scale and suggests that the degree of DOM processing during downstream transport is a function of landscape characteristics and WRT.

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.

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.

Characterization of the major fragance gene from an aromatic japonica rice and analysis of its diversity in Asian cultivated rice

PubMed Central

Bourgis, F.; Guyot, R.; Gherbi, H.; Tailliez, E.; Amabile, I.; Salse, J.; Lorieux, M.; Delseny, M.

2008-01-01

In Asian cultivated rice (Oryza sativa L.), aroma is one of the most valuable traits in grain quality and 2-ACP is the main volatile compound contributing to the characteristic popcorn-like odour of aromatic rices. Although the major locus for grain fragrance (frg gene) has been described recently in Basmati rice, this gene has not been characterised in true japonica varieties and molecular information available on the genetic diversity and evolutionary origin of this gene among the different varieties is still limited. Here we report on characterisation of the frg gene in the Azucena variety, one of the few aromatic japonica cultivars. We used a RIL population from a cross between Azucena and IR64, a non-aromatic indica, the reference genomic sequence of Nipponbare (japonica) and 93–11 (indica) as well as an Azucena BAC library, to identify the major fragance gene in Azucena. We thus identified a betaine aldehyde dehydrogenase gene, badh2, as the candidate locus responsible for aroma, which presented exactly the same mutation as that identified in Basmati and Jasmine-like rices. Comparative genomic analyses showed very high sequence conservation between Azucena and Nipponbare BADH2, and a MITE was identified in the promotor region of the BADH2 allele in 93–11. The badh2 mutation and MITE were surveyed in a representative rice collection, including traditional aromatic and non-aromatic rice varieties, and strongly suggested a monophylogenetic origin of this badh2 mutation in Asian cultivated rices. Altogether these new data are discussed here in the light of current hypotheses on the origin of rice genetic diversity. PMID:18491070

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.

Synthesis, spectroscopic characterization, antimicrobial evaluation and molecular docking study of novel triazine-quinazolinone based hybrids

NASA Astrophysics Data System (ADS)

Dinari, Mohammad; Gharahi, Fateme; Asadi, Parvin

2018-03-01

A new series of 1,3,5-triazine incorporating aromatic quinazolinone moieties as a potential antimicrobial agents is reported. The first chlorine group of the cyanuric chloride (1) was replaced by aniline and the second one was replaced by various aromatic amines. The prepared monochlorotriazine was allowed to react with hydrazine and subsequently it was reacted with 2-methyl-4H-benzo[1,3]oxazin-4-one to obtain novel triazine-quinazolinone based hybrids (9a-f). The chemical structure and purity of the hybrid compounds were evaluated by different techniques such as thin layer chromatography, melting point, Fourier-transform infrared (FTIR), 1H and 13C NMR spectra and elemental analysis. Antimicrobial activity of the hybrid compounds were study by three Gram-negative bacteria (Salmonella entritidis, Escherichia coli, Pseudomonas aeruginosa) and three Gram-positive bacteria (Staphylococcus aureus, Listeria monocitogenes, Bacillus subtilis) as well as Candida albicansas a yeast-like fungus using the serial broth dilution method. Among them, compound 9d with benzenesulfonamide group showed higher antimicrobial activity with a minimum inhibitory concentration (MIC) value of 16 μg/mL. Furthermore, compounds 5d, 9a and 9b showed good activity against several tested strains. In addition, docking simulation was perform to position best antibacterial compounds in to the S. aureus dihydrofolate reductase (DHFR) active site to determine the probable binding conformations.

Evolution of interstellar organic compounds under asteroidal hydrothermal conditions

NASA Astrophysics Data System (ADS)

Vinogradoff, V.; Bernard, S.; Le Guillou, C.; Remusat, L.

2018-05-01

Carbonaceous chondrites (CC) contain a diversity of organic compounds. No definitive evidence for a genetic relationship between these complex organic molecules and the simple organic molecules detected in the interstellar medium (ISM) has yet been reported. One of the many difficulties arises from the transformations of organic compounds during accretion and hydrothermal alteration on asteroids. Here, we report results of hydrothermal alteration experiments conducted on a common constituent of interstellar ice analogs, Hexamethylenetetramine (HMT - C6H12N4). We submitted HMT to asteroidal hydrothermal conditions at 150 °C, for various durations (up to 31 days) and under alkaline pH. Organic products were characterized by gas chromatography mass spectrometry, infrared spectroscopy and synchrotron-based X-ray absorption near edge structure spectroscopy. Results show that, within a few days, HMT has evolved into (1) a very diverse suite of soluble compounds dominated by N-bearing aromatic compounds (> 150 species after 31 days), including for instance formamide, pyridine, pyrrole and their polymers (2) an aromatic and N-rich insoluble material that forms after only 7 days of experiment and then remains stable through time. The reaction pathways leading to the soluble compounds likely include HMT dissociation, formose and Maillard-type reactions, e.g. reactions of sugar derivatives with amines. The present study demonstrates that, if interstellar organic compounds such as HMT had been accreted by chondrite parent bodies, they would have undergone chemical transformations during hydrothermal alteration, potentially leading to the formation of high molecular weight insoluble organic molecules. Some of the diversity of soluble and insoluble organic compounds found in CC may thus result from asteroidal hydrothermal alteration.

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.

Facilitated and selective oxidation of thiophenic sulfur compounds using MoOx/Al₂O₃-H₂O₂ system under ultrasonic irradiation.

PubMed

Akbari, Azam; Omidkhah, Mohammadreza; Towfighi Darian, Jafar

2015-03-01

Oxidative desulfurization of thiophenic sulfur compounds of benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyl dibenzothiophene (4,6-DMDBT) with MoOx/Al₂O₃ catalyst and H₂O₂ oxidant has been facilitated and more selective under ultrasonic irradiation. The catalyst with the optimum 10% of Mo loading consisted of isolated tetrahedral molybdenum oxide species based on FTIR analysis. The increase of Mo loading to 15% and 20% caused to generation of polymolybdate and MoO₃ crystals which decreased desulfurization activity. Sonication enhanced the apparent reaction rate constants in oxidation of all three sulfur compounds. An increase in the Arrhenius factor (A0), which is the total number of collisions per second, could explain the acceleration in the rate constants by sonication. The apparent activated energy (Ea) of BT oxidation was reduced from 96.6 to 75.3 kJ/mol by using ultrasound. This indicated that ultrasound had also a chemical effect, like a catalytic influence, in the acceleration of BT removal. DBT oxidation was reduced when investigated in the presence of tetralin, naphthalene and 2-methyl naphthalene as the model aromatic compounds of actual light oils. A higher selectivity toward DBT elimination in the presence of aromatics was obtained by sonication when compared with the silent treatment. Ultrasound cleaned the catalyst surface from adsorbed aromatics. On the basis of the obtained results, a mechanistic proposal for this desulfurization was explained. Oxidation was performed by nucleophilic attack of sulfur atom to the molybdenum peroxide species of tetrahedral molybdates, which was more advanced by sonication. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

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.

CLOSED-LOOP STRIPPING ANALYSIS (CLSA) OF ...

EPA Pesticide Factsheets

Synthetic musk compounds are used as inexpensive fragrance materials for the production of perfumes and as additives to soap, detergent, and shampoo. They have been found in surface water, fish tissues, and human breast milk. The ubiquity of this class of compounds in the environment is attributable to high use and release into the environment. Current techniques for separating these compounds from fish tissues require tedious sample clean-up procedures. To obtain fat-free extracts, gel permeation chromatography (GPC), column chromatography using alumina, and silica gel, and thin layer chromatography (TLC clean-up procedures are frequently employed. Despite the considerable effort and resources devoted to these processes, a fraction of the lipids and lipid-like compounds frequently remains in the extracts. These low-level lipids foul injection liners, contaminate columns, and yield elevated baselines during gas chromatographic analysis of synthetic musk compounds. In this study, a simple method for the determination of synthetic musk compounds in fish tissues has been developed. Closed-loop stripping of saponified fish tissues in a I -L Wheaton purge- and-trap vessel, is used to strip compounds with high vapor pressures such as synthetic musks from the matrix onto a solid sorbent (Abselut Nexus). This technique is useful for screening biological tissues that contain lipids for musk compounds. Analytes are desorbed from the sorbent trap sequentially with polar an

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

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...

Modal gating of muscle nicotinic acetylcholine receptors

NASA Astrophysics Data System (ADS)

Vij, Ridhima

Many ion channels exhibit multiple patterns of kinetic activity in single-channel currents. This behavior is rare in WT mouse muscle nicotinic acetylcholine receptors (AChRs), where A2C↔A2O gating events are well-described by single exponentials. Also, single-channel open probability (PO) is essentially homogeneous at a given agonist concentration in the WT receptors. Here I report that perturbations of almost all the residues in loop C (alpha188-alpha199, at the agonist binding site) generate heterogeneity in PO ('modes'). Such unsettled activity was apparent with an alanine substitution at all positions in loop C (except alphaY190 and alphaY198) and with different side chain substitutions at alphaP197 for both adult- and fetal-type AChRs. I used single channel electrophysiology along with site-directed mutagenesis to study modal gating in AChRs consequent to mutations/deletions in loop C. The multiple patterns of kinetic activity arose from the difference in agonist affinity rather than in intrinsic AChR gating. Out of the four different agonists used to study the modal behavior, acetylcholine (ACh) showed a higher degree of kinetic heterogeneity compared to others. The time constant for switching between modes was long (~mins), suggesting that they arise from alternative, stable protein conformations. By studying AChRs having only 1 functional binding site, I attempted to find the source of the affinity difference, which was traced mainly to the alphadelta agonist site. Affinity at the neurotransmitter binding site is mainly determined by a core of five aromatic residues (alphaY93, alphaW149, alphaY190, alphaY198 and deltaW57). Phenylalanine substitutions at all aromatic residues except alphaY93 resulted in elimination of modes. Modes were also eliminated by alanine mutation at deltaW57 on the complementary side but not at other aromatics. Also, by substituting four gamma subunit residues into the delta subunit on the complementary beta sheet, I found that modes were reduced. Based on our results, we propose that WT loop C has an important role in determining resting affinity, in part by making stable interactions with the complementary surface of the alphadelta binding pocket. We suggest a possible structural basis for the fluctuations caused by loop C perturbations and propose that at the alphadelta agonist binding site, both loop C and the complementary subunit surface can adopt alternative conformations and interact with each other with respect to the aromatic core, to cause the variations in affinity.

An evaluation of electronic cigarette formulations and aerosols for harmful and potentially harmful constituents (HPHCs) typically derived from combustion.

PubMed

Wagner, Karl A; Flora, Jason W; Melvin, Matt S; Avery, Karen C; Ballentine, Regina M; Brown, Anthony P; McKinney, Willie J

2018-06-01

U.S. FDA draft guidance recommends reporting quantities of designated harmful and potentially harmful constituents (HPHCs) in e-cigarette e-liquids and aerosols. The HPHC list comprises potential matrix-related compounds, flavors, nicotine, tobacco-related impurities, leachables, thermal degradation products, and combustion-related compounds. E-cigarettes contain trace levels of many of these constituents due to tobacco-derived nicotine and thermal degradation. However, combustion-related HPHCs are not likely to be found due to the relatively low operating temperatures of most e-cigarettes. The purpose of this work was to use highly sensitive, selective, and validated analytical methods to determine if these combustion-related HPHCs (three aromatic amines, five volatile organic compounds, and the polycyclic aromatic hydrocarbon benzo[a]pyrene) are detectable in commercial refill e-liquids, reference e-cigarette e-liquids, and aerosols generated from rechargeable e-cigarettes with disposable cartridges (often referred to as "cig-a-likes"). In addition, the transfer efficiency of these constituents from e-liquid to aerosol was evaluated when these HPHCs were added to the e-liquids prior to aerosol formation. This work demonstrates that combustion-related HPHCs are not present at measurable levels in the commercial and reference e-liquids or e-cigarette aerosols tested. Additionally, when combustion-related HPHCs are added to the e-liquids, they transfer to the aerosol with transfer efficiencies ranging from 49% to 99%. Copyright © 2018 The Authors. Published by Elsevier Inc. All rights reserved.

Photooxidation products of polycyclic aromatic compounds containing sulfur.

PubMed

Bobinger, Stefan; Andersson, Jan T

2009-11-01

Photooxidation of crude oil components is an important process that removes pollutants from the environment. Polycyclic aromatic compounds (PACs) are known to be toxic to many life forms, but little is known about their photooxidation products in the aqueous phase. We here identify a large number of photoproducts from 11 benzothiophenes, a polycyclic aromatic sulfur heterocycle that is a major representative of PACs in crude oil. The investigated compounds contain two to four methyl groups and an ethyl or an n-octyl group. In water, the products arise through oxidation of alkyl side chains to aldehydes and carboxylic acids or through an opening in one of the aromatic rings. The product analysis was performed using gas chromatography with mass spectrometric or atomic emission detection. The main product is always a sulfobenzoic acid, which strongly lowers the pH of the solution. With long alkyl substituents, surfactants are formed, which may possess solubilizing properties in water. The larger the number of alkyl groups, the faster is the photooxidation. Several of the identified acidic compounds were also found when whole crude oil was photooxidized, showing that simulation with individual compounds reflects the situation in whole crude.

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.

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

A novel enhanced diffusion sampler for collecting gaseous pollutants without air agitation.

PubMed

Pan, Xuelian; Zhuo, Shaojie; Zhong, Qirui; Chen, Yuanchen; Du, Wei; Cheng, Hefa; Wang, Xilong; Zeng, Eddy Y; Xing, Baoshan; Tao, Shu

2018-03-06

A novel enhanced diffusion sampler for collecting gaseous phase polycyclic aromatic hydrocarbons (PAHs) without air agitation is proposed. The diffusion of target compounds into a sampling chamber is facilitated by continuously purging through a closed-loop flow to create a large concentration difference between the ambient air and the air in the sampling chamber. A glass-fiber filter-based prototype was developed. It was demonstrated that the device could collect gaseous PAHs at a much higher rate (1.6 ± 1.4 L/min) than regular passive samplers, while the ambient air is not agitated. The prototype was also tested in both the laboratory and field for characterizing the concentration gradients over a short distance from the soil surface. The sampler has potential to be applied in other similar situations to characterize the concentration profiles of other chemicals.

Epigenetic Programming of Breast Cancer and Nutrition Prevention

DTIC Science & Technology

2011-05-01

is to test the role of xenobiotics and food compounds that bind the aromatic hydrocarbon receptor (AhR). AhR-ligands include the dioxin -like and...tumor promoter 2,3,7,8 tetrachlorobenzo-p- dioxin (TCDD). The activated AhR regulates transcription through binding to xenobiotic response elements (XRE...phytoalexin resveratrol, selected as a prototype dietary AhR antagonist, antagonizes at physiologically relevant doses (1  mol /L) the TCDD-induced

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)

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.

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

Characterization of products from hydrothermal carbonization of pine.

PubMed

Wu, Qiong; Yu, Shitao; Hao, Naijia; Wells, Tyrone; Meng, Xianzhi; Li, Mi; Pu, Yunqiao; Liu, Shouxin; Ragauskas, Arthur J

2017-11-01

This study aims to reveal the structural features and reaction pathways for solid-liquid products from hydrothermal carbonization of Loblolly pine, where the solid products can be used as catalysts, adsorbents and electrode materials while liquid products can be treated yielding fuels and platform chemicals. Results revealed when treated at 240°C, cellulose and hemicellulose were degraded, in part, to 5-hydroxy-methyl furfural and furfural which were further transformed to aromatic structures via ring opening and Diels Alder reactions. Lignin degradation and formation of carbon-carbon bonds, forming aromatic motifs in the presence of furanic compounds connected via aliphatic bridges, ether or condensation reactions. After hydrothermal treatment, condensed aromatic carbon materials with methoxy groups were recovered with high fixed carbon content and HHV. The recovered liquid products are lignin-like value-added chemicals consisting of furfural and polyaromatic structure with alkanes and carboxyl, their total hydroxyl group content decreased when increasing reaction time. Copyright © 2017 Elsevier Ltd. All rights reserved.

Characterization of products from hydrothermal carbonization of pine

DOE PAGES

Wu, Qiong; Yu, Shitao; Hao, Naijia; ...

2017-07-27

This study aims to reveal the structural features and reaction pathways for solid–liquid products from hydrothermal carbonization of Loblolly pine, where the solid products can be used as catalysts, adsorbents and electrode materials while liquid products can be treated yielding fuels and platform chemicals. Results revealed when treated at 240 °C, cellulose and hemicellulose were degraded, in part, to 5-hydroxy-methyl furfural and furfural which were further transformed to aromatic structures via ring opening and Diels Alder reactions. Lignin degradation and formation of carbon–carbon bonds, forming aromatic motifs in the presence of furanic compounds connected via aliphatic bridges, ether or condensationmore » reactions. After hydrothermal treatment, condensed aromatic carbon materials with methoxy groups were recovered with high fixed carbon content and HHV. As a result, the recovered liquid products are lignin-like value-added chemicals consisting of furfural and polyaromatic structure with alkanes and carboxyl, their total hydroxyl group content decreased when increasing reaction time.« less

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

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.

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

Direct Aqueous Photochemistry of Isoprene High-NOx Secondary Organic Aerosol

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

Nguyen, Tran B.; Laskin, Alexander; Laskin, Julia

2012-05-17

Secondary organic aerosol (SOA) generated from the high-NOx photooxidation of isoprene was dissolved in water and irradiated with {lambda} > 290 nm light to simulate direct photolytic processing of organics in atmospheric water droplets. High-resolution mass spectrometry was used to characterize the composition at four time intervals (0, 1, 2, and 4 h). Photolysis resulted in the decomposition of high molecular weight (MW) oligomers, reducing the average length of organics by 2 carbon units. Approximately 65% by count of SOA molecules decomposed during photolysis, accompanied by the formation of new products. An average of 30 % of the organic massmore » was modified after 4 h of direct photolysis. In contrast, only a small fraction of the mass (<2 %), belonging primarily to organic nitrates, decomposed in the absence of irradiation by hydrolysis. We observed a statistically-significant increase in average O/C, decrease in H/C, and increase in N/C ratios resulting from photolysis. Furthermore, the concentration of aromatic compounds increased significantly during photolysis. Approximately 10 % of photodegraded compounds and 50 % of the photoproducts contain nitrogen. Organic nitrates and multifunctional oligomers were identified as compounds degraded by photolysis. Low-MW 0N (compounds with 0 nitrogen atoms in their structure) and 2N compounds were the dominant photoproducts. Fragmentation experiments using tandem mass spectrometry (MSn, n = 2-3) indicate that the 2N products are likely heterocyclic/aromatic and are tentatively identified as furoxans. Although the exact mechanism is unclear, these 2N heterocyclic compounds are produced by reactions between photochemically-formed aqueous NOx species and SOA organics.« less

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

Actions of a versatile fluorene-degrading bacterial isolate on polycyclic aromatic compounds.

PubMed Central

Grifoll, M; Selifonov, S A; Gatlin, C V; Chapman, P J

1995-01-01

Pseudomonas cepacia F297 grew with fluorene as a sole source of carbon and energy; its growth yield corresponded to an assimilation of about 40% of fluorene carbon. The accumulation of a ring meta-cleavage product during growth and the identification of 1-indanone in growth media and washed-cell suspensions suggest that strain F297 metabolizes fluorene by mechanisms analogous to those of naphthalene degradation. In addition to fluorene, strain F297 utilized for growth a wide variety of polycyclic aromatic compounds (PACs), including naphthalene, 2,3-dimethylnaphthalene, phenanthrene, anthracene, and dibenzothiophene. Fluorene-induced cells of the strain also transformed 2,6-dimethylnaphthalene, biphenyl, dibenzofuran, acenaphthene, and acenaphthylene. The identification of products formed from those substrates (by gas chromatography-mass spectrometry) in washed-cell suspensions indicates that P. cepacia F297 carries out the following reactions: (i) aromatic ring oxidation and cleavage, apparently using the pyruvate released for growth, (ii) methyl group oxidations, (iii) methylenic oxidations, and (iv) S oxidations of aromatic sulfur heterocycles. Strain F297 grew with a creosote-PAC mixture, producing an almost complete removal of all aromatic compounds containing 2 to 3 rings in 14 days, as demonstrated by gas chromatography analysis of the remaining PACs recovered from cultures. The identification of key chemicals confirmed that not only are certain compounds depleted but also the anticipated reaction products are found. PMID:7487007

Actions of a versatile fluorene-degrading bacterial isolate on polycyclic aromatic compounds.

PubMed

Grifoll, M; Selifonov, S A; Gatlin, C V; Chapman, P J

1995-10-01

Pseudomonas cepacia F297 grew with fluorene as a sole source of carbon and energy; its growth yield corresponded to an assimilation of about 40% of fluorene carbon. The accumulation of a ring meta-cleavage product during growth and the identification of 1-indanone in growth media and washed-cell suspensions suggest that strain F297 metabolizes fluorene by mechanisms analogous to those of naphthalene degradation. In addition to fluorene, strain F297 utilized for growth a wide variety of polycyclic aromatic compounds (PACs), including naphthalene, 2,3-dimethylnaphthalene, phenanthrene, anthracene, and dibenzothiophene. Fluorene-induced cells of the strain also transformed 2,6-dimethylnaphthalene, biphenyl, dibenzofuran, acenaphthene, and acenaphthylene. The identification of products formed from those substrates (by gas chromatography-mass spectrometry) in washed-cell suspensions indicates that P. cepacia F297 carries out the following reactions: (i) aromatic ring oxidation and cleavage, apparently using the pyruvate released for growth, (ii) methyl group oxidations, (iii) methylenic oxidations, and (iv) S oxidations of aromatic sulfur heterocycles. Strain F297 grew with a creosote-PAC mixture, producing an almost complete removal of all aromatic compounds containing 2 to 3 rings in 14 days, as demonstrated by gas chromatography analysis of the remaining PACs recovered from cultures. The identification of key chemicals confirmed that not only are certain compounds depleted but also the anticipated reaction products are found.

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.

Complete Sequence of a 184-Kilobase Catabolic Plasmid from Sphingomonas aromaticivorans F199†

PubMed Central

Romine, Margaret F.; Stillwell, Lisa C.; Wong, Kwong-Kwok; Thurston, Sarah J.; Sisk, Ellen C.; Sensen, Christoph; Gaasterland, Terry; Fredrickson, Jim K.; Saffer, Jeffrey D.

1999-01-01

The complete 184,457-bp sequence of the aromatic catabolic plasmid, pNL1, from Sphingomonas aromaticivorans F199 has been determined. A total of 186 open reading frames (ORFs) are predicted to encode proteins, of which 79 are likely directly associated with catabolism or transport of aromatic compounds. Genes that encode enzymes associated with the degradation of biphenyl, naphthalene, m-xylene, and p-cresol are predicted to be distributed among 15 gene clusters. The unusual coclustering of genes associated with different pathways appears to have evolved in response to similarities in biochemical mechanisms required for the degradation of intermediates in different pathways. A putative efflux pump and several hypothetical membrane-associated proteins were identified and predicted to be involved in the transport of aromatic compounds and/or intermediates in catabolism across the cell wall. Several genes associated with integration and recombination, including two group II intron-associated maturases, were identified in the replication region, suggesting that pNL1 is able to undergo integration and excision events with the chromosome and/or other portions of the plasmid. Conjugative transfer of pNL1 to another Sphingomonas sp. was demonstrated, and genes associated with this function were found in two large clusters. Approximately one-third of the ORFs (59 of them) have no obvious homology to known genes. PMID:10049392

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.

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

Flavor characteristics of seven grades of black tea produced in Turkey.

PubMed

Alasalvar, Cesarettin; Topal, Bahar; Serpen, Arda; Bahar, Banu; Pelvan, Ebru; Gökmen, Vural

2012-06-27

Seven grades of black tea [high-quality black tea (grades 1-3) and low-quality black tea (grades 4-7)], processed by ÇAYKUR Tea Processing Plant (Rize, Turkey), were compared for their differences in descriptive sensory analysis (DSA), aroma-active compounds (volatile compounds), and taste-active compounds (sugar, organic acid, and free amino acid compositions). Ten flavor attributes such as 'after taste', 'astringency', 'bitter', 'caramel-like', 'floral/sweet', 'green/grassy', 'hay-like', 'malty', 'roasty', and 'seaweed' were identified. Intensities for a number of flavor attributes ('after taste', 'caramel-like', 'malty', and 'seaweed') were not significantly different (p > 0.05) among seven grades of black tea. A total of 57 compounds in seven grades of black tea (14 aldehydes, eight alcohols, eight ketones, two esters, four aromatic hydrocarbons, five aliphatic hydrocarbons, nine terpenes, two pyrazines, one furan, two acids, and two miscellaneous compounds) were tentatively identified. Of these, aldeyhdes comprised more than 50% to the total volatile compounds identified. In general, high-grade quality tea had more volatiles than low-grade quality tea. With respect to taste-active compounds, five sugars, six organic acids, and 18 free amino acids were positively identified in seven grades of black tea, of which fructose, tannic acid, and theanine predominated, respectively. Some variations (p < 0.05), albeit to different extents, were observed among volatile compounds, sugars, organic acids, and free amino acids in seven grades of black tea. The present study suggests that a certain flavor attributes correlate well with taste- and aroma-active compounds. High- and low-quality black teas should not be distinguished solely on the basis of their DSA and taste- and aroma-active compounds. The combination of taste-active compounds together with aroma-active compounds renders combination effects that provide the characteristic flavor of each grade of black tea.

Internal standards for use in the comprehensive analysis of polychlorinated aromatic hydrocarbons using gas chromatography combined with multiphoton ionization mass spectrometry.

PubMed

Li, Adan; Imasaka, Totaro

2016-10-28

To decrease health-risks to humans, non-toxic compounds were evaluated for use as internal standards for calibrating data obtained by gas chromatography/multiphoton ionization mass spectrometry (GC-MPI-MS) using an ultraviolet femtosecond laser as the ionization source. The retention time in the mass chromatogram was calibrated using a retention index, in which a series of n-alkanes was employed as internal standards for evaluating the retention times for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs). To compensate for changes in signal intensity in MPI-MS, the dependence of signal intensity on the laser pulse energy was investigated for the dioxin-like compounds, in addition to five non-toxic aromatic hydrocarbons, that were used as internal standards. Based on their similar behavior,the non-toxic PCDD/PCDF, its 13 C-isotope, and pentachlorobenzene behave similarly, we conclude that they can be used for calibrating the signal intensities in MPI-MS. Copyright © 2016 Elsevier B.V. All rights reserved.

Prediction of cyclohexane-water distribution coefficient for SAMPL5 drug-like compounds with the QMPFF3 and ARROW polarizable force fields.

PubMed

Kamath, Ganesh; Kurnikov, Igor; Fain, Boris; Leontyev, Igor; Illarionov, Alexey; Butin, Oleg; Olevanov, Michael; Pereyaslavets, Leonid

2016-11-01

We present the performance of blind predictions of water-cyclohexane distribution coefficients for 53 drug-like compounds in the SAMPL5 challenge by three methods currently in use within our group. Two of them utilize QMPFF3 and ARROW, polarizable force-fields of varying complexity, and the third uses the General Amber Force-Field (GAFF). The polarizable FF's are implemented in an in-house MD package, Arbalest. We find that when we had time to parametrize the functional groups with care (batch 0), the polarizable force-fields outperformed the non-polarizable one. Conversely, on the full set of 53 compounds, GAFF performed better than both QMPFF3 and ARROW. We also describe the torsion-restrain method we used to improve sampling of molecular conformational space and thus the overall accuracy of prediction. The SAMPL5 challenge highlighted several drawbacks of our force-fields, such as our significant systematic over-estimation of hydrophobic interactions, specifically for alkanes and aromatic rings.

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.

Intermolecular hydrogen bonds in hetero-complexes of biologically active aromatic molecules probed by the methods of vibrational spectroscopy

NASA Astrophysics Data System (ADS)

Semenov, M. A.; Blyzniuk, Iu. N.; Bolbukh, T. V.; Shestopalova, A. V.; Evstigneev, M. P.; Maleev, V. Ya.

2012-09-01

By the methods of vibrational spectroscopy (Infrared and Raman) the investigation of the hetero-association of biologically active aromatic compounds: flavin-mononucleotide (FMN), ethidium bromide (EB) and proflavine (PRF) was performed in aqueous solutions. It was shown that between the functional groups (Cdbnd O and NH2) the intermolecular hydrogen bonds are formed in the hetero-complexes FMN-EB and FMN-PRF, additionally stabilizing these structures. An estimation of the enthalpy of Н-bonding obtained from experimental shifts of carbonyl vibrational frequencies has shown that the H-bonds do not dominate in the magnitude of experimentally measured total enthalpy of the hetero-association reactions. The main stabilization is likely due to intermolecular interactions of the molecules in these complexes and their interaction with water environment.

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...

Microbial communities related to volatile organic compound emission in automobile air conditioning units.

PubMed

Diekmann, Nina; Burghartz, Melanie; Remus, Lars; Kaufholz, Anna-Lena; Nawrath, Thorben; Rohde, Manfred; Schulz, Stefan; Roselius, Louisa; Schaper, Jörg; Mamber, Oliver; Jahn, Dieter; Jahn, Martina

2013-10-01

During operation of mobile air conditioning (MAC) systems in automobiles, malodours can occur. We studied the microbial communities found on contaminated heat exchanger fins of 45 evaporators from car MAC systems which were operated in seven different regions of the world and identified corresponding volatile organic compounds. Collected biofilms were examined by scanning electron microscopy and fluorescent in situ hybridization. The detected bacteria were loosely attached to the metal surface. Further analyses of the bacteria using PCR-based single-strand conformation polymorphism and sequencing of isolated 16S rRNA gene fragments identified highly divergent microbial communities with multiple members of the Alphaproteobacteriales, Methylobacteria were the prevalent bacteria. In addition, Sphingomonadales, Burkholderiales, Bacillales, Alcanivorax spp. and Stenotrophomonas spp. were found among many others depending on the location the evaporators were operated. Interestingly, typical pathogenic bacteria related to air conditioning systems including Legionella spp. were not found. In order to determine the nature of the chemical compounds produced by the bacteria, the volatile organic compounds were examined by closed loop stripping analysis and identified by combined gas chromatography/mass spectrometry. Sulphur compounds, i.e. di-, tri- and multiple sulphides, acetylthiazole, aromatic compounds and diverse substituted pyrazines were detected. Mathematical clustering of the determined microbial community structures against their origin identified a European/American/Arabic cluster versus two mainly tropical Asian clusters. Interestingly, clustering of the determined volatiles against the origin of the corresponding MAC revealed a highly similar pattern. A close relationship of microbial community structure and resulting malodours to the climate and air quality at the location of MAC operation was concluded.

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.

COMMENT: Comment on 'Particle size dependent exchange bias and cluster-glass states in LaMn0.7Fe0.3O3 '

NASA Astrophysics Data System (ADS)

Geshev, J.

2009-02-01

Thakur et al (2008 J. Phys.: Condens. Matter 20 195215) have recently reported magnetization hysteresis loops shifted along the field axis of the cluster-glass compound LaMn0.7Fe0.3O3, attributed there to exchange bias induced at ferromagnetic/spin-glass-like interfaces. The present comment affirms that their results are insufficient for assigning the phenomenon solely to exchange bias since the corresponding field shift, if any, cannot be separated from that of a minor hysteresis loop of a ferromagnet, naturally displaced from the origin.

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

Synthesis, Spectral investigation (¹H, ¹³C) and Anti-microbial Screening of benzophenone imines.

PubMed

Khosa, Muhammad Kaleem; Jamal, Muhammad Asghar; Saif, Muhammad Jawad; Muneer, Majid; Rehman, Fazalur; Farman, Muhammad; Shoaib, Hafiz Muhammad; Shahid, Muhammad; Hameed, Shabnam

2015-11-01

New series of benzophenone imines with general formula Ph2-C=NR; R = Benzyl, 4-Fluorobenzyl, Naphthyl, Phenyl, 4-Nitrophenyl were synthesized by condensation of dichlorodiphenylmethane and different aromatic primary amines (1:1) Those imines were characterized by different physiochemical and spectroscopic techniques like melting point, elemental analysis, FT-IR, multinuclear NMR (¹H, ¹³C). After characterization, imines were subjected to anti-microbial activities. All compounds showed promising activity against different bacterial strains like Escherichia coli, Bacillussubtilis, Pasturellam ultocida and Staphylococcus aureus as well as fungal strains like Alternata alternaria, Ganoderma lucidium, Penicillium notatum and Trichoderma harzianum using Amoxicillin and Flucanazole as a standard drugs respectively.

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

Influence of Fruit Ripening on Color, Organic Acid Contents, Capsaicinoids, Aroma Compounds, and Antioxidant Capacity of Shimatogarashi (Capsicum frutescens).

PubMed

Manikharda; Takahashi, Makoto; Arakaki, Mika; Yonamine, Kaoru; Hashimoto, Fumio; Takara, Kensaku; Wada, Koji

2018-01-01

Shimatogarashi (Capsicum frutescens) is a typical chili pepper domesticated in southern Japan. Important traits of Shimatogarashi peppers, such as color; proportion of organic acids, capsaicinoids, and aromatic compounds; and antioxidant activity in three stages of maturity (green (immature), orange (turning), and red (mature) stages) were characterized. The results indicated that the concentration of organic acids, including ascorbic, citric, and malic acid, increased during ripening. In addition, the amount of capsaicinoids, which are responsible for the pungent taste of chili peppers, increased as the fruit matured to the orange and red stages. The volatile compound profile of Shimatogarashi was dominated by the presence of esters, which mainly contributed to fruity notes. The total amount of volatile compounds analyzed by gas chromatography-headspace solid-phase microextraction (GC-HS-SPME), especially esters, decreased as the fruit changed in color from green to red. This was in contrast to the amount of terpenoids, especially limonene, which increased at the red stage, denoting a change in flavor from fruity to a more citrus-like aroma. Based on the total phenolic content (TPC), the oxygen radical absorbance capacity (ORAC) and the diphenylpicrylhydrazyl (DPPH) free radical method, the antioxidant capacity of Shimatogarashi showed an increase at the mature red stage. However, while the red stage showed higher pungency and antioxidant capacity as well as an attractive color, the results of aromatic compound analysis revealed that the immature green stage had the advantages of having pleasant fruity smell, making it suitable for use in condiments.

Microwave-assisted extraction of polycyclic aromatic compounds from coal.

PubMed

Kerst, M; Andersson, J T

2001-08-01

Microwave-assisted extraction (MAE) of polycyclic aromatic compounds (PACs) from coal is shown to give the same pattern of compounds as Soxhlet extraction. MAE requires only 10 mL solvent and 10 min extraction time whereas Soxhlet uses 200 mL and takes 24 h. Although the yields were lower, dichloromethane (DCM) was preferred to pyridine, N-methyl-2-pyrrolidone (NMP), and NMP with CS2 because the pattern of the PACs is shown to be independent of solvent and DCM is a much more convenient solvent to work with.

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

Utilization of lignocellulosic polysaccharides

NASA Astrophysics Data System (ADS)

Fenske, John James

Lignocellulosic biomass represents a vast supply of fermentable carbohydrates and functional aromatic compounds. Conversion of lignocellulosics to ethanol and other useful products would be of widespread economical and environmental benefit. Better understanding of the behavior of different lignocellulosic feedstocks in fermentation protocols as well as catalytic activities involved in lignocellulosic depolymerization will further enhance the commercial viability of biomass-to-ethanol conversion processes. The relative toxicity of the combined non-xylose components in prehydrolysates derived from three different lignocellulosic biomass feedstocks (poplar, corn stover and switchgrass, or Panicum virgatum L.) was determined using a Pichia stipits fermentation assay. The relative toxicity of the prehydrolysates, in decreasing order, was poplar-derived prehydrolysates > switchgrass-derived prehydrolysates > corn stover-derived prehydrolysates. Ethanol yields averaged 74%, 83% and 88% of control values for poplar, switchgrass and corn stover prehydrolysates, respectively. Volumetric ethanol productivities (g ethanol lsp{-1} hsp{-1}) averaged 32%, 70% and 102% of control values for poplar, switchgrass and corn stover prehydrolysates, respectively. Ethanol productivities correlated closely with acetate concentrations in the prehydrolysates; however, regression lines correlating acetate concentrations and ethanol productivities were found to be feedstock-dependent. Differences in the relative toxicity of xylose-rich prehydrolysates derived from woody and herbaceous feedstocks are likely due to the relative abundance of a variety of inhibitory compounds, e.g. acetate and aromatic compounds. Fourteen aromatic monomers present in prehydrolysates prepared from corn stover, switchgrass, and poplar were tentatively identified by comparison with published mass spectra. The concentrations of the aromatic monomers totaled 112, 141 and 247 mg(l)sp{-1} for corn stover, switchgrass and poplar prehydrolysates, respectively. The woody and herbaceous feedstocks differed in both amount and type of aromatic monomers. The cellulases of Trichoderma reesei are the most widely studied for use in the depolymerization of lignocellulosics. The Trichoderma cellobiohydrolases CBH1 and CBH2 are traditionally categorized as exo-acting cellulases. A simple individual-based model was created to explore the potential effects of native endo activity on substrate-velocity profiles. The model results indicate that an enzyme with a small amount of endo activity will show an apparent substrate inhibition as substrate levels are increased. Actual hydrolysis studies using affinity chromatography-purified CBH2 preparations from three laboratories indicate that CBH2 has native endo activity, while CBH1 does not.

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.

Schiff Bases of Benzothiazol-2-ylamine and Thiazolo[5,4-b] pyridin-2-ylamine as Anticonvulsants: Synthesis, Characterization and Toxicity Profiling.

PubMed

Shukla, Rashmi; Singh, Ajeet P; Sonar, Pankaj K; Mishra, Mudita; Saraf, Shailendra K

2016-01-01

Schiff bases have a broad spectrum of biological activities like antiinflammatory, analgesic, antimicrobial, anticonvulsant, antitubercular, anticancer, antioxidant, anthelmintic and so forth. Thus, after a thorough perusal of literature, it was decided to conjugate benzothiazol-2-ylamine/thiazolo [5, 4-b] pyridin-2-ylamine with aromatic and heteroaromatic aldehydes to get a series of Schiff bases. Synthesis, characterization, in-silico toxicity profiling and anticonvulsant activity of the Schiff bases of Benzothiazol-2-ylamine and Thiazolo [5, 4-b] pyridin-2-ylamine. Aniline/4-aminopyridine was converted to the corresponding thiourea derivatives, which were cyclized to obtain benzothiazol-2-ylamine/thiazolo [5, 4-b] pyridin-2-ylamine. Finally, these were condensed with various aromatic and heteroaromatic aldehydes to obtain Schiff bases of benzothiazol-2-ylamine and thiazolo [5, 4-b] pyridin-2-ylamine. The synthesized compounds were characterized and screened for their anticonvulsant activity using maximal electroshock (MES) test and isoniazid (INH) induced convulsions test. In-silico toxicity profiling of all the synthesized compounds was done through "Lazar" and "Osiris" properties explorer. Majority of the compounds were more potent against MES induced convulsions than INH induced convulsions. Schiff bases of benzothiazol-2-ylamine were more effective than thiazolo [5, 4-b] pyridin-2-ylamine against MES induced convulsions. The compound benzothiazol-2-yl-(1H-indol-2-ylmethylene)-amine (VI) was the most potent member of the series against both types of convulsions. Compound VI exhibited the most significant activity profile in both the models. The compounds did not exhibit any carcinogenicity or acute toxicity in the in-silico studies. Thus, it may be concluded that the Schiff bases of benzothiazol-2-ylamine exhibit the potential to be promising and non-toxic anticonvulsant agents.

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.

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.

Molecular Markers in the Quelccaya Ice Cap, Peru Describe 20th Century Biomass Burning Variability

NASA Astrophysics Data System (ADS)

Makou, M. C.; Thompson, L. G.; Eglinton, T. I.; Montluçon, D. B.

2007-12-01

Organic geochemical analytical methods were applied to Andean ice core samples, resulting in a multi- molecular biomass burning record spanning 1915 to 2001 AD. The Quelccaya Ice Cap in Peru is situated on the eastern flank of the Andes at 14°S and is well situated to receive aeolian inputs of organic matter derived from Amazonian forest fire events. Compounds of interest, which occur in trace quantities in ice, were recovered by stir bar sorptive extraction and analyzed by gas chromatography/time-of-flight mass spectrometry coupled with thermal desorption. These methods permitted identification and quantitation of numerous biomarkers in sample volumes of as little as 10 ml. At least one wet and dry season sample was analyzed for every year. Observed biomarkers that may be derived from vegetation fires include several polycyclic aromatic hydrocarbons (PAHs), atraric acid, 2-ethylhexyl p-methoxycinnamate, and a range of other aromatic compounds. Abrupt changes in compound abundances were superimposed on decadal variability. Systematic offsets between wet and dry season abundances were not observed, suggesting that the biomass burning signal is not biased by seasonal depositional effects, such as dust delivery. Inputs likely reflect a combination of sources from anthropogenic burning of the Amazon rainforest as well as natural fires related to aridity, and include both high and low elevation vegetation. These compounds and techniques can be applied to older ice in this and other core locations as an independent estimate of aridity.

Design, synthesis and structure-activity relationship of novel quinoxalin-2-carboxamides as 5-HT3 receptor antagonists for the management of depression.

PubMed

Mahesh, Radhakrishnan; Devadoss, Thangaraj; Pandey, Dilip Kumar; Bhatt, Shvetank; Yadav, Shushil Kumar

2010-11-15

A novel series of quinoxalin-2-carboxamides were designed based on the ligand-based approach, employing a three-point pharmacophore model; it consists of an aromatic residue and a linking carbonyl group and a basic nitrogen. The target new chemical entities were synthesized from the key intermediate, quinoxalin-2-carboxylic acid, by coupling it with various amines in the presence of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC·HCl) and 1-hydroxybenzotriazole (HOBt). The obtained compounds' structures were confirmed by spectral data. The target new chemical entities were evaluated for their 5-HT(3) receptor antagonisms in longitudinal muscle myenteric plexus preparation from guinea pig ileum against 5-HT(3) agonist, 2-methyl-5-HT, which was expressed in the form of pA(2) value. All the synthesized compounds showed antagonism towards 5-HT(3) receptor; based on this result, a structure-activity relationship was derived, which reveals that the aromatic residue in 5-HT(3) receptor antagonists may have hydrophobic interaction with 5-HT(3) receptor. Regardless of their antagonistic potentials, all the synthesized molecules were screened for their anti-depressant potentials by using forced swim test in mice model; interestingly none of the tested compounds affect the locomotion of mice in the tested dose levels. Compounds with significant pA(2) values exhibited good anti-depressant-like activity as compared to the vehicle-treated group. Copyright © 2010 Elsevier Ltd. All rights reserved.

Resolving the chemical structures of off-odorants and potentially harmful substances in toys-example of children's swords.

PubMed

Denk, Philipp; Velasco-Schön, Cristina; Buettner, Andrea

2017-09-01

Most children's toys on the market are primarily made out of plastic and other complex composite materials. Consumer complaints about offensive odors or irritating effects associated with toy products have increased in recent years. One example is the strongly perceivable negative odor reported for a particular series of toy swords. Characterizing the presence of contaminants, including those that have the potential to be deleterious to health, in such products is a significant analytical challenge due to the high baseline abundance of chemical constituents of the materials used in the products. In the present study, the nature of offensive odorants associated with toy sword products was examined by gas chromatography (GC). After initial sensory evaluations, the volatile compounds from the toy products were recovered using solvent extraction and solvent-assisted flavor evaporation. The extracts were analyzed using GC-olfactometry (GC-O) and two-dimensional GC-O coupled with mass spectrometry (GC-GC-MS/O). A total of 26 odor-active compounds, including aromatic hydrocarbons and phenols, were identified among numerous non-odorous volatile by-products. These substances also included polycyclic aromatic hydrocarbons, which were analyzed by GC-MS. Representative substances were naphthalene and 1,2-dihydronaphthalene that exhibited moldy, mothball-like odor impressions, and phenol derivatives with leather-like, phenolic, horse-stable-like smells. The odorants detected correlated with the assigned attributes from the sensory analyses. This study clearly shows that the detection and identification of such odorous contaminants can provide key indications of potentially harmful yet unknown substances in everyday products such as toys. Graphical abstract ᅟ.

Organic waste compounds as contaminants in Milwaukee-area streams

USGS Publications Warehouse

Baldwin, Austin K.; Corsi, Steven R.; Magruder, Christopher; Magruder, Matthew; Bruce, Jennifer L.

2015-09-22

Organic waste compounds (OWCs) are ingredients and by-products of common agricultural, industrial, and household substances that can contaminate our streams through sources like urban runoff, sewage overflows, and leaking septic systems. To better understand how OWCs are affecting Milwaukee-area streams, the U.S. Geological Survey, in cooperation with the Milwaukee Metropolitan Sewerage District, conducted a three-year study to investigate the presence and potential toxicity of 69 OWCs in base flow, stormflow, pore water, and sediment at 14 stream sites and 3 Milwaukee harbor locations. This fact sheet summarizes the major findings of this study, including detection frequencies and concentrations, potential toxicity, the prevalence of polycyclic aromatic hydrocarbons (PAHs), and the influence of urbanization.

[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.

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.

Intermolecular hydrogen bonds in hetero-complexes of biologically active aromatic molecules probed by the methods of vibrational spectroscopy.

PubMed

Semenov, M A; Blyzniuk, Iu N; Bolbukh, T V; Shestopalova, A V; Evstigneev, M P; Maleev, V Ya

2012-09-01

By the methods of vibrational spectroscopy (Infrared and Raman) the investigation of the hetero-association of biologically active aromatic compounds: flavin-mononucleotide (FMN), ethidium bromide (EB) and proflavine (PRF) was performed in aqueous solutions. It was shown that between the functional groups (CO and NH(2)) the intermolecular hydrogen bonds are formed in the hetero-complexes FMN-EB and FMN-PRF, additionally stabilizing these structures. An estimation of the enthalpy of Н-bonding obtained from experimental shifts of carbonyl vibrational frequencies has shown that the H-bonds do not dominate in the magnitude of experimentally measured total enthalpy of the hetero-association reactions. The main stabilization is likely due to intermolecular interactions of the molecules in these complexes and their interaction with water environment. Copyright © 2012 Elsevier B.V. All rights reserved.

Cardiac toxicity of 5-ring polycyclic aromatic hydrocarbons is differentially dependent on the aryl hydrocarbon receptor 2 isoform during zebrafish development

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

Incardona, John P., E-mail: john.incardona@noaa.gov; Linbo, Tiffany L.; Scholz, Nathaniel L.

Petroleum-derived compounds, including polycyclic aromatic hydrocarbons (PAHs), commonly occur as complex mixtures in the environment. Recent studies using the zebrafish experimental model have shown that PAHs are toxic to the embryonic cardiovascular system, and that the severity and nature of this developmental cardiotoxicity varies by individual PAH. In the present study we characterize the toxicity of the relatively higher molecular weight 5-ring PAHs benzo[a]pyrene (BaP), benzo[e]pyrene (BeP), and benzo[k]fluoranthene (BkF). While all three compounds target the cardiovascular system, the underlying role of the ligand-activated aryl hydrocarbon receptor (AHR2) and the tissue-specific induction of the cytochrome p450 metabolic pathway (CYP1A) weremore » distinct for each. BaP exposure (40 {mu}M) produced AHR2-dependent bradycardia, pericardial edema, and myocardial CYP1A immunofluorescence. By contrast, BkF exposure (4-40 {mu}M) caused more severe pericardial edema, looping defects, and erythrocyte regurgitation through the atrioventricular valve that were AHR2-independent (i.e., absent myocardial or endocardial CYP1A induction). Lastly, exposure to BeP (40 {mu}M) yielded a low level of CYP1A+ signal in the vascular endothelium of the head and trunk, without evident toxic effects on cardiac function or morphogenesis. Combined with earlier work on 3- and 4-ring PAHs, our findings provide a more complete picture of how individual PAHs may drive the cardiotoxicity of mixtures in which they predominate. This will improve toxic injury assessments and risk assessments for wild fish populations that spawn in habitats altered by overlapping petroleum-related human impacts such as oil spills, urban stormwater runoff, or sediments contaminated by legacy industrial activities. -- Highlights: Black-Right-Pointing-Pointer PAH compounds with 5 rings in different arrangements caused differential tissue-specific patterns of CYP1A induction in zebrafish embryos. Black-Right-Pointing-Pointer These compounds produced differential cardiac developmental toxicity that did not strictly correlate with associated CYP1A induction. Black-Right-Pointing-Pointer Cardiotoxicity of benzo(a)pyrene was partially dependent on the AHR2 isoform, while benzo(k)fluoranthene cardiotoxicity was not. Black-Right-Pointing-Pointer Individual PAH compounds have distinct toxicokinetic pathways in fish embryos, and act through different toxic mechanisms.« less

AccR Is a Master Regulator Involved in Carbon Catabolite Repression of the Anaerobic Catabolism of Aromatic Compounds in Azoarcus sp. CIB*

PubMed Central

Valderrama, J. Andrés; Shingler, Victoria; Carmona, Manuel; Díaz, Eduardo

2014-01-01

Here we characterized the first known transcriptional regulator that accounts for carbon catabolite repression (CCR) control of the anaerobic catabolism of aromatic compounds in bacteria. The AccR response regulator of Azoarcus sp. CIB controls succinate-responsive CCR of the central pathways for the anaerobic catabolism of aromatics by this strain. Phosphorylation of AccR to AccR-P triggers a monomer-to-dimer transition as well as the ability to bind to the target promoter and causes repression both in vivo and in vitro. Substitution of the Asp60 phosphorylation target residue of the N-terminal receiver motif of AccR to a phosphomimic Glu residue generates a constitutively active derivative that behaves as a superrepressor of the target genes. AccR-P binds in vitro to a conserved inverted repeat (ATGCA-N6-TGCAT) present at two different locations within the PN promoter of the bzd genes for anaerobic benzoate degradation. Because the DNA binding-proficient C-terminal domain of AccR is monomeric, we propose an activation mechanism in which phosphorylation of Asp60 of AccR alleviates interdomain repression mediated by the N-terminal domain. The presence of AccR-like proteins encoded in the genomes of other β-proteobacteria of the Azoarcus/Thauera group further suggests that AccR constitutes a master regulator that controls anaerobic CCR in these bacteria. PMID:24302740

Synthesis, Structural Characterization and Physicochemical Properties of Polymers Formed by Diazotization of 3-Amino-L-tyrosine and Closely Related Compounds

DTIC Science & Technology

1998-07-06

the possibility that a diazotization at the aliphatic (alpha) amino group might lead to deamination with the formation of a cinnamic acid derivative...symmetric chlorinated/nitrated cinnamic acid derivative, and might not provide unequivocal connectivity information, although it could suggest ring...substituted aromatic ring, i.e., it is more like the spectrum of p-coumaric acid than the desired 3-amino-4-hydroxy- cinnamic acid , which would be

Dechlorination of Aromatic Xenobiotic Compounds by Anaerobic Microorganisms

DTIC Science & Technology

1988-07-01

DCB-l likely can also live as a scavenger because it was isolated on rumen fluid and responded with improved growth when rumen fluid or trypticase... rumen fluid markedly enhanced the dechlorinating activity. The activity was increased from ca 13 IM to 75 pM per day and the lag period was reduced from...4 weeks to 3 days in presence of either 0.1 percent yeast extract or 5 percent rumen fluid. The study also suggested that the dechlorinating activity

Protein Quantification by Derivatization-Free High-Performance Liquid Chromatography of Aromatic Amino Acids

PubMed Central

Hesse, Almut

2016-01-01

Amino acid analysis is considered to be the gold standard for quantitative peptide and protein analysis. Here, we would like to propose a simple HPLC/UV method based on a reversed-phase separation of the aromatic amino acids tyrosine (Tyr), phenylalanine (Phe), and optionally tryptophan (Trp) without any derivatization. The hydrolysis of the proteins and peptides was performed by an accelerated microwave technique, which needs only 30 minutes. Two internal standard compounds, homotyrosine (HTyr) and 4-fluorophenylalanine (FPhe) were used for calibration. The limit of detection (LOD) was estimated to be 0.05 µM (~10 µg/L) for tyrosine and phenylalanine at 215 nm. The LOD for a protein determination was calculated to be below 16 mg/L (~300 ng BSA absolute). Aromatic amino acid analysis (AAAA) offers excellent accuracy and a precision of about 5% relative standard deviation, including the hydrolysis step. The method was validated with certified reference materials (CRM) of amino acids and of a pure protein (bovine serum albumin, BSA). AAAA can be used for the quantification of aromatic amino acids, isolated peptides or proteins, complex peptide or protein samples, such as serum or milk powder, and peptides or proteins immobilized on solid supports. PMID:27559481

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.

Hydrological changes of DOM composition and biodegradability of rivers in temperate monsoon climates

NASA Astrophysics Data System (ADS)

Shin, Yera; Lee, Eun-Ju; Jeon, Young-Joon; Hur, Jin; Oh, Neung-Hwan

2016-09-01

The spatial and hydrological dynamics of dissolved organic matter (DOM) composition and biodegradability were investigated for the five largest rivers in the Republic of Korea (South Korea) during the years 2012-2013 using incubation experiments and spectroscopic measurements, which included parallel factor analysis (PARAFAC). The lower reaches of the five rivers were selected as windows showing the integrated effects of basin biogeochemistry of different land use under Asian monsoon climates, providing an insight on consistency of DOM dynamics across multiple sites which could be difficult to obtain from a study on an individual river. The mean dissolved organic carbon (DOC) concentrations of the five rivers were relatively low, ranging from 1.4 to 3.4 mg L-1, due to the high slope and low percentage of wetland cover in the basin. Terrestrial humic- and fulvic-like components were dominant in all the rivers except for one, where protein-like compounds were up to ∼80%. However, terrestrial components became dominant in all five of the rivers after high precipitation during the summer monsoon season, indicating the strong role of hydrology on riverine DOM compositions for the basins under Asian monsoon climates. Considering that 64% of South Korea is forested, our results suggest that the forests could be a large source of riverine DOM, elevating the DOM loads during monsoon rainfall. Although more DOM was degraded when DOM input increased, regardless of its sources, the percent biodegradability was reduced with increased proportions of terrestrially derived aromatic compounds. The shift in DOM quality towards higher percentages of aromatic terrestrial compounds may alter the balance of the carbon cycle of coastal ecosystems by changing microbial metabolic processes if climate extremes such as heavy storms and typhoons become more frequent due to climate change.

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.

Conservative Tryptophan Mutants of the Protein Tyrosine Phosphatase YopH Exhibit Impaired WPD-Loop Function and Crystallize with Divanadate Esters in Their Active Sites

PubMed Central

Moise, Gwendolyn; Gallup, Nathan M.; Alexandrova, Anastassia N.; Hengge, Alvan C.; Johnson, Sean J.

2016-01-01

Catalysis in protein tyrosine phosphatases (PTPs) involves movement of a protein loop called the WPD loop that brings a conserved aspartic acid into the active site to function as a general acid. Mutation of the tryptophan in the WPD loop of the PTP YopH to any other residue with a planar, aromatic side chain (phenylalanine, tyrosine, or histidine) disables general acid catalysis. Crystal structures reveal these conservative mutations leave this critical loop in a catalytically unproductive, quasi-open position. Although the loop positions in crystal structures are similar for all three conservative mutants, the reasons inhibiting normal loop closure differ for each mutant. In the W354F and W354Y mutants, steric clashes result from six-membered rings occupying the position of the five-membered ring of the native indole side chain. The histidine mutant dysfunction results from new hydrogen bonds stabilizing the unproductive position. The results demonstrate how even modest modifications can disrupt catalytically important protein dynamics. Crystallization of all the catalytically compromised mutants in the presence of vanadate gave rise to vanadate dimers at the active site. In W354Y and W354H, a divanadate ester with glycerol is observed. Such species have precedence in solution and are known from the small molecule crystal database. Such species have not been observed in the active site of a phosphatase, as a functional phosphatase would rapidly catalyze their decomposition. The compromised functionality of the mutants allows the trapping of species that undoubtedly form in solution and are capable of binding at the active sites of PTPs, and, presumably, other phosphatases. In addition to monomeric vanadate, such higher-order vanadium-based molecules are likely involved in the interaction of vanadate with PTPs in solution. PMID:26445170

Aliphatic and polycyclic aromatic hydrocarbons characterisation of Coimbra and Oporto PM2.5 urban aerosol

NASA Astrophysics Data System (ADS)

Rocha, A. C.; Mirante, F.; Gonçalves, C.; Nunes, T.; Alves, C.; Evtyugina, M.; Kowacz, M.; Pio, C.; Rocha, C.; Vasconcelos, T.

2009-04-01

The concentration of organic pollutants in urban areas is mostly due to incomplete combustion from vehicles, industries and domestic heating. Some of these compounds, principally the aliphatic (ALIPH) and polycyclic aromatic hydrocarbons (PAHs) promote harmful effects in human health. The determination of the ALIPH and PAHs concentration levels and their possible emission sources are useful for air quality management and source apportionment studies. In order to estimate and compare the ambient concentrations and establish the main sources of these compounds, the fine fraction of the atmospheric particulate matter (PM2.5) was collected simultaneously in Oporto and Coimbra during summer and winter seasons using a high volume sampler. The organic compounds were extracted from the particulate matter, under reflux with dichloromethane and the total organic extract (TOE) was fractionated by flash chromatography using five different eluents with increasing polarity. The hydrocarbon fractions were analysed by gas chromatography/mass spectrometry (GC/MS). Here we present and discuss the qualitative and quantitative composition of the aliphatic and aromatic fractions present in PM2.5 samples from both cities. The homologous series of C14 to C34 n-alkanes, isoprenoid hydrocarbons (pristane and phytane), PAHs and some petroleum markers have been identified and quantified. With the purpose of identifying the possible sources, various molecular diagnostic ratios were calculated. The global carbon preference index (CPI) closer to the unity, the large concentration of the unresolved complex mixture (UCM) and the presence of PAHs indicate that motor vehicle exhaust was the main emission source of the aliphatic and polycyclic aromatic fractions of Oporto and Coimbra aerosol, especially in the first city. Also, the remarkable presence of petroleum biomarkers such, as hopanes, confirms the previous results. Concentration ratios between PAHs were calculated and used to assign emission sources. The abundance and the sources of these organic pollutants for the two cities are discussed and compared taking into account the local/regional characteristics. Acknowledgement: The authors would like to thank Fundação para a Ciência e Tecnologia (FCT) for the financial support through the project POCI/AMB/60267/2004 which provided funding for the work presented here.

Solid-Phase Microextraction Coupled to Capillary Atmospheric Pressure Photoionization-Mass Spectrometry for Direct Analysis of Polar and Nonpolar Compounds.

PubMed

Mirabelli, Mario F; Zenobi, Renato

2018-04-17

A novel capillary ionization source based on atmospheric pressure photoionization (cAPPI) was developed and used for the direct interfacing between solid-phase microextraction (SPME) and mass spectrometry (MS). The efficiency of the source was evaluated for direct and dopant-assisted photoionization, analyzing both polar (e.g., triazines and organophosphorus pesticides) and nonpolar (polycyclic aromatic hydrocarbons, PAHs) compounds. The results show that the range of compound polarity, which can be addressed by direct SPME-MS can be substantially extended by using cAPPI, compared to other sensitive techniques like direct analysis in real time (DART) and dielectric barrier discharge ionization (DBDI). The new source delivers a very high sensitivity, down to sub parts-per-trillion (ppt), making it a viable alternative when compared to previously reported and less comprehensive direct approaches.

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.

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...

Structural basis of the therapeutic anti-PD-L1 antibody atezolizumab.

PubMed

Zhang, Fei; Qi, Xiaoqiang; Wang, Xiaoxiao; Wei, Diyang; Wu, Jiawei; Feng, Lingling; Cai, Haiyan; Wang, Yugang; Zeng, Naiyan; Xu, Ting; Zhou, Aiwu; Zheng, Ying

2017-10-27

Monoclonal antibodies targeting PD-1/PD-L1 signaling pathway have achieved unprecedented success in cancer treatment over the last few years. Atezolizumab is the first PD-L1 monoclonal antibody approved by US FDA for cancer therapy; however the molecular basis of atezolizumab in blocking PD-1/PD-L1 interaction is not fully understood. Here we have solved the crystal structure of PD-L1/atezolizumab complex at 2.9 angstrom resolution. The structure shows that atezolizumab binds the front beta-sheet of PD-L1 through three CDR loops from the heavy chain and one CDR loop from the light chain. The binding involves extensive hydrogen-bonding and hydrophobic interactions. Notably there are multiple aromatic residues from the CDR loops forming Pi-Pi stacking or cation-Pi interactions within the center of the binding interface and the buried surface area is more than 2000 Å 2 , which is the largest amongst all the known PD-L1/antibody structures. Mutagenesis study revealed that two hot-spot residues (E58, R113) of PD-L1 contribute significantly to the binding of atezolizumab. The structure also shows that atezolizumab binds PD-L1 with a distinct heavy and light chain orientation and it blocks PD-1/PD-L1 interaction through competing with PD-1 for the same PD-L1 surface area. Taken together, the complex structure of PD-L1/atezolizumab solved here revealed the molecular mechanism of atezolizumab in immunotherapy and provides basis for future monoclonal antibody optimization and rational design of small chemical compounds targeting PD-L1 surface.

Structural basis of the therapeutic anti-PD-L1 antibody atezolizumab

PubMed Central

Wei, Diyang; Wu, Jiawei; Feng, Lingling; Cai, Haiyan; Wang, Yugang; Zeng, Naiyan; Xu, Ting; Zhou, Aiwu; Zheng, Ying

2017-01-01

Monoclonal antibodies targeting PD-1/PD-L1 signaling pathway have achieved unprecedented success in cancer treatment over the last few years. Atezolizumab is the first PD-L1 monoclonal antibody approved by US FDA for cancer therapy; however the molecular basis of atezolizumab in blocking PD-1/PD-L1 interaction is not fully understood. Here we have solved the crystal structure of PD-L1/atezolizumab complex at 2.9 angstrom resolution. The structure shows that atezolizumab binds the front beta-sheet of PD-L1 through three CDR loops from the heavy chain and one CDR loop from the light chain. The binding involves extensive hydrogen-bonding and hydrophobic interactions. Notably there are multiple aromatic residues from the CDR loops forming Pi-Pi stacking or cation-Pi interactions within the center of the binding interface and the buried surface area is more than 2000 Å2, which is the largest amongst all the known PD-L1/antibody structures. Mutagenesis study revealed that two hot-spot residues (E58, R113) of PD-L1 contribute significantly to the binding of atezolizumab. The structure also shows that atezolizumab binds PD-L1 with a distinct heavy and light chain orientation and it blocks PD-1/PD-L1 interaction through competing with PD-1 for the same PD-L1 surface area. Taken together, the complex structure of PD-L1/atezolizumab solved here revealed the molecular mechanism of atezolizumab in immunotherapy and provides basis for future monoclonal antibody optimization and rational design of small chemical compounds targeting PD-L1 surface. PMID:29163822

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.

Changes in the dissolved organic matter leaching from soil under severe temperature and N-deposition.

PubMed

Nguyen, Hang Vo-Minh; Choi, Jung Hyun

2015-06-01

In this study, we conducted growth chamber experiments using three types of soil (wetland, rice paddy, and forest) under the conditions of a severe increase in the temperature and N-deposition in order to investigate how extreme weather influences the characteristics of the dissolved organic matter (DOM) leaching from different soil types. This leachate controls the quantity and quality of DOM in surface water systems. After 5 months of incubation, the dissolved organic carbon (DOC) concentrations decreased in the range of 21.1 to 88.9 %, while the specific UV absorption (SUVA) values increased substantially in the range of 19.9 to 319.9 % for all of the samples. Higher increases in the SUVA values were observed at higher temperatures, whereas the opposite trend was observed for samples with N-addition. The parallel factor analysis (PARAFAC) results showed that four fluorescence components: terrestrial humic-like (component 1 (C1)), microbial humic-like (component 2 (C2)), protein-like (component 3 (C3)), and anthropogenic humic-like (component 4 (C4)) constituted the fluorescence matrices of soil samples. During the experiment, labile DOM from the soils was consumed and transformed into resistant aromatic carbon structures and less biodegradable components via microbial processes. The principle component analysis (PCA) results indicated that severe temperatures and N-deposition could enhance the contribution of the aromatic carbon compounds and humic-like components in the soil samples.

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%.

Design, Synthesis and Biological Evaluation of Novel Peptide-Like Analogues as Selective COX-2 Inhibitors

PubMed Central

Ahmaditaba, Mohammad Ali; Houshdar Tehrani, Mohammad Hassan; Zarghi, Afshin; Shahosseini, Sorayya; Daraei, Bahram

2018-01-01

A new series of peptide-like derivatives containing different aromatic amino acids and possessing pharmacophores of COX-2 inhibitors as SO2Me or N3 attached to the para position of an end phenyl ring was synthesized for evaluation as selective cyclooxygenase-2 (COX-2) inhibitors. The synthetic reactions were based on the solid phase peptide synthesis method using Wang resin. One of the analogues, i.e., compound 2d, as the representative of these series was recognized as the most effective and the highest selective COX-2 inhibitor with IC50 value of 0.08 μM and COX-2 selectivity index of 351.2, among the other synthesized compounds. Molecular docking study was operated to determine possible binding models of compound 2d to COX-2 enzyme. The study showed that the p-azido-phenyl fragment of 2d occupied inside the secondary COX-2 binding site (Arg513, and His90). The structure-activity relationships acquired disclosed that compound 2d with 4-(azido phenyl) group as pharmacophore and histidine as amino acid gives the essential geometry to provide inhibition of the COX-2 enzyme with high selectivity. Compound 2d can be a good candidate for the development of new hits of COX-2 inhibitors.

Are there physicochemical differences between allosteric and competitive ligands?

PubMed Central

Lu, Jing; Carlson, Heather A.

2017-01-01

Previous studies have compared the physicochemical properties of allosteric compounds to non-allosteric compounds. Those studies have found that allosteric compounds tend to be smaller, more rigid, more hydrophobic, and more drug-like than non-allosteric compounds. However, previous studies have not properly corrected for the fact that some protein targets have much more data than other systems. This generates concern regarding the possible skew that can be introduced by the inherent bias in the available data. Hence, this study aims to determine how robust the previous findings are to the addition of newer data. This study utilizes the Allosteric Database (ASD v3.0) and ChEMBL v20 to systematically obtain large datasets of both allosteric and competitive ligands. This dataset contains 70,219 and 9,511 unique ligands for the allosteric and competitive sets, respectively. Physically relevant compound descriptors were computed to examine the differences in their chemical properties. Particular attention was given to removing redundancy in the data and normalizing across ligand diversity and varied protein targets. The resulting distributions only show that allosteric ligands tend to be more aromatic and rigid and do not confirm the increase in hydrophobicity or difference in drug-likeness. These results are robust across different normalization schemes. PMID:29125840

Structure and function of CYP108D1 from Novosphingobium aromaticivorans DSM12444: an aromatic hydrocarbon-binding P450 enzyme.

PubMed

Bell, Stephen G; Yang, Wen; Yorke, Jake A; Zhou, Weihong; Wang, Hui; Harmer, Jeffrey; Copley, Rachel; Zhang, Aili; Zhou, Ruimin; Bartlam, Mark; Rao, Zihe; Wong, Luet Lok

2012-03-01

CYP108D1 from Novosphingobium aromaticivorans DSM12444 binds a range of aromatic hydrocarbons such as phenanthrene, biphenyl and phenylcyclohexane. Its structure, which is reported here at 2.2 Å resolution, is closely related to that of CYP108A1 (P450terp), an α-terpineol-oxidizing enzyme. The compositions and structures of the active sites of these two enzymes are very similar; the most significant changes are the replacement of Glu77 and Thr103 in CYP108A1 by Thr79 and Val105 in CYP108D1. Other residue differences lead to a larger and more hydrophobic access channel in CYP108D1. These structural features are likely to account for the weaker α-terpineol binding by CYP108D1 and, when combined with the presence of three hydrophobic phenylalanine residues in the active site, promote the binding of aromatic hydrocarbons. The haem-proximal surface of CYP108D1 shows a different charge distribution and topology to those of CYP101D1, CYP101A1 and CYP108A1, including a pronounced kink in the proximal loop of CYP108D1, which may result in poor complementarity with the [2Fe-2S] ferredoxins Arx, putidaredoxin and terpredoxin that are the respective redox partners of these three P450 enzymes. The unexpectedly low reduction potential of phenylcyclohexane-bound CYP108D1 (-401 mV) may also contribute to the low activity observed with these ferredoxins. CYP108D1 appears to function as an aromatic hydrocarbon hydroxylase that requires a different electron-transfer cofactor protein.

The geochemical and genetic role of organic substances in postmagmatic derivatives of alkaline plutons

NASA Astrophysics Data System (ADS)

Ermolaeva, V. N.; Chukanov, N. V.; Pekov, I. V.; Kogarko, L. N.

2009-12-01

Solid bituminous substances (SBS) are common components of the late hydrothermal mineral assemblages of peralkaline pegmatites. SBS are formed in a reductive setting as a result of progressive sorption of minor carbon-bearing molecules (CO, CO2, CH4, C2H6, C2H4, etc.), their polymerization, transformation into aromatic compounds (reformation), and selective oxidation on microporous zeolite-like Ti-, Nb-, and Zrsilicates serving as sorbents and catalysts. The oxygen-bearing aromatic compounds with hydrophile functional groups (-OH, -C=O, -COOH, -COO) act as complexing agents with respect to Th, REE, U, Zr, Ti, Nb, Ba, Sr, Ca, resulting in transfer of these bitumenophile elements under low-temperature hydrothermal conditions in the form of water-soluble macroassociates of the micelle type. Th, REE, and to a lesser extent, U, Zr, Ti, and Nb concentrate at the late stage of the hydrothermal process as microphases impregnating SBS or macroscopic segregations of Th and REE minerals. At the final stage, homogeneous SBS break down into organic (partly together with Ca, Sr, Ba, and Pb) and mineral (with Th, Ln, Y, Ti, Nb, Ca, Na, K, Si) microphases.

Pyridoxamine driven selective turn-off detection of picric acid using glutathione stabilized fluorescent copper nanoclusters and its applications with chemically modified cellulose strips.

PubMed

Patel, Ravi; Bothra, Shilpa; Kumar, Rajender; Crisponi, Guido; Sahoo, Suban K

2018-04-15

The present work reports the interaction of various vitamin B 6 cofactors with the red emitting glutathione stabilized copper nanoclusters (GSH-CuNCs). Addition of pyridoxamine (PM) resulted a new turn-on band at 410nm due to the possible adsorption over the surface of GSH-CuNCs. The nano-assembly PM-GSH-CuNCs was applied for the selective detection of nitro-aromatic compounds. Upon addition of picric acid (PA), the fluorescence of PM-GSH-CuNCs was selectively quenched at 410nm and ~ 625nm among the other tested nitro-aromatic compounds. With a linearity range from 9.9μM to 43μM, the concentration of PA can be detected down to 2.74μM. The high selectivity exhibited by the nano-assembly allows to detect PA in real samples like tap water, river water and matchstick. Advantageously, the nano-assembly PM-GSH-CuNCs was chemically adsorbed over the cellulosic strips and applied for the naked-eye detection of PA down to 1μM. Copyright © 2017 Elsevier B.V. All rights reserved.

Removal of crude oil polycyclic aromatic hydrocarbons via organoclay-microbe-oil interactions.

PubMed

Ugochukwu, Uzochukwu C; Fialips, Claire I

2017-05-01

Clay minerals are quite vital in biogeochemical processes but the effect of organo-clays in the microbial degradation of crude oil polycyclic aromatic hydrocarbons is not well understood. The role of organo-saponite and organo-montmorillonite in comparison with the unmodified clays in crude oil polycyclic aromatic hydrocarbons (PAHs) removal via adsorption and biodegradation was studied by carrying out microcosm experiments in aqueous clay/oil systems with a hydrocarbon degrading microbial community that is predominantly alcanivorax spp. Montmorillonite and saponite samples were treated with didecyldimethylammonium bromide to produce organo-montmorillonite and organo-saponite used in this study. Obtained results indicate that clays with high cation exchange capacity (CEC) such as montmorillonite produced organo-clay (organomontmorillonite) that was not stimulatory to biodegradation of crude oil polycyclic aromatic compounds, especially the low molecular weight (LMW) ones, such as dimethylnaphthalenes. It is suggested that interaction between the organic phase of the organo-clay and the crude oil PAHs which is hydrophobic in nature must have reduced the availability of the polycyclic aromatic hydrocarbons for biodegradation. Organo-saponite did not enhance the microbial degradation of dimethylnaphthalenes but enhanced the biodegradation of some other PAHs such as phenanthrene. The unmodified montmorillonite enhanced the microbial degradation of the PAHs and is most likely to have done so as a result of its high surface area that allows the accumulation of microbes and nutrients enhancing their contact. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of thenardite on the direct detection of aromatic amino acids: implications for the search for life in the solar system

NASA Astrophysics Data System (ADS)

Doc Richardson, C.; Hinman, Nancy W.; Scott, Jill R.

2009-10-01

With the discovery of Na-sulphate minerals on Mars and Europa, recent studies using these minerals have focused on their ability to assist in the detection of bio/organic signatures. This study further investigates the ability of thenardite (Na2SO4) to effectively facilitate the ionization and identification of aromatic amino acids (phenylalanine, tyrosine and tryptophan) using a technique called geomatrix-assisted laser desorption/ionization in conjunction with a Fourier transform ion cyclotron resonance mass spectrometry. This technique is based on the ability of a mineral host to facilitate desorption and ionization of bio/organic molecules for detection. Spectra obtained from each aromatic amino acid alone and in combination with thenardite show differences in ionization mechanism and fragmentation patterns. These differences are due to chemical and structural differences between the aromatic side chains of their respective amino acid. Tyrosine and tryptophan when combined with thenardite were observed to undergo cation-attachment ([M+Na]+), due to the high alkali ion affinity of their aromatic side chains. In addition, substitution of the carboxyl group hydrogen by sodium led to formation of [M-H+Na]Na+ peaks. In contrast, phenylalanine mixed with thenardite showed no evidence of Na+ attachment. Understanding how co-deposition of amino acids with thenardite can affect the observed mass spectra is important for future exploration missions that are likely to use laser desorption mass spectrometry to search for bio/organic compounds in extraterrestrial environments.

Effect of Thenardite on the Direct Detection of Aromatic Amino Acids: Implications for the Search for Life in the Solar System

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

C. Doc Richardson; Nancy W. Hinman; Jill R. Scott

2009-10-01

With the discovery of Na-sulfate minerals on Mars and Europa, recent studies using these minerals have focused on their ability to assist in the detection of bio/organic signatures. This study further investigates the ability of thenardite (Na2SO4) to effectively facilitate the ionization and identification of aromatic amino acids (phenylalanine, tyrosine, and tryptophan) using a technique called geomatrix-assisted laser desorption/ionization (GALDI) in conjunction with a Fourier transform mass spectrometry (FTICR-MS). This technique is based on the ability of a mineral host to facilitate the ionization and detection of bio/organic molecules. Spectra obtained from each aromatic amino acid alone and in combinationmore » with thenardite show differences in ionization mechanism and fragmentation patterns. These differences are due to chemical and structural differences between the aromatic side chains of their respective amino acid. Tyrosine and tryptophan when combined with thenardite were observed to undergo cation-attachment ([M+Na]+), due to the high alkali affinity of their aromatic side chains. Subsequent cation substitution of the carboxyl group led to formation double cation-attached peaks ([M-H+Na]Na+). In contrast, phenylalanine mixed with thenardite showed no evidence of Na+ interaction. Understanding how codeposition of amino acids with thenardite can affect the observed mass spectra is important for future exploration missions that are likely to use laser desorption mass spectrometry to search for bio/organic compounds in extraterrestrial environments.« less

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 external pore loop interacts with S6 and S3-S4 linker in domain 4 to assume an essential role in gating control and anticonvulsant action in the Na+ channel

PubMed Central

Yang, Ya-Chin; Hsieh, Jui-Yi

2009-01-01

Carbamazepine, phenytoin, and lamotrigine are widely prescribed anticonvulsants in neurological clinics. These drugs bind to the same receptor site, probably with the diphenyl motif in their structure, to inhibit the Na+ channel. However, the location of the drug receptor remains controversial. In this study, we demonstrate close proximity and potential interaction between an external aromatic residue (W1716 in the external pore loop) and an internal aromatic residue (F1764 in the pore-lining part of the sixth transmembrane segment, S6) of domain 4 (D4), both being closely related to anticonvulsant and/or local anesthetic binding to the Na+ channel. Double-mutant cycle analysis reveals significant cooperativity between the two phenyl residues for anticonvulsant binding. Concomitant F1764C mutation evidently decreases the susceptibility of W1716C to external Cd2+ and membrane-impermeable methanethiosulfonate reagents. Also, the W1716E/F1764R and G1715E/F1764R double mutations significantly alter the selectivity for Na+ over K+ and markedly shift the activation curve, respectively. W1716 and F1764 therefore very likely form a link connecting the outer and inner compartments of the Na+ channel pore (in addition to the selectivity filter). Anticonvulsants and local anesthetics may well traverse this “S6 recess” without trespassing on the selectivity filter. Furthermore, we found that Y1618K, a point mutation in the S3-4 linker (the extracellular extension of D4S4), significantly alters the consequences of carbamazepine binding to the Na+ channel. The effect of Y1618K mutation, however, is abolished by concomitant point mutations in the vicinity of Y1618, but not by those in the internally located inactivation machinery, supporting a direct local rather than a long-range allosteric action. Moreover, Y1618 could interact with D4 pore residues W1716 and L1719 to have a profound effect on both channel gating and anticonvulsant action. We conclude that there are direct interactions among the external S3-4 linker, the external pore loop, and the internal S6 segment in D4, making the external pore loop a pivotal point critically coordinating ion permeation, gating, and anticonvulsant binding in the Na+ channel. PMID:19635852

The external pore loop interacts with S6 and S3-S4 linker in domain 4 to assume an essential role in gating control and anticonvulsant action in the Na(+) channel.

PubMed

Yang, Ya-Chin; Hsieh, Jui-Yi; Kuo, Chung-Chin

2009-08-01

Carbamazepine, phenytoin, and lamotrigine are widely prescribed anticonvulsants in neurological clinics. These drugs bind to the same receptor site, probably with the diphenyl motif in their structure, to inhibit the Na(+) channel. However, the location of the drug receptor remains controversial. In this study, we demonstrate close proximity and potential interaction between an external aromatic residue (W1716 in the external pore loop) and an internal aromatic residue (F1764 in the pore-lining part of the sixth transmembrane segment, S6) of domain 4 (D4), both being closely related to anticonvulsant and/or local anesthetic binding to the Na(+) channel. Double-mutant cycle analysis reveals significant cooperativity between the two phenyl residues for anticonvulsant binding. Concomitant F1764C mutation evidently decreases the susceptibility of W1716C to external Cd(2+) and membrane-impermeable methanethiosulfonate reagents. Also, the W1716E/F1764R and G1715E/F1764R double mutations significantly alter the selectivity for Na(+) over K(+) and markedly shift the activation curve, respectively. W1716 and F1764 therefore very likely form a link connecting the outer and inner compartments of the Na(+) channel pore (in addition to the selectivity filter). Anticonvulsants and local anesthetics may well traverse this "S6 recess" without trespassing on the selectivity filter. Furthermore, we found that Y1618K, a point mutation in the S3-4 linker (the extracellular extension of D4S4), significantly alters the consequences of carbamazepine binding to the Na(+) channel. The effect of Y1618K mutation, however, is abolished by concomitant point mutations in the vicinity of Y1618, but not by those in the internally located inactivation machinery, supporting a direct local rather than a long-range allosteric action. Moreover, Y1618 could interact with D4 pore residues W1716 and L1719 to have a profound effect on both channel gating and anticonvulsant action. We conclude that there are direct interactions among the external S3-4 linker, the external pore loop, and the internal S6 segment in D4, making the external pore loop a pivotal point critically coordinating ion permeation, gating, and anticonvulsant binding in the Na(+) channel.

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.

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.

Mixing of sulfur between pyritic and organic phases during coal conversion processes: Annual final report, March 1, 1986-February 28, 1987

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

Dunkerton, L.V.; Nigam, A.; Mitra, S.

1987-05-01

In preparation for using /sup 33/S NMR for characterization of organic sulfur types in coal, previously prepared substituted dibenzothiophene model compounds were converted to their corresponding sulfones and their sulfur-33 nmr recorded. The sulfur-33 NMR spectra of dibenzothiophene-5,5-dioxide (2), 2-(p-methylphenylsulfonyl) dibenzothiophene-5,5-dioxide (4), and 2-(methylsulfonyl) dibenzothiophene-5,5-dioxide (6) are reported. The chemical shifts were in the +2 to -21 ppM range. The line widths ranged 70 to 200 Hz. The changes in /sup 13/C chemical shift experienced by aromatic carbons upon oxidizing the sulfide to its sulfone were also studied and the data used to identify which sulfone was formed in multiplemore » thioether-containing aromatics after partial oxidation. Continuing results on the use of the substituted dibenzothiophenes to monitor mixing of sulfur between pyritic and organic phases are also reported. Non-isothermal hydrodesulfurization of model organic sulfur compounds was carried out in a cola-like environment. The model sulfur compounds represented different types of carbon-sulfur bonds commonly encountered in coal. Similar experiments were carried out in the presence of troilite (iron sulfide) to investigate the possibility of sulfur migration from the organic compound to the iron sulfide. Next, iron pyrite was hydrodesulfurized in the presence of some organic molecules to see if sulfur could be incorporated into the organic molecules during the process. Results show that sulfur from organic compounds can be absorbed by troilite, and, similarly, sulfur from pyrite can form new carbon-sulfur bonds during hydrodesulfurization. Based on these observations, it is suggested that during coal conversion reactions it is possible to have intermigration of sulfur between the organic and the inorganic phases.« less

Chemical Composition of Soil Horizons and Aggregate Size Fractions Under the Hawaiian Fern Dicranopteris and Angiosperm Cheirodendrom

NASA Astrophysics Data System (ADS)

Stewart, C. E.; Amatangelo, K.; Neff, J.

2007-12-01

Soil organic matter (SOM) inherits much of its chemical nature from the dominant vegetation, including phenolic (lignin-derived), aromatic, and aliphatic (cutin and wax-derived) compounds. However, relatively stable recalcitrant compounds may also be formed as a result of condensation and complexation reactions through decomposition and protected with association with mineral particles. The Hawaiian fern species Dicranopteris decomposes more slowly than the angiosperm, Cheirodendrom due to high concentrations of recalcitrant C compounds. These aliphatic fern leaf waxes are well-preserved and may comprise a large portion of the recalcitrant organic matter in these soils. Our objective was to determine the chemical composition of the SOM under the O- (litter-dominated) and the A- (mineral) horizons formed under fern and angiosperm vegetation. To determine the effect of mineral-association, we fractioned the soil into four size classes; 850-590 μm, 590-180 μm, 180-53 μm and <53 μm and characterized the SOM via pyrolysis-gas chromatography-mass spectrometry (py-GC/MS). As the soils developed from the O- to the A-horizon, there was a decrease of lignin-derived phenolic compounds and an increase in more recalcitrant, aromatic and aliphatic C. Soils under ferns had greater relative concentrations of phenolic compounds, while the angiosperms had greater concentrations of fatty-acid methyl esters and furans (some polysaccharide-derived). Differences between size fractions were most evident in the O-horizon of both species. Recalcitrant fern-derived cutin and leaf waxes (alkene and alkanes structures) occurred in the 180-53 μm fraction, which has been shown to be the most stable of the aggregate-size fractions. Soils developed under fern versus angiosperm vegetation have distinct chemical signatures, which likely determine the recalcitrance of the SOM.

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.

Molecular Insights into Arctic Soil Organic Matter Degradation under Warming

DOE PAGES

Chen, Hongmei; Yang, Ziming; Chu, Rosalie K.; ...

2018-03-23

Molecular composition of the Arctic soil organic carbon (SOC) and its susceptibility to microbial degradation are uncertain due to heterogeneity and unknown SOC compositions. By using ultrahigh-resolution mass spectrometry, we determined the susceptibility and compositional changes of extractable dissolved organic matter (EDOM) in an anoxic warming incubation experiment (up to 122 days) with a tundra soil from Alaska (United States). EDOM was extracted with 10 mM NH 4HCO 3 from both the organic- and mineral-layer soils during incubation at both -2 and 8°C. Based on their O:C and H:C ratios, EDOM molecular formulas were qualitatively grouped into nine biochemical classesmore » of compounds, among which lignin-like compounds dominated both the organic and the mineral soils and were the most stable, whereas amino sugars, peptides, and carbohydrate-like compounds were the most biologically labile. These results corresponded with shifts in EDOM elemental composition in which the ratios of O:C and N:C decreased, while the average C content in EDOM, molecular mass, and aromaticity increased after 122 days of incubation. This research demonstrates that certain EDOM components, such as amino sugars, peptides, and carbohydrate-like compounds, are disproportionately more susceptible to microbial degradation than others in the soil, and these results should be considered in SOC degradation models to improve predictions of Arctic climate feedbacks.« less

Molecular Insights into Arctic Soil Organic Matter Degradation under Warming

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

Chen, Hongmei; Yang, Ziming; Chu, Rosalie K.

Molecular composition of the Arctic soil organic carbon (SOC) and its susceptibility to microbial degradation are uncertain due to heterogeneity and unknown SOC compositions. By using ultrahigh-resolution mass spectrometry, we determined the susceptibility and compositional changes of extractable dissolved organic matter (EDOM) in an anoxic warming incubation experiment (up to 122 days) with a tundra soil from Alaska (United States). EDOM was extracted with 10 mM NH 4HCO 3 from both the organic- and mineral-layer soils during incubation at both -2 and 8°C. Based on their O:C and H:C ratios, EDOM molecular formulas were qualitatively grouped into nine biochemical classesmore » of compounds, among which lignin-like compounds dominated both the organic and the mineral soils and were the most stable, whereas amino sugars, peptides, and carbohydrate-like compounds were the most biologically labile. These results corresponded with shifts in EDOM elemental composition in which the ratios of O:C and N:C decreased, while the average C content in EDOM, molecular mass, and aromaticity increased after 122 days of incubation. This research demonstrates that certain EDOM components, such as amino sugars, peptides, and carbohydrate-like compounds, are disproportionately more susceptible to microbial degradation than others in the soil, and these results should be considered in SOC degradation models to improve predictions of Arctic climate feedbacks.« less

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.

Bioremediation of oil spills by whale microbes. Final report, 1994-1995

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

Craig, A.M.; Wachenheim, D.

1995-06-01

Baleen whale forestomach anaerobic microbes were studied for their ability to detoxify recalcitrant environmental pollutants; these include components of crude oil and some chlorinated aromatic compounds which are constituents of oil spills not biodegraded by aerobic microbes. In this study, forestomach rumen samples were collected on two occasions on the North Slope. When incubated with anthracene and naphthalene (PAH), these pollutants were degraded in the majority of sample sets. All simple aromatic hydrocarbons (benzine, toluene, xylenes, ethylbenzene) were degraded. PCBs were biodegraded by microbes from only two of the whales. Variable results were found with picric acid, trinitrotoluene (TNT), andmore » atrazine, and were likely due to analytical difficulties. Whale forestomach bacteria have adapted to an ecological niche where flow rates, mixing, and catabolism occur at rapid rates. These rates and the ability to metabolize complex molecules far exceed those of aerobic sediment and soil bacteria in biodegradation of environmental pollutants.« less

Computational and experimental study of the interactions between ionic liquids and volatile organic compounds.

PubMed

Gao, Tingting; Andino, Jean M; Alvarez-Idaboy, J Raul

2010-09-07

Computational chemistry calculations were performed to investigate the interactions of ionic liquids with different classes of volatile organic compounds (VOCs), including alcohols, aldehydes, ketones, alkanes, alkenes, alkynes and aromatic compounds. At least one VOC was studied to represent each class. Initially, 1-butyl-3-methylimindazolium chloride (abbreviated as C(4)mimCl) was used as the test ionic liquid compound. Calculated interaction lengths between atoms in the ionic liquid and the VOC tested as well as thermodynamic data suggest that C(4)mimCl preferentially interacts with alcohols as compared to other classes of volatile organic compounds. The interactions of methanol with different kinds of ionic liquids, specifically 1-butyl-3-methylimidazolium bromine (C(4)mimBr) and 1-butyl-3-methylimidazolium tetrafluoroborate (C(4)mimBF(4)) were also studied. In comparing C(4)mimCl, C(4)mimBr, and C(4)mimBF(4), the computational results suggest that C(4)mimCl is more likely to interact with methanol. Laboratory experiments were performed to provide further evidence for the interaction between C(4)mimCl and different classes of VOCs. Fourier transform infrared spectroscopy was used to probe the ionic liquid surface before and after exposure to the VOCs that were tested. New spectral features were detected after exposure of C(4)mimCl to various alcohols. The new features are characteristic of the alcohols tested. No new IR features were detected after exposure of the C(4)mimCl to the aldehyde, ketone, alkane, alkene, alkyne or aromatic compounds studied. In addition, after exposing the C(4)mimCl to a multi-component mixture of various classes of compounds (including an alcohol), the only new peaks that were detected were characteristic of the alcohol that was tested. These experimental results demonstrated that C(4)mimCl is selective to alcohols, even in complex mixtures. The findings in this work provide information for future gas-phase alcohol sensor design.

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

Graphene nanosheets and graphite oxide as promising adsorbents for removal of organic contaminants from aqueous solution.

PubMed

Ji, Liangliang; Chen, Wei; Xu, Zhaoyi; Zheng, Shourong; Zhu, Dongqiang

2013-01-01

Graphenes are an emerging class of carbon nanomaterials whose adsorption properties toward organic compounds have not been well understood. In the present study, graphene nanosheets were prepared by reoxidation and abrupt heating of graphite oxide, which was prepared by sequential chemical oxidation of commercial nonporous graphite powder. Adsorption properties of three aromatic compounds (naphthalene, 2-naphthol, and 1-naphthylamine) and one pharmaceutical compound (tylosin) on graphene nanosheets and graphite oxide were examined to explore the potential of these two adsorbents for the removal of organic contaminants from aqueous solutions. Compared with the literature data of adsorption on carbon nanotubes, adsorption of bulky, flexible tylosin on graphene nanosheets exhibited markedly faster adsorption kinetics, which can be attributed to their opened-up layer structure. Graphene nanosheets and graphite oxide showed similar sequences of adsorption affinity: 1-naphthylamine > 2-naphthol > tylosin > naphthalene (with much larger differences observed on graphite oxide). It was proposed that the strong adsorption of the three aromatic compounds was mainly due to π-π electron donor-acceptor interactions with the graphitic surfaces of adsorbents. Additionally, Lewis acid-base interaction was likely an important factor contributing to the strong adsorption of 1-naphthylamine and tylosin, especially for the O-functionality-abundant graphite oxide. After being normalized on the basis of adsorbent surface area, adsorption affinities of all four tested adsorbates on graphene nanosheets were very close to those on nonporous graphite powder, reflecting complete accessibility of the adsorbent surface area in adsorption. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Fluorescence evolution of leachates during treatment processes from two contrasting landfills.

PubMed

Sun, W L; Liu, T T; Cui, F; Ni, J R

2008-10-01

Landfill leachates are composed of a complex mixture of organic matter, including a wide range of potentially fluorescent organic compounds. The fluorescence excitation-emission matrix (FEEM) of leachates during treatment processes is investigated. Particular attention is paid to the fluorescence evolution of leachates during treatment processes. Two typical types of landfill, landfill A (a direct municipal solid waste (MSW) landfill) and landfill B (disposal of bottom ashes from MSW incinerators), in a city in Southern China were selected. The results show that two characteristic and intense excitation-emission peaks located at Ex/Em = 310-330 nm/395-410 nm (peak alpha) and Ex/Em = 250-260 nm/450-460 nm (peak alpha') are observed. As the aromatic chemicals, capable of emitting fluorescence, are more recalcitrant to biodegradation than aliphatic chemicals, enhancement of the dissolved organic carbon normalized fluorescence intensities is demonstrated during treatment processes of leachate A and leachate B. This is confirmed by the variation of ultraviolet absorptivity of leachates at 254 nm. Peak alpha' and peak alpha are attributed to a mixture of xenobiotic organic compounds with low molecular weight and relatively stable aromatic fulvic-like matters with high molecular weight, respectively. Humic substances are more resistant to biodegradation than xenobiotic organic compounds, so a significant reduction in the Ialpha'/Ialpha values (fluorescence intensity ratios of peak alpha' and peak a) of leachate A was observed during treatment processes. However, no evident variation for the Ialpha/Ialpha values of leachate B was found during treatment processes owing to the low concentrations of xenobiotic organic compounds in leachate B after incineration.

Disturbances of Ligand Potency and Enhanced Degradation of the Human Glycine Receptor at Affected Positions G160 and T162 Originally Identified in Patients Suffering from Hyperekplexia

PubMed Central

Atak, Sinem; Langlhofer, Georg; Schaefer, Natascha; Kessler, Denise; Meiselbach, Heike; Delto, Carolyn; Schindelin, Hermann; Villmann, Carmen

2015-01-01

Ligand-binding of Cys-loop receptors is determined by N-terminal extracellular loop structures from the plus as well as from the minus side of two adjacent subunits in the pentameric receptor complex. An aromatic residue in loop B of the glycine receptor (GlyR) undergoes direct interaction with the incoming ligand via a cation-π interaction. Recently, we showed that mutated residues in loop B identified from human patients suffering from hyperekplexia disturb ligand-binding. Here, we exchanged the affected human residues by amino acids found in related members of the Cys-loop receptor family to determine the effects of side chain volume for ion channel properties. GlyR variants were characterized in vitro following transfection into cell lines in order to analyze protein expression, trafficking, degradation and ion channel function. GlyR α1 G160 mutations significantly decrease glycine potency arguing for a positional effect on neighboring aromatic residues and consequently glycine-binding within the ligand-binding pocket. Disturbed glycinergic inhibition due to T162 α1 mutations is an additive effect of affected biogenesis and structural changes within the ligand-binding site. Protein trafficking from the ER toward the ER-Golgi intermediate compartment, the secretory Golgi pathways and finally the cell surface is largely diminished, but still sufficient to deliver ion channels that are functional at least at high glycine concentrations. The majority of T162 mutant protein accumulates in the ER and is delivered to ER-associated proteasomal degradation. Hence, G160 is an important determinant during glycine binding. In contrast, T162 affects primarily receptor biogenesis whereas exchanges in functionality are secondary effects thereof. PMID:26733802

Anaerobic biodegradation of aromatic compounds.

PubMed

Jothimani, P; Kalaichelvan, G; Bhaskaran, A; Selvaseelan, D Augustine; Ramasamy, K

2003-09-01

Many aromatic compounds and their monomers are existing in nature. Besides they are introduced into the environment by human activity. The conversion of these aromatic compounds is mainly an aerobic process because of the involvement of molecular oxygen in ring fission and as an electron acceptor. Recent literatures indicated that ring fission of monomers and obligomers mainly occurs in anaerobic environments through anaerobic respiration with nitrate, sulphate, carbon dioxide or carbonate as electron acceptors. These anaerobic processes will help to work out the better situation for bioremediation of contaminated environments. While there are plenty of efforts to reduce the release of these chemicals to the environment, already contaminated sites need to be remediated not only to restore the sites but to prevent the leachates spreading to nearby environment. Basically microorganisms are better candidates for breakdown of these compounds because of their wider catalytic mechanisms and the ability to act even in the absence of oxygen. These microbes can be grouped based on their energy mechanisms. Normally, the aerobic counterparts employ the enzymes like mono-and-dioxygenases. The end product is basically catechol, which further may be metabolised to CO2 by means of quinones reductases cycles. In the absense of reductases compounds, the reduced catechols tend to become oxidised to form many quinone compounds. The quinone products are more recalcitrant and lead to other aesthetic problems like colour in water, unpleasant odour, etc. On the contrary, in the reducing environment this process is prevented and in a cascade of pathways, the cleaved products are converted to acetyl co-A to be integrated into other central metabolite paths. The central metabolite of anaerobic degradation is invariably co-A thio-esters of benzoic acid or hydroxy benzoic acid. The benzene ring undergoes various substitution and addition reactions to form chloro-, nitro-, methyl- compounds. For complete degradation the side chains must be removed first and then the benzene ring is activated by carboxylation or hydroxylation or co-A thioester formation. In the next step the activated ring is converted to a form that can be collected in the central pool of metabolism. The third step is the channeling reaction in which the products of the catalysis are directed into central metabolite pool. The enzymes involved in these mechanisms are mostly benzyl co-A ligase, benzyl alcohol dehydrogenase. Other enzymes involved in this path are yet to be purified though many of the reactions products that have been theoretically postulated have been identified. This is mainly due to the instability of intermediate compounds as well as the association of the enzyme substrate is femoral and experimental conditions need to be sophisticated further for isolation of these enzymes. The first structural genes of benzoate and hydroxy benzoate ligases were isolated from Rhodopseudomonas palustris. This gene cluster of 30 kb size found in Rhodopseudomonas palustris coded for the Bad A protein. Similarly, some of the bph A,B,C and D cluster of genes coding for the degradation of pentachlorobenzenes were located in Pseudomonas pseudoalgaligenesKF 707.

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...

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 Infrared Spectra of Polycyclic Aromatic Hydrocarbons with Excess Peripheral H Atoms (Hn-PAHs) and their Relation to the 3.4 and 6.9 µm PAH Emission Features

PubMed Central

Sandford, Scott A.; Bernstein, Max P.; Materese, Christopher K.

2015-01-01

Polycyclic aromatic hydrocarbons (PAHs) are likely responsible for the family of infrared emission features seen in a wide variety of astrophysical environments. A potentially important subclass of these materials are PAHs whose edges contain excess H atoms (Hn-PAHs). This type of compound may be present in space, but it has been difficult to assess this possibility because of a lack of suitable laboratory spectra to assist with analysis of astronomical data. We present 4000-500 cm−1 (2.5–20 µm) infrared spectra of 23 Hn-PAHs and related molecules isolated in argon matrices under conditions suitable for interpretation of astronomical data. Spectra of molecules with mixed aromatic and aliphatic domains show characteristics that distinguish them from fully aromatic PAH equivalents. Two major changes occur as PAHs become more hydrogenated: (1) aromatic C-H stretching bands near 3.3 µm weaken and are replaced with stronger aliphatic bands near 3.4 µm, and (2) aromatic C-H out-of-plane bending mode bands in the 11–15 µm region shift and weaken concurrent with growth of a strong aliphatic -CH2-deformation mode near 6.9 µm. Implications for interpreting astronomical spectra are discussed with emphasis on the 3.4 and 6.9 µm features. Laboratory data is compared with emission spectra from IRAS 21282+5050, an object with normal PAH emission features, and IRAS 22272+5435 and IRAS 0496+3429, two protoplanetary nebulae with abnormally large 3.4 µm features. We show that ‘normal’ PAH emission objects contain relatively few Hn-PAHs in their emitter populations, but less evolved protoplanetary nebulae may contain significant abundances of these molecules. PMID:26435553

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.

Natural Product Molecular Fossils.

PubMed

Falk, Heinz; Wolkenstein, Klaus

The natural products synthesized by organisms that were living a long time ago gave rise to their molecular fossils. These can consist of either the original unchanged compounds or they may undergo peripheral transformations in which their skeletons remain intact. In cases when molecular fossils can be traced to their organismic source, they are termed "geological biomarkers".This contribution describes apolar and polar molecular fossils and, in particular biomarkers, along the lines usually followed in organic chemistry textbooks, and points to their bioprecursors when available. Thus, the apolar compounds are divided in linear and branched alkanes followed by alicyclic compounds and aromatic and heterocyclic molecules, and, in particular, the geoporphyrins. The polar molecular fossils contain as functional groups or constituent units ethers, alcohols, phenols, carbonyl groups, flavonoids, quinones, and acids, or are polymers like kerogen, amber, melanin, proteins, or nucleic acids. The final sections discuss the methodology used and the fundamental processes encountered by the biomolecules described, including diagenesis, catagenesis, and metagenesis.

Diagenesis of metabolites and a discussion of the origin of petroleum hydrocarbons

USGS Publications Warehouse

Breger, I.A.

1960-01-01

Proteins and carbohydrates are rapidly degraded to compounds of no direct interest in the problem of the origin of petroleum. Lignin, if carried into marine basins in the form of humic substances, is probably the major progenitor of kerogen rather than the precursor of petroleum. Pigments are but minor contributors to petroleum. The fate of fatty acids in a marine environment is not completely understood. Although they may not be directly decarboxylated biochemically, it is shown how they can be converted into oxygenated or dehydrogenated acids more reactive than the parent compounds. Illustrations are also given for Diels-Alder reactions that could account for the formation from these compounds of the alicyclic and aromatic hydrocarbons in petroleum. It is most likely that crude oil is generated in sediments containing concentrations of lipids, the character of which governs the nature of the oil that is formed. ?? 1960.

Specific interaction between negative atmospheric ions and organic compounds in atmospheric pressure corona discharge ionization mass spectrometry.

PubMed

Sekimoto, Kanako; Sakai, Mami; Takayama, Mitsuo

2012-06-01

The interaction between negative atmospheric ions and various types of organic compounds were investigated using atmospheric pressure corona discharge ionization (APCDI) mass spectrometry. Atmospheric negative ions such as O(2)(-), HCO(3)(-), COO(-)(COOH), NO(2)(-), NO(3)(-), and NO(3)(-)(HNO(3)) having different proton affinities served as the reactant ions for analyte ionization in APCDI in negative-ion mode. The individual atmospheric ions specifically ionized aliphatic and aromatic compounds with various functional groups as atmospheric ion adducts and deprotonated analytes. The formation of the atmospheric ion adducts under certain discharge conditions is most likely attributable to the affinity between the analyte and atmospheric ion and the concentration of the atmospheric ion produced under these conditions. The deprotonated analytes, in contrast, were generated from the adducts of the atmospheric ions with higher proton affinity attributable to efficient proton abstraction from the analyte by the atmospheric ion.

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.

Spectroscopic characterization of digestates obtained from sludge mixed to increasing amounts of fruit and vegetable wastes

NASA Astrophysics Data System (ADS)

Provenzano, Maria Rosaria; Cavallo, Ornella; Malerba, Anna Daniela; Di Maria, Francesco; Ricci, Anna; Gigliotti, Giovanni

2015-04-01

Anaerobic digestion (AD) represents an efficient waste-treatment technology during which microorganisms break down biodegradable material in absence of oxygen yielding a biogas containing methane. The aim of this work was to investigate the transformations occurring in the organic matter during the co-digestion of waste mixed sludge (WMS) with an increasing amount of fruit and vegetable wastes (FVW) in a pilot scale apparatus reproducing a full-scale digester in an existing wastewater treatment plant. Samples comprised: sludge, FVW, sludge mixed with 10-20-30-40% FVW. Ingestates and digestates were analyzed by means of emission fluorescence spectroscopy and FTIR associated to Fourier self deconvolution (FSD) of spectra. With increasing the amount of FVW from 10% to 20% at which percentage biogas production reached the maximum value, FTIR spectra and FSD traces of digestates exhibited a decrease of intensity of peaks assigned to polysaccharides and aliphatics and an increase of peak assigned to aromatics as a result of the biodegradation of rapidly degradable materials and concentration of aromatic recalcitrant compounds. Digestates with 30 and 40% FVW exhibited a relative increase of intensity of peaks assigned to aliphatics likely as a result of the increasing amount of rapidly degradable materials and the consequent reduction of the hydraulic retention time. This may cause inhibition of methanogenesis and accumulation of volatile fatty acids. The highest emission fluorescence intensity was observed for the digestate with 20% FVW confirming the concentration of aromatic recalcitrant compounds in the substrate obtained at the highest biogas production.

Fluorescence Excitation-Emission Matrix Regional Integration to Quantify Spectra for Dissolved Organic Matter

USGS Publications Warehouse

Chen, W.; Westerhoff, P.; Leenheer, J.A.; Booksh, K.

2003-01-01

Excitation-emission matrix (EEM) fluorescence spectroscopy has been widely used to characterize dissolved organic matter (DOM) in water and soil. However, interpreting the >10,000 wavelength-dependent fluorescence intensity data points represented in EEMs has posed a significant challenge. Fluorescence regional integration, a quantitative technique that integrates the volume beneath an EEM, was developed to analyze EEMs. EEMs were delineated into five excitation-emission regions based on fluorescence of model compounds, DOM fractions, and marine waters or freshwaters. Volumetric integration under the EEM within each region, normalized to the projected excitation-emission area within that region and dissolved organic carbon concentration, resulted in a normalized region-specific EEM volume (??i,n). Solid-state carbon nuclear magnetic resonance (13C NMR), Fourier transform infrared (FTIR) analysis, ultraviolet-visible absorption spectra, and EEMs were obtained for standard Suwannee River fulvic acid and 15 hydrophobic or hydrophilic acid, neutral, and base DOM fractions plus nonfractionated DOM from wastewater effluents and rivers in the southwestern United States. DOM fractions fluoresced in one or more EEM regions. The highest cumulative EEM volume (??T,n = ????i,n) was observed for hydrophobic neutral DOM fractions, followed by lower ??T,n values for hydrophobic acid, base, and hydrophilic acid DOM fractions, respectively. An extracted wastewater biomass DOM sample contained aromatic protein- and humic-like material and was characteristic of bacterial-soluble microbial products. Aromatic carbon and the presence of specific aromatic compounds (as indicated by solid-state 13C NMR and FTIR data) resulted in EEMs that aided in differentiating wastewater effluent DOM from drinking water DOM.

On the Interaction between Carbon Dioxide and Nanomaterials with High Accuracy ab initio and DFT Calculations

NASA Astrophysics Data System (ADS)

Vogiatzis, Konstantinos D.; Mavrandonakis, Antreas; Klopper, Wim; Froudakis, George

2009-08-01

The separation, capture and storage of carbon dioxide from the flue gas is an environmental and economical problem of significant importance. Zeolites and activated carbons have been used from the industries in order to reduce the emissions of CO2. A new family of materials, the metal-organic frameworks (MOFs), has been recently proposed as an efficient substitute of the abovementioned materials. In particular, materials based on zinc complexes with imidazo-like aromatic compounds which builds frameworks similar with those of Zeolites (Zeolite-Imidazolium Frameworks, ZIFs), have the potential for efficient separation of CO2 from CO and CH4. [1]. Weak interactions between carbon dioxide and heterocyclic aromatic compounds are being examined with high accuracy ab initio methods. CO2 has zero dipole moment but a significant quadrupole moment enables it to operate as a weak acid or weak base, according to his environment. Nitrogen-containing aromatic compounds act as electron donors, while CO2 acts as an electron acceptor. Electrostatic interactions induce a non-permanent dipole moment on CO2 and the complex is stabilized by in-plane hydrogen bonds between the charged oxygens of CO2 and nearby hydrogen of the aromatic molecule. In addition, dispersion forces from the electron correlation contribute to the interaction energy. By using explicitly correlated methods (MP2-F12/aug-cc-pVTZ) [2] and by adding the contribution from the triples excitations, calculated with a smaller basis (6-311++G**), we reach to an approximate CCSD(T) complete basis set result. [3] Extrapolation schemes were used in order to reach the MP2 basis set limit and compare it with the CCSD(T)/CBS result. Those results are in excellent agreement with the explicitly correlated MP2-F12. In addition, our complexes are being investigated with DFT methods that calculate separately the dispersion energy (DFT-D) [4] and modified MP2 which scaling of spin pair correlation [5]. DFT-D results are in good agreement with CCSD(T)/CBS results, providing us a computational cheap method with high accuracy. The quantization of the interaction is examined by changing the aromaticity of the heterocyclic molecules and by talking into account the electron correlation. [6] The electron density of the nitrogen that binds CO2 is gradually decreasing by substituting carbons with nitrogens in pyridine (pyrimidine, pyrazine, triazine), leading to lower binding energy.

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

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.

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).

Au99(SPh)42 nanomolecules: aromatic thiolate ligand induced conversion of Au144(SCH2CH2Ph)60.

PubMed

Nimmala, Praneeth Reddy; Dass, Amala

2014-12-10

A new aromatic thiolate protected gold nanomolecule Au99(SPh)42 has been synthesized by reacting the highly stable Au144(SCH2CH2Ph)60 with thiophenol, HSPh. The ubiquitous Au144(SR)60 is known for its high stability even at elevated temperature and in the presence of excess thiol. This report demonstrates for the first time the reactivity of the Au144(SCH2CH2Ph)60 with thiophenol to form a different 99-Au atom species. The resulting Au99(SPh)42 compound, however, is unreactive and highly stable in the presence of excess aromatic thiol. The molecular formula of the title compound is determined by high resolution electrospray mass spectrometry (ESI-MS) and confirmed by the preparation of the 99-atom nanomolecule using two ligands, namely, Au99(SPh)42 and Au99(SPh-OMe)42. This mass spectrometry study is an unprecedented advance in nanoparticle reaction monitoring, in studying the 144-atom to 99-atom size evolution at such high m/z (∼12k) and resolution. The optical and electrochemical properties of Au99(SPh)42 are reported. Other substituents on the phenyl group, HS-Ph-X, where X = -F, -CH3, -OCH3, also show the Au144 to Au99 core size conversion, suggesting minimal electronic effects for these substituents. Control experiments were conducted by reacting Au144(SCH2CH2Ph)60 with HS-(CH2)n-Ph (where n = 1 and 2), bulky ligands like adamantanethiol and cyclohexanethiol. It was observed that conversion of Au144 to Au99 occurs only when the phenyl group is directly attached to the thiol, suggesting that the formation of a 99-atom species is largely influenced by aromaticity of the ligand and less so on the bulkiness of the ligand.

Response of Rhodococcus erythropolis strain IBBPo1 to toxic organic solvents

PubMed Central

Stancu, Mihaela Marilena

2015-01-01

Abstract Recently, there has been a lot of interest in the utilization of rhodococci in the bioremediation of petroleum contaminated environments. This study investigates the response of Rhodococcus erythropolis IBBPo1 cells to 1% organic solvents (alkanes, aromatics). A combination of microbiology, biochemical, and molecular approaches were used to examine cell adaptation mechanisms likely to be pursued by this strain after 1% organic solvent exposure. R. erythropolis IBBPo1 was found to utilize 1% alkanes (cyclohexane, n-hexane, n-decane) and aromatics (toluene, styrene, ethylbenzene) as the sole carbon source. Modifications in cell viability, cell morphology, membrane permeability, lipid profile, carotenoid pigments profile and 16S rRNA gene were revealed in R. erythropolis IBBPo1 cells grown 1 and 24 h on minimal medium in the presence of 1% alkanes (cyclohexane, n-hexane, n-decane) and aromatics (toluene, styrene, ethylbenzene). Due to its environmental origin and its metabolic potential, R. erythropolis IBBPo1 is an excellent candidate for the bioremediation of soils contaminated with crude oils and other toxic compounds. Moreover, the carotenoid pigments produced by this nonpathogenic Gram-positive bacterium have a variety of other potential applications. PMID:26691458

Forming a Two-Ring Polycyclic Aromatic Hydrocarbon without a Benzene Intermediate: the Reaction of Propargyl with Acetylene

NASA Astrophysics Data System (ADS)

Osborn, David; Savee, John; Selby, Talitha; Welz, Oliver; Taatjes, Craig

The reaction of acetylene (HCCH) with a resonance-stabilized free radical is a commonly invoked mechanism for the generation of polycyclic aromatic hydrocarbons (PAH), which are likely precursors of soot particles in combustion. In this work, we examine the sequential addition of acetylene to the propargyl radical (H2CCCH) at temperatures of 800 and 1000 K. Using time-resolved multiplexed photoionization mass spectrometry with tunable ionizing radiation, we identified the isomeric forms of the C5H5 and C7H7 intermediates in this reaction sequence, and confirmed that the final C9H8 product is the two-ring aromatic compound indene. We identified two different resonance-stabilized C5H5 intermediates, with different temperature dependencies. Furthermore, the C7H7 intermediate is the tropyl radical (c-C7H7) , not the benzyl radical (C6H5CH2) , as is usually assumed in combustion environments. These experimental results are in general agreement with the latest electronic structure / master equation results of da Silva et al. This work shows a pathway for PAH formation that bypasses benzene / benzyl intermediates.

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.

Research Advances: Less Expensive and More Convenient Gaucher's Disease Treatment; Structural Loop Regions: Key to Multidrug-Resistance Transporters?; New Method Identifies Proteins in Old Artwork

ERIC Educational Resources Information Center

King, Angela G.

2006-01-01

The X-ray structure of EmrD, a multidrug transporter protein from Escherichia coli, common bacteria known to cause several food-borne illnesses was determined by scientists at The Scripps Research Institute. The hydrophobic residues in the EmrD internal cavity are likely to contribute to the general mechanism transporting various compounds through…

Derived Emission Rates and Photochemical Production Rates of Volatile Organic Compounds (VOCs) Associated with Oil and Natural Gas Operations in the Uintah Basin, UT During a Wintertime Ozone Formation Event

NASA Astrophysics Data System (ADS)

Koss, A.; De Gouw, J. A.; Warneke, C.; Gilman, J.; Lerner, B. M.; Graus, M.; Yuan, B.; Edwards, P. M.; Brown, S. S.; Wild, R. J.; Roberts, J. M.; Bates, T. S.; Quinn, P.

2014-12-01

The Uintah Basin, an oil and natural gas extraction field in Utah, experienced extremely high levels of volatile organic compounds (VOCs) and ozone during the winter of 2013 - up to 100 ppmv carbon and 150 ppbv O3. Here we interpret VOCs measured during an ozone formation event from 31 Jan 2013 to 8 Feb 2013. Ratios of VOCs show strong diurnal cycles and week-long trends. A simple analysis was applied to ratios of aromatic VOCs measured by proton transfer reaction mass spectrometer (PTR-MS) to explain these trends and to estimate emission rates of aromatic VOCs from oil and natural gas extraction, VOC emission ratios relative to benzene, and ambient [OH]. The analysis incorporates the following assumptions: (1) the source composition of emitted VOCs and their emission rates were temporally and spatially constant, and (2) the removal of VOCs was governed by reaction with OH, diurnal profile of which is constrained by measured photolysis rates. The main findings are (1) the emission rate of methane, extrapolated from the emission rate of benzene, is on the same order as an independent estimate from aircraft measurements of methane in 2012, (2) the derived aromatic emission ratios are consistent with source contributions from both oil and gas producing wells, and (3) calculated daily OH concentrations are low, peaking at 1x106 molecules cm-3. The analysis was extended to investigate secondary production of oxygenated VOCs measured by PTR-MS. The analysis is able to explain daytime production, but it does not adequately explain nighttime behavior, which may be affected by complex deposition to snow and ice surfaces. The relative carbon mass of primary and secondary compounds was calculated and compared to observations. At the end of the ozone formation event (day 6), our analysis predicts that secondary (oxidized) VOCs should comprise about 40% of total carbon mass. However, only 12% of these compounds are accounted for by measured oxygenated VOCs and organic aerosol. Additionally, formation rates of measured oxygenated VOCs did not sum to the total primary compound oxidation rate. The disparity is likely due to both incomplete measurements of oxygenated products and VOC loss to deposition.

Quantitative estimation of pesticide-likeness for agrochemical discovery.

PubMed

Avram, Sorin; Funar-Timofei, Simona; Borota, Ana; Chennamaneni, Sridhar Rao; Manchala, Anil Kumar; Muresan, Sorel

2014-12-01

The design of chemical libraries, an early step in agrochemical discovery programs, is frequently addressed by means of qualitative physicochemical and/or topological rule-based methods. The aim of this study is to develop quantitative estimates of herbicide- (QEH), insecticide- (QEI), fungicide- (QEF), and, finally, pesticide-likeness (QEP). In the assessment of these definitions, we relied on the concept of desirability functions. We found a simple function, shared by the three classes of pesticides, parameterized particularly, for six, easy to compute, independent and interpretable, molecular properties: molecular weight, logP, number of hydrogen bond acceptors, number of hydrogen bond donors, number of rotatable bounds and number of aromatic rings. Subsequently, we describe the scoring of each pesticide class by the corresponding quantitative estimate. In a comparative study, we assessed the performance of the scoring functions using extensive datasets of patented pesticides. The hereby-established quantitative assessment has the ability to rank compounds whether they fail well-established pesticide-likeness rules or not, and offer an efficient way to prioritize (class-specific) pesticides. These findings are valuable for the efficient estimation of pesticide-likeness of vast chemical libraries in the field of agrochemical discovery. Graphical AbstractQuantitative models for pesticide-likeness were derived using the concept of desirability functions parameterized for six, easy to compute, independent and interpretable, molecular properties: molecular weight, logP, number of hydrogen bond acceptors, number of hydrogen bond donors, number of rotatable bounds and number of aromatic rings.

Bench-scale evaluation of in situ bioremediation strategies for soil at a former manufactured gas plant site.

PubMed

Li, Jun; Pignatello, Joseph J; Smets, Barth F; Grasso, Domenico; Monserrate, Esteban

2005-03-01

We examined the biodegradation and desorption of a set of 15 polycyclic aromatic hydrocarbon (PAH) compounds in coal tar-contaminated soil at a former manufactured gas plant site to evaluate the feasibility of in situ bioremediation. Experiments were conducted in well-mixed aerobic soil suspensions containing various additives over a 93- to 106-d period. In general, both biotransformation and desorption decreased with PAH ring size, becoming negligible for the six-ring PAH compounds. Biodegradation by indigenous microorganisms was strongly accelerated by addition of inorganic nutrients (N, P, K, and trace metals). The rates of biotransformation of PAH compounds by indigenous microorganisms in nutrient-amended flasks outpaced their maximum (i.e., chelate-enhanced) rates of desorption to an infinite sink (Tenax) in sterilized systems run in parallel, suggesting that indigenous organisms facilitated desorption. Biodegradation by indigenous organisms in nutrient-amended flasks appeared to be unaffected by the addition of a site-derived bacterial enrichment culture, resulting in approximately 100-fold higher aromatic dioxygenase levels, and by the addition of 0.01 M chelating agent (citrate or pyrophosphate), although such chelating agents greatly enhanced desorption in microbially inactivated flasks. The strong ability of nutrients to enhance degradation of the bioavailable PAHs indicates that their persistence for many decades at this site likely results from nutrient-limited natural biodegradation, and it also suggests that an effective strategy for their bioremediation could consist simply of adding inorganic nutrients.

Leaching of polycyclic aromatic hydrocarbons from power plant lignite ash--influence of parameters important for environmental pollution.

PubMed

Pergal, Miodrag M; Relić, Dubravka; Tešić, Zivoslav Lj; Popović, Aleksandar R

2014-03-01

Nikola Tesla B power plant (TENT B), located at the Sava River, in Obrenovac, 50 km west from the Serbian's capital, Belgrade, is the second largest coal-fired power plant in the country, consisting of two blocks, each of 620 MW capacity. In order to investigate the threat polycyclic aromatic hydrocarbons (PAHs) from deposited coal ash, obtained by coal combustion in this power plant, can represent for the surrounding environment, samples of coal ash were submitted to extraction with river water used for transport of coal ash to the dump, as well as with water of different ionic strength and acidity. It was found that, out of 16 EPA priority PAHs, only naphthalene, acenaphthylene, fluorene, phenantrene, fluoranthene, and pyrene were found in measurable concentrations in the different extracts. Their combined concentration was around 0.1 μg/L, so they do not, in terms of leached concentrations, represent serious danger for the surrounding environment. In all cases of established (and leached) PAH compounds, changes of ionic strength, acidity, or the presence of organic compounds in river water may to some extent influence the leached concentrations. However, under the examined conditions, similar to those present in the environment, leached concentrations were not more than 50 % greater than the concentrations leached by distilled water. Therefore, water desorption is likely the most important mechanism responsible for leaching of PAH compounds from filter coal ash.

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

Guinea Pig Chymase Is Leucine-specific

PubMed Central

Caughey, George H.; Beauchamp, Jeremy; Schlatter, Daniel; Raymond, Wilfred W.; Trivedi, Neil N.; Banner, David; Mauser, Harald; Fingerle, Jürgen

2008-01-01

To explore guinea pigs as models of chymase biology, we cloned and expressed the guinea pig ortholog of human chymase. In contrast to rats and mice, guinea pigs appear to express just one chymase, which belongs to the α clade, like primate chymases and mouse mast cell protease-5. The guinea pig enzyme autolyzes at Leu residues in the loop where human chymase autolyzes at Phe. In addition, guinea pig α-chymase selects P1 Leu in a combinatorial peptide library and cleaves Ala-Ala-Pro-Leu-4-nitroanilide but has negligible activity toward substrates with P1 Phe and does not cleave angiotensin I. This contrasts with human chymase, which cleaves after Phe or Tyr, prefers P1 Phe in peptidyl 4-nitroanilides, and avidly hydrolyzes angiotensin I at Phe8 to generate bioactive angiotensin II. The guinea pig enzyme also is inactivated more effectively by α1-antichymotrypsin, which features P1 Leu in the reactive loop. Unlike mouse, rat, and hamster α-chymases, guinea pig chymase lacks elastase-like preference for P1 Val or Ala. Partially humanized A216G guinea pig chymase acquires human-like P1 Phe- and angiotensin-cleaving capacity. Molecular models suggest that the wild type active site is crowded by the Ala216 side chain, which potentially blocks access by bulky P1 aromatic residues. On the other hand, the guinea pig pocket is deeper than in Val-selective chymases, explaining the preference for the longer aliphatic side chain of Leu. These findings are evidence that chymase-like peptidase specificity is sensitive to small changes in structure and provide the first example of a vertebrate Leu-selective peptidase. PMID:18353771

Calcium and organic matter removal by carbonation process with waste incineration flue gas towards improvement of leachate biotreatment performance.

PubMed

Zhang, Cheng; Zhu, Xuedong; Wu, Liang; Li, Qingtao; Liu, Jianyong; Qian, Guangren

2017-09-01

Municipal solid wastes incineration (MSWI) flue gas was employed as the carbon source for in-situ calcium removal from MSWI leachate. Calcium removal efficiency was 95-97% with pH of 10.0-11.0 over 100min of flue gas aeration, with both bound Ca and free Ca being removed effectively. The fluorescence intensity of tryptophan, protein-like and humic acid-like compounds increased after carbonation process. The decrease of bound Ca with the increase of precipitate indicated that calcium was mainly converted to calcium carbonate precipitate. It suggested that the interaction between dissolved organic matter and Ca 2+ was weakened. Moreover, 10-16% of chemical oxygen demand removal and the decrease of ultraviolet absorption at 254nm indicated that some organics, especially aromatic compound decreased via adsorption onto the surface of calcium carbonate. The results indicate that introduce of waste incineration flue gas could be a feasible way for calcium removal from leachate. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

Sources of SOA gaseous precursors in contrasted urban environments: a focus on mono-aromatic compounds and intermediate volatility compounds

NASA Astrophysics Data System (ADS)

Salameh, Therese; Borbon, Agnès; Ait-Helal, Warda; Afif, Charbel; Sauvage, Stéphane; Locoge, Nadine; Bonneau, Stéphane; Sanchez, Olivier

2016-04-01

Among Volatile Organic Compounds (VOC), the mono-aromatic compounds so-called BTEX (Benzene, Toluene, Ethylbenzene, and Xylenes) and the intermediate volatility organic compounds (IVOC) with C>12 are two remarkable chemical families having high impact on health, as well as on the production of secondary pollutants like secondary organic aerosols (SOA) and ozone. However, the nature and relative importance of their sources and, consequently, their impact on SOA formation at urban scale is still under debate. On the one hand, BTEX observations in urban areas of northern mid-latitudes do not reconcile with emission inventories; the latter pointing to solvent use as the dominant source compared to traffic. Moreover, a recent study by Borbon et al. (2013) has shown an enrichment in the C7-C9 aromatic fraction in Paris atmosphere by a factor of 3 compared to other cities. Causes would be: (i) differences in gasoline composition, (ii) differences in vehicle fleet composition, and (iii) differences in solvent use related sources. On the other hand, many smog chamber studies have highlighted IVOCs as important SOA precursors over the last decade but their origin and importance in urban areas relative to other precursors like BTEX is still poorly addressed. Here we combined large VOC datasets to investigate sources of BTEX and IVOC in contrasted urban areas by source-receptor approaches and laboratory experiments. Ambient data include multi-site speciated ambient measurements of C2 to C17 VOCs (traffic, urban background, and tunnel) from air quality networks (ie. AIRPARIF in Paris) and intensive field campaigns (MEGAPOLI-Paris, TRANSEMED in Beirut and Istanbul, PHOTOPAQ in Brussels). Preliminary results for Paris suggest that traffic dominates BTEX concentrations while traffic and domestic heating for IVOC (>70%). In parallel, the detailed composition of the fuel liquid phase was determined at the laboratory for typical fuels distributed in Ile de France region (diesel, SP95, SP95 E10, and SP98) and was used to constraint evaporative emissions in order to predict the headspace vapour composition (Harley and Coulter-Burke, 2000). Modelled and observed compositions are in good agreement (differences up to 20%). Therefore, the implemented model is a relevant tool to test the sensitivity of BTEX and other VOCs ambient composition to evaporative emissions of fuels with regards to their composition. Such analysis will be extended to other target cities and similarities/differences will be presented regarding regional characteristics. This work was supported by the Ile de France region, Life and PHOTOPAQ grant, PICS-CNRS, ENVIMED and ChArMEx. We would like to thank Laurence Dépelchin and Thierry Léonardis for technical support and AIRPARIF for providing the data. Borbon, A., et al. (2013) Emission ratios of anthropogenic VOC in northern mid-latitude megacities: observations vs. emission inventories in Los Angeles and Paris, J. Geophys. Res. 118, 2041 - 2057. Harley, R. and Coulter-Burke, S. (2000) Relating Liquid Fuel and Headspace Vapor Composition for California Reformulated Gasoline Samples Containing Ethanol, Environ. Sci. Technol. 34, 4088-4094. Ait-Helal, W.; Borbon, A.; Sauvage, S.; et al., Atmos. Chem. Phys. vol. 14 , No. 19 , p. 10439-10464

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.

Dioxins and dioxin-like compounds in composts and digestates from European countries as determined by the in vitro bioassay and chemical analysis.

PubMed

Beníšek, Martin; Kukučka, Petr; Mariani, Giulio; Suurkuusk, Gert; Gawlik, Bernd M; Locoro, Giovanni; Giesy, John P; Bláha, Luděk

2015-03-01

Aerobic composting and anaerobic digestion plays an important role in reduction of organic waste by transforming the waste into humus, which is an excellent soil conditioner. However, applications of chemical-contaminated composts on soils may have unwanted consequences such as accumulation of persistent compounds and their transfer into food chains. The present study investigated burden of composts and digestates collected in 16 European countries (88 samples) by the compounds causing dioxin-like effects as determined by use of an in vitro transactivation assay to quantify total concentrations of aryl hydrocarbon receptor-(AhR) mediated potency. Measured concentrations of 2,3,7,8-Tetrachlorodibeno-p-dioxin (2,3,7,8-TCDD) equivalents (TEQbio) were compared to concentrations of polycyclic aromatic hydrocarbons (PAHs) and selected chlorinated compounds, including polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs), co-planar polychlorinated biphenyls (PCBs), indicator PCB congeners and organochlorine pesticides (OCPs). Median concentrations of TEQbio (dioxin-like compounds) determined by the in vitro assay in crude extracts of various types of composts ranged from 0.05 to 1.2 with a maximum 8.22μg (TEQbio)kg(-1) dry mass. Potencies were mostly associated with less persistent compounds such as PAHs because treatment with sulfuric acid removed bioactivity from most samples. The pan-European investigation of contamination by organic contaminants showed generally good quality of the composts, the majority of which were in compliance with conservative limits applied in some countries. Results demonstrate performance and added value of rapid, inexpensive, effect-based monitoring, and points out the need to derive corresponding effect-based trigger values for the risk assessment of complex contaminated matrices such as composts. Copyright © 2014 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.

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

A credit-card library approach for disrupting protein-protein interactions.

PubMed

Xu, Yang; Shi, Jin; Yamamoto, Noboru; Moss, Jason A; Vogt, Peter K; Janda, Kim D

2006-04-15

Protein-protein interfaces are prominent in many therapeutically important targets. Using small organic molecules to disrupt protein-protein interactions is a current challenge in chemical biology. An important example of protein-protein interactions is provided by the Myc protein, which is frequently deregulated in human cancers. Myc belongs to the family of basic helix-loop-helix leucine zipper (bHLH-ZIP) transcription factors. It is biologically active only as heterodimer with the bHLH-ZIP protein Max. Herein, we report a new strategy for the disruption of protein-protein interactions that has been corroborated through the design and synthesis of a small parallel library composed of 'credit-card' compounds. These compounds are derived from a planar, aromatic scaffold and functionalized with four points of diversity. From a 285 membered library, several hits were obtained that disrupted the c-Myc-Max interaction and cellular functions of c-Myc. The IC50 values determined for this small focused library for the disruption of Myc-Max dimerization are quite potent, especially since small molecule antagonists of protein-protein interactions are notoriously difficult to find. Furthermore, several of the compounds were active at the cellular level as shown by their biological effects on Myc action in chicken embryo fibroblast assays. In light of our findings, this approach is considered a valuable addition to the armamentarium of new molecules being developed to interact with protein-protein interfaces. Finally, this strategy for disrupting protein-protein interactions should prove applicable to other families of proteins.

An unusual strategy for the anoxic biodegradation of phthalate.

PubMed

Ebenau-Jehle, Christa; Mergelsberg, Mario; Fischer, Stefanie; Brüls, Thomas; Jehmlich, Nico; von Bergen, Martin; Boll, Matthias

2017-01-01

In the past two decades, the study of oxygen-independent degradation of widely abundant aromatic compounds in anaerobic bacteria has revealed numerous unprecedented enzymatic principles. Surprisingly, the organisms, metabolites and enzymes involved in the degradation of o-phthalate (1,2-dicarboxybenzene), mainly derived from phthalate esters that are annually produced at the million ton scale, are sparsely known. Here, we demonstrate a previously unknown capacity of complete phthalate degradation in established aromatic compound-degrading, denitrifying model organisms of the genera Thauera, Azoarcus and 'Aromatoleum'. Differential proteome analyses revealed phthalate-induced gene clusters involved in uptake and conversion of phthalate to the central intermediate benzoyl-CoA. Enzyme assays provided in vitro evidence for the formation of phthaloyl-CoA by a succinyl-CoA- and phthalate-specific CoA transferase, which is essential for the subsequent oxygen-sensitive decarboxylation to benzoyl-CoA. The extreme instability of the phthaloyl-CoA intermediate requires highly balanced CoA transferase and decarboxylase activities to avoid its cellular accumulation. Phylogenetic analysis revealed phthaloyl-CoA decarboxylase as a novel member of the UbiD-like, (de)carboxylase enzyme family. Homologs of the encoding gene form a phylogenetic cluster and are found in soil, freshwater and marine bacteria; an ongoing global distribution of a possibly only recently evolved degradation pathway is suggested.

Molecular evidence of heavy-oil weathering following the M/V Cosco Busan spill: insights from Fourier transform ion cyclotron resonance mass spectrometry.

PubMed

Lemkau, Karin L; McKenna, Amy M; Podgorski, David C; Rodgers, Ryan P; Reddy, Christopher M

2014-04-01

Recent studies have highlighted a critical need to investigate oil weathering beyond the analytical window afforded by conventional gas chromatography (GC). In particular, techniques capable of detecting polar and higher molecular weight (HMW; > 400 Da) components abundant in crude and heavy fuel oils (HFOs) as well as transformation products. Here, we used atmospheric pressure photoionization Fourier transform ion cyclotron resonance mass spectrometry (APPI FT-ICR MS) to identify molecular transformations in oil-residue samples from the 2007 M/V Cosco Busan HFO spill (San Francisco, CA). Over 617 days, the abundance and diversity of oxygen-containing compounds increased relative to the parent HFO, likely from bio- and photodegradation. HMW, highly aromatic, alkylated compounds decreased in relative abundance concurrent with increased relative abundance of less alkylated stable aromatic structures. Combining these results with GC-based data yielded a more comprehensive understanding of oil spill weathering. For example, dealkylation trends and the overall loss of HMW species observed by FT-ICR MS has not previously been documented and is counterintuitive given losses of lower molecular weight species observed by GC. These results suggest a region of relative stability at the interface of these techniques, which provides new indicators for studying long-term weathering and identifying sources.

An unusual strategy for the anoxic biodegradation of phthalate

PubMed Central

Ebenau-Jehle, Christa; Mergelsberg, Mario; Fischer, Stefanie; Brüls, Thomas; Jehmlich, Nico; von Bergen, Martin; Boll, Matthias

2017-01-01

In the past two decades, the study of oxygen-independent degradation of widely abundant aromatic compounds in anaerobic bacteria has revealed numerous unprecedented enzymatic principles. Surprisingly, the organisms, metabolites and enzymes involved in the degradation of o-phthalate (1,2-dicarboxybenzene), mainly derived from phthalate esters that are annually produced at the million ton scale, are sparsely known. Here, we demonstrate a previously unknown capacity of complete phthalate degradation in established aromatic compound-degrading, denitrifying model organisms of the genera Thauera, Azoarcus and ‘Aromatoleum'. Differential proteome analyses revealed phthalate-induced gene clusters involved in uptake and conversion of phthalate to the central intermediate benzoyl-CoA. Enzyme assays provided in vitro evidence for the formation of phthaloyl-CoA by a succinyl-CoA- and phthalate-specific CoA transferase, which is essential for the subsequent oxygen-sensitive decarboxylation to benzoyl-CoA. The extreme instability of the phthaloyl-CoA intermediate requires highly balanced CoA transferase and decarboxylase activities to avoid its cellular accumulation. Phylogenetic analysis revealed phthaloyl-CoA decarboxylase as a novel member of the UbiD-like, (de)carboxylase enzyme family. Homologs of the encoding gene form a phylogenetic cluster and are found in soil, freshwater and marine bacteria; an ongoing global distribution of a possibly only recently evolved degradation pathway is suggested. PMID:27392087

A cluster of bacterial genes for anaerobic benzene ring biodegradation

PubMed Central

Egland, Paul G.; Pelletier, Dale A.; Dispensa, Marilyn; Gibson, Jane; Harwood, Caroline S.

1997-01-01

A reductive benzoate pathway is the central conduit for the anaerobic biodegradation of aromatic pollutants and lignin monomers. Benzene ring reduction requires a large input of energy and this metabolic capability has, so far, been reported only in bacteria. To determine the molecular basis for this environmentally important process, we cloned and analyzed genes required for the anaerobic degradation of benzoate and related compounds from the phototrophic bacterium, Rhodopseudomonas palustris. A cluster of 24 genes was identified that includes twelve genes likely to be involved in anaerobic benzoate degradation and additional genes that convert the related compounds 4-hydroxybenzoate and cyclohexanecarboxylate to benzoyl-CoA. Genes encoding benzoyl-CoA reductase, a novel enzyme able to overcome the resonance stability of the aromatic ring, were identified by directed mutagenesis. The gene encoding the ring-cleavage enzyme, 2-ketocyclohexanecarboxyl-CoA hydrolase, was identified by assaying the enzymatic activity of the protein expressed in Escherichia coli. Physiological data and DNA sequence analyses indicate that the benzoate pathway consists of unusual enzymes for ring reduction and cleavage interposed among enzymes homologous to those catalyzing fatty acid degradation. The cloned genes should be useful as probes to identify benzoate degradation genes from other metabolically distinct groups of anaerobic bacteria, such as denitrifying bacteria and sulfate-reducing bacteria. PMID:9177244

Origin and distribution of thiophenes and furans in gas discharges from active volcanoes and geothermal systems.

PubMed

Tassi, Franco; Montegrossi, Giordano; Capecchiacci, Francesco; Vaselli, Orlando

2010-03-31

The composition of non-methane organic volatile compounds (VOCs) determined in 139 thermal gas discharges from 18 different geothermal and volcanic systems in Italy and Latin America, consists of C(2)-C(20) species pertaining to the alkanes, alkenes, aromatics and O-, S- and N-bearing classes of compounds. Thiophenes and mono-aromatics, especially the methylated species, are strongly enriched in fluids emissions related to hydrothermal systems. Addition of hydrogen sulphide to dienes and electrophilic methylation involving halogenated radicals may be invoked for the formation of these species. On the contrary, the formation of furans, with the only exception of C(4)H(8)O, seems to be favoured at oxidizing conditions and relatively high temperatures, although mechanisms similar to those hypothesized for the production of thiophenes can be suggested. Such thermodynamic features are typical of fluid reservoirs feeding high-temperature thermal discharges of volcanoes characterised by strong degassing activity, which are likely affected by conspicuous contribution from a magmatic source. The composition of heteroaromatics in fluids naturally discharged from active volcanoes and geothermal areas can then be considered largely dependent on the interplay between hydrothermal vs. magmatic contributions. This implies that they can be used as useful geochemical tools to be successfully applied in both volcanic monitoring and geothermal prospection.

Origin and Distribution of Thiophenes and Furans in Gas Discharges from Active Volcanoes and Geothermal Systems

PubMed Central

Tassi, Franco; Montegrossi, Giordano; Capecchiacci, Francesco; Vaselli, Orlando

2010-01-01

The composition of non-methane organic volatile compounds (VOCs) determined in 139 thermal gas discharges from 18 different geothermal and volcanic systems in Italy and Latin America, consists of C2–C20 species pertaining to the alkanes, alkenes, aromatics and O-, S- and N-bearing classes of compounds. Thiophenes and mono-aromatics, especially the methylated species, are strongly enriched in fluids emissions related to hydrothermal systems. Addition of hydrogen sulphide to dienes and electrophilic methylation involving halogenated radicals may be invoked for the formation of these species. On the contrary, the formation of furans, with the only exception of C4H8O, seems to be favoured at oxidizing conditions and relatively high temperatures, although mechanisms similar to those hypothesized for the production of thiophenes can be suggested. Such thermodynamic features are typical of fluid reservoirs feeding high-temperature thermal discharges of volcanoes characterised by strong degassing activity, which are likely affected by conspicuous contribution from a magmatic source. The composition of heteroaromatics in fluids naturally discharged from active volcanoes and geothermal areas can then be considered largely dependent on the interplay between hydrothermal vs. magmatic contributions. This implies that they can be used as useful geochemical tools to be successfully applied in both volcanic monitoring and geothermal prospection. PMID:20480029

Koopmans' analysis of chemical hardness with spectral-like resolution.

PubMed

Putz, Mihai V

2013-01-01

Three approximation levels of Koopmans' theorem are explored and applied: the first referring to the inner quantum behavior of the orbitalic energies that depart from the genuine ones in Fock space when the wave-functions' Hilbert-Banach basis set is specified to solve the many-electronic spectra of spin-orbitals' eigenstates; it is the most subtle issue regarding Koopmans' theorem as it brings many critics and refutation in the last decades, yet it is shown here as an irrefutable "observational" effect through computation, specific to any in silico spectra of an eigenproblem; the second level assumes the "frozen spin-orbitals" approximation during the extracting or adding of electrons to the frontier of the chemical system through the ionization and affinity processes, respectively; this approximation is nevertheless workable for great deal of chemical compounds, especially organic systems, and is justified for chemical reactivity and aromaticity hierarchies in an homologue series; the third and the most severe approximation regards the extension of the second one to superior orders of ionization and affinities, here studied at the level of chemical hardness compact-finite expressions up to spectral-like resolution for a paradigmatic set of aromatic carbohydrates.

Koopmans' Analysis of Chemical Hardness with Spectral-Like Resolution

PubMed Central

2013-01-01

Three approximation levels of Koopmans' theorem are explored and applied: the first referring to the inner quantum behavior of the orbitalic energies that depart from the genuine ones in Fock space when the wave-functions' Hilbert-Banach basis set is specified to solve the many-electronic spectra of spin-orbitals' eigenstates; it is the most subtle issue regarding Koopmans' theorem as it brings many critics and refutation in the last decades, yet it is shown here as an irrefutable “observational” effect through computation, specific to any in silico spectra of an eigenproblem; the second level assumes the “frozen spin-orbitals” approximation during the extracting or adding of electrons to the frontier of the chemical system through the ionization and affinity processes, respectively; this approximation is nevertheless workable for great deal of chemical compounds, especially organic systems, and is justified for chemical reactivity and aromaticity hierarchies in an homologue series; the third and the most severe approximation regards the extension of the second one to superior orders of ionization and affinities, here studied at the level of chemical hardness compact-finite expressions up to spectral-like resolution for a paradigmatic set of aromatic carbohydrates. PMID:23970834

Virtual screening of ABCC1 transporter nucleotidebinding domains as a therapeutic target in multidrug resistant cancer

PubMed Central

Rungsardthong, Kanin; Mares- Sámano, Sergio; Penny, Jeffrey

2012-01-01

ABCC1 is a member of the ATP-binding Cassette super family of transporters, actively effluxes xenobiotics from cells. Clinically, ABCC1 expression is linked to cancer multidrug resistance. Substrate efflux is energised by ATP binding and hydrolysis at the nucleotide-binding domains (NBDs) and inhibition of these events may help combat drug resistance. The aim of this study is to identify potential inhibitors of ABCC1 through virtual screening of National Cancer Institute (NCI) compounds. A threedimensional model of ABCC1 NBD2 was generated using MODELLER whilst the X-ray crystal structure of ABCC1 NBD1 was retrieved from the Protein Data Bank. A pharmacophore hypothesis was generated based on flavonoids known to bind at the NBDs using PHASE, and used to screen the NCI database. GLIDE was employed in molecular docking studies for all hit compounds identified by pharmacophore screening. The best potential inhibitors were identified as compounds possessing predicted binding affinities greater than ATP. Approximately 5% (13/265) of the hit compounds possessed lower docking scores than ATP in ABCC1 NBD1 (NSC93033, NSC662377, NSC319661, NSC333748, NSC683893, NSC226639, NSC94231, NSC55979, NSC169121, NSC166574, NSC73380, NSC127738, NSC115534), whereas approximately 7% (7/104) of docked NCI compounds were predicted to possess lower docking scores than ATP in ABCC1 NBD2 (NSC91789, NSC529483, NSC211168, NSC318214, NSC116519, NSC372332, NSC526974). Analyses of docking orientations revealed P-loop residues of each NBD and the aromatic amino acids Trp653 (NBD1) and Tyr1302 (NBD2) were key in interacting with high-affinity compounds. On the basis of docked orientation and docking score the compounds identified may be potential inhibitors of ABCC1 and require further pharmacological analysis. Abbreviations ABC - ATP-binding cassette, DHS - dehydrosilybin, MDR - multidrug resistance, NBD - nucleotide-binding domain, PDB - protein data bank. PMID:23144549

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

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.

Separation and characterization of gall bladder bile metabolites from speckled trout, Salvelinus fontinalis, exposed to individual polycyclic aromatic compounds.

PubMed

Leonard, J D; Hellou, J

2001-03-01

Speckled trout, Salvelinus fontinalis, were orally exposed to individual polycyclic aromatic compounds (PACs) represented by benzo[a]pyrene, carbazole, chrysene, dibenzofuran, dibenzothiophene, fluorene, phenanthrene, and pyrene. Fish were sacrificed 7 d after exposure and the gall bladder removed for bile analysis. High pressure liquid chromatography (HPLC) with fluorescence (F) and ultraviolet (UV) detection was used to determine the presence of PAC derivatives in the bile without pretreatment. Glucuronide conjugates were predominant in all exposures with variable amounts (0-53%) of phenols and starting material. Identification of compounds was confirmed by selective extraction of less polar nonconjugated PACs and enzymatic hydrolysis of water-soluble material. This was followed by HPLC and/or gas chromatography-mass spectrometry (GCMS) characterization of the produced phenols. Total metabolite levels varied widely among compounds.

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.

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.

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.

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.

Protective effects of 4-phenylbutyrate derivatives on the neuronal cell death and endoplasmic reticulum stress.

PubMed

Mimori, Seisuke; Okuma, Yasunobu; Kaneko, Masayuki; Kawada, Koichi; Hosoi, Toru; Ozawa, Koichiro; Nomura, Yasuyuki; Hamana, Hiroshi

2012-01-01

Endoplasmic reticulum (ER) stress responses play an important role in neurodegenerative diseases. Sodium 4-phenylbutyrate (4-PBA) is a terminal aromatic substituted fatty acid that has been used for the treatment of urea cycle disorders. 4-PBA possesses in vitro chemical chaperone activity and reduces the accumulation of Parkin-associated endothelin receptor-like receptor (Pael-R), which is involved in autosomal recessive juvenile parkinsonism (AR-JP). In this study, we show that terminal aromatic substituted fatty acids, including 3-phenylpropionate (3-PPA), 4-PBA, 5-phenylvaleric acid, and 6-phenylhexanoic acid, prevented the aggregation of lactalbumin and bovine serum albumin. Aggregation inhibition increased relative to the number of carbons in the fatty acids. Moreover, these compounds protected cells against ER stress-induced neuronal cell death. The cytoprotective effect correlated with the in vitro chemical chaperone activity. Similarly, cell viability decreased on treatment with tunicamycin, an ER stress inducer, and was dependent on the number of carbons in the fatty acids. Moreover, the expression of glucose-regulated proteins 94 and 78 (GRP94, 78) decreased according to the number of carbons in the fatty acids. Furthermore, we investigated the effects of these compounds on the accumulation of Pael-R in neuroblastoma cells. 3-PPA and 4-PBA significantly suppressed neuronal cell death caused by ER stress induced by the overexpression of Pael-R. Overexpressed Pael-R accumulated in the ER of cells. With 3-PPA and 4-PBA treatment, the localization of the overexpressed Pael-R shifted away from the ER to the cytoplasmic membrane. These results suggest that terminal aromatic substituted fatty acids are potential candidates for the treatment of neurodegenerative diseases.

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.

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

Gasoline-Related Compounds in Lakes Mead and Mohave, Nevada, 2004-06

USGS Publications Warehouse

Lico, Michael S.; Johnson, B. Thomas

2007-01-01

The distribution of man-made organic compounds, specifically gasoline-derived compounds, was investigated from 2004 to 2006 in Lakes Mead and Mohave and one of its tributary streams, Las Vegas Wash. Compounds contained in raw gasoline (benzene, toluene, ethylbenzene, xylenes; also known as BTEX compounds) and those produced during combustion of gasoline (polycyclic aromatic hydrocarbon compounds; also known as PAH compounds) were detected at every site sampled in Lakes Mead and Mohave. Water-quality analyses of samples collected during 2004-06 indicate that motorized watercraft are the major source of these organic compounds to the lakes. Concentrations of BTEX increase as the boating season progresses and decrease to less than detectable levels during the winter when few boats are on the water. Volatilization and microbial degradation most likely are the primary removal mechanisms for BTEX compounds in the lakes. Concentrations of BTEX compounds were highest at sampling points near marinas or popular launching areas. Methyl tert-butyl ether (MTBE) was detected during 2004 but concentrations decreased to less than the detection level during the latter part of the study; most likely due to the removal of MTBE from gasoline purchased in California. Distribution of PAH compounds was similar to that of BTEX compounds, in that, concentrations were highest at popular boating areas and lowest in areas where fewer boats traveled. PAH concentrations were highest at Katherine Landing and North Telephone Cove in Lake Mohave where many personal watercraft with carbureted two-stroke engines ply the waters. Lake-bottom sediment is not a sink for PAH as indicated by the low concentrations detected in sediment samples from both lakes. PAH compounds most likely are removed from the lakes by photochemical degradation. PAH compounds in Las Vegas Wash, which drains the greater Las Vegas metropolitan area, were present in relatively high concentrations in sediment from the upstream reaches. Concentrations of PAH compounds were low in water and sediment samples collected farther downstream, thus the bottom sediment in the upstream part of the wash may be an effective trap for these compounds. Bioavailable PAH compounds were present in all samples as determined using the Fluoroscan method. Microtox acute toxicity profiles indicated that Callville Bay in Lake Mead and the two Lake Mohave sites had only minor evidence that toxic compounds are present.

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.

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...

Quantitative Estimation of the Electronic Effects of Substituents in Five-membered Nitrogen-containing Aromatic Heterocycles

NASA Astrophysics Data System (ADS)

Lopyrev, Valentin A.; Larina, Ludmila I.; Vakul'skaya, Tamara I.

1986-05-01

Data, characterising quantitatively the effect of substituents on the reactivity and physicochemical properties of five-membered nitrogen-containing heterocyclic compounds, which have accumulated in the literature during the last 15 years, are compiled in the review and discussed. The possibility of applying the Hammett and Jaffe equations in the determination of the direction of transmission of the electronic effects of substituents is analysed and the likely usefulness of this approach to the study of electronic influences by taking into account separately the inductive and resonance constants is demonstrated. The bibliography includes 215 references.

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.

The relationship of chromophoric dissolved organic matter parallel factor analysis fluorescence and polycyclic aromatic hydrocarbons in natural surface waters.

PubMed

Li, Sijia; Chen, Ya'nan; Zhang, Jiquan; Song, Kaishan; Mu, Guangyi; Sun, Caiyun; Ju, Hanyu; Ji, Meichen

2018-01-01

Polycyclic aromatic hydrocarbons (PAHs), a large group of persistent organic pollutants (POPs), have caused wide environmental pollution and ecological effects. Chromophoric dissolved organic matter (CDOM), which consists of complex compounds, was seen as a proxy of water quality. An attempt was made to understand the relationships of CDOM absorption parameters and parallel factor analysis (PARAFAC) components with PAHs under seasonal variation in the riverine, reservoir, and urban waters of the Yinma River watershed in 2016. These different types of water bodies provided wide CDOM and PAHs concentration ranges with CDOM absorption coefficients at a wavelength of 350 nm (a CDOM (350)) of 1.17-20.74 m -1 and total PAHs of 0-1829 ng/L. CDOM excitation-emission matrix (EEM) presented two fluorescent components, e.g., terrestrial humic-like (C1) and tryptophan-like (C2) were identified using PARAFAC. Tryptophan-like associated protein-like fluorescence often dominates the EEM signatures of sewage samples. Our finding is that seasonal CDOM EEM-PARAFAC and PAHs concentration showed consistent tendency indicated that PAHs were un-ignorable pollutants. However, the disparities in seasonal CDOM-PAH relationships relate to the similar sources of CDOM and PAHs, and the proportion of PAHs in CDOM. Overlooked and poorly appreciated, quantifying the relationship between CDOM and PAHs has important implications, because these results simplify ecological and health-based risk assessment of pollutants compared to the traditional chemical measurements.

Species-Specific Inactivation of Triosephosphate Isomerase from Trypanosoma brucei: Kinetic and Molecular Dynamics Studies.

PubMed

Vázquez-Raygoza, Alejandra; Cano-González, Lucia; Velázquez-Martínez, Israel; Trejo-Soto, Pedro Josué; Castillo, Rafael; Hernández-Campos, Alicia; Hernández-Luis, Francisco; Oria-Hernández, Jesús; Castillo-Villanueva, Adriana; Avitia-Domínguez, Claudia; Sierra-Campos, Erick; Valdez-Solana, Mónica; Téllez-Valencia, Alfredo

2017-11-24

Human African Trypanosomiasis (HAT), a disease that provokes 2184 new cases a year in Sub-Saharan Africa, is caused by Trypanosoma brucei . Current treatments are limited, highly toxic, and parasite strains resistant to them are emerging. Therefore, there is an urgency to find new drugs against HAT. In this context, T. brucei depends on glycolysis as the unique source for ATP supply; therefore, the enzyme triosephosphate isomerase (TIM) is an attractive target for drug design. In the present work, three new benzimidazole derivatives were found as TbTIM inactivators (compounds 1 , 2 and 3 ) with an I 50 value of 84, 82 and 73 µM, respectively. Kinetic analyses indicated that the three molecules were selective when tested against human TIM (HsTIM) activity. Additionally, to study their binding mode in TbTIM, we performed a 100 ns molecular dynamics simulation of TbTIM-inactivator complexes. Simulations showed that the binding of compounds disturbs the structure of the protein, affecting the conformations of important domains such as loop 6 and loop 8. In addition, the physicochemical and drug-like parameters showed by the three compounds suggest a good oral absorption. In conclusion, these molecules will serve as a guide to design more potent inactivators that could be used to obtain new drugs against HAT.

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.

Iodinated contrast media electro-degradation: process performance and degradation pathways.

PubMed

Del Moro, Guido; Pastore, Carlo; Di Iaconi, Claudio; Mascolo, Giuseppe

2015-02-15

The electrochemical degradation of six of the most widely used iodinated contrast media was investigated. Batch experiments were performed under constant current conditions using two DSA® electrodes (titanium coated with a proprietary and patented mixed metal oxide solution of precious metals such as iridium, ruthenium, platinum, rhodium and tantalum). The degradation removal never fell below 85% (at a current density of 64 mA/cm(2) with a reaction time of 150 min) when perchlorate was used as the supporting electrolyte; however, when sulphate was used, the degradation performance was above 80% (at a current density of 64 mA/cm(2) with a reaction time of 150 min) for all of the compounds studied. Three main degradation pathways were identified, namely, the reductive de-iodination of the aromatic ring, the reduction of alkyl aromatic amides to simple amides and the de-acylation of N-aromatic amides to produce aromatic amines. However, as amidotrizoate is an aromatic carboxylate, this is added via the decarboxylation reaction. The investigation did not reveal toxicity except for the lower current density used, which has shown a modest toxicity, most likely for some reaction intermediates that are not further degraded. In order to obtain total removal of the contrast media, it was necessary to employ a current intensity between 118 and 182 mA/cm(2) with energy consumption higher than 370 kWh/m(3). Overall, the electrochemical degradation was revealed to be a reliable process for the treatment of iodinated contrast media that can be found in contaminated waters such as hospital wastewater or pharmaceutical waste-contaminated streams. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

FORMATION OF POLYCYCLIC AROMATIC HYDROCARBONS AND CARBONACEOUS SOLIDS IN GAS-PHASE CONDENSATION EXPERIMENTS

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

Jaeger, C.; Huisken, F.; Henning, Th.

2009-05-01

Carbonaceous grains represent a major component of cosmic dust. In order to understand their formation pathways, they have been prepared in the laboratory by gas-phase condensation reactions such as laser pyrolysis and laser ablation. Our studies demonstrate that the temperature in the condensation zone determines the formation pathway of carbonaceous particles. At temperatures lower than 1700 K, the condensation by-products are mainly polycyclic aromatic hydrocarbons (PAHs) that are also the precursors or building blocks for the condensing soot grains. The low-temperature condensates contain PAH mixtures that are mainly composed of volatile three to five ring systems. At condensation temperatures highermore » than 3500 K, fullerene-like carbon grains and fullerene compounds are formed. Fullerene fragments or complete fullerenes equip the nucleating particles. Fullerenes can be identified as soluble components. Consequently, condensation products in cool and hot astrophysical environments such as cool and hot asymptotic giant branch stars or Wolf-Rayet stars should be different and should have distinct spectral properties.« less

Organochlorine compounds and polycyclic aromatic hydrocarbons in surface sediment from Baiyangdian Lake, North China: concentrations, sources profiles and potential risk.

PubMed

Hu, Guocheng; Luo, Xiaojun; Li, Fengchao; Dai, Jiayin; Guo, Jianyang; Chen, Shejun; Hong, Cao; Mai, Bixian; Xu, Muqi

2010-01-01

Organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs) were determined in nineteen surface sediment samples collected from Baiyangdian Lake and its inflowing river (Fuhe River) in North China. Total concentrations of OCPs, PCBs and PAHs in sediments ranged from 5.4 to 707.6 ng/g, 2.3 to 197.8 ng/g, and 101.3 to 6360.5 ng/g, respectively. The levels of contaminants in Fuhe River were significantly higher than those in Baiyandian Lake. For hexachlorocyclohexane (HCHs) and dichlorodiphenytrichloroethanes (DDTs), alpha-HCH and p,p'-DDT were predominant isomers; while for PCBs, PCB 28/31, PCB 40/103, PCB 60, PCB 101, and PCB 118 were predominant congeners. Possible sources derived from historical usage for OCPs and incomplete combustion fuel, wood, and coal and exhaustion of boats or cars for PAHs. Risk assessment of sediment indicated that sediments in Fuhe River were likely to pose potential biological adverse impact.

Relationships Between Dissolved Organic Matter Composition and Photochemistry in Lakes of Diverse Trophic Status.

PubMed

Maizel, Andrew C; Li, Jing; Remucal, Christina K

2017-09-05

The North Temperate Lakes Long-Term Ecological Research site includes seven lakes in northern Wisconsin that vary in hydrology, trophic status, and landscape position. We examine the molecular composition of dissolved organic matter (DOM) within these lakes using Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS) and quantify DOM photochemical activity using probe compounds. Correlations between the relative intensity of individual molecular formulas and reactive species production demonstrate the influence of DOM composition on photochemistry. For example, highly aromatic, tannin-like formulas correlate positively with triplet formation rates, but negatively with triplet quantum yields, as waters enriched in highly aromatic formulas exhibit much higher rates of light absorption, but only slightly higher rates of triplet production. While commonly utilized optical properties also correlate with DOM composition, the ability of FT-ICR MS to characterize DOM subpopulations provides unique insight into the mechanisms through which DOM source and environmental processing determine composition and photochemical activity.

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.

Analysis of Mixed Aryl/Alkyl Esters by Pyrolysis Gas Chromatography-Mass Spectrometry in the Presence of Perchlorate

NASA Technical Reports Server (NTRS)

Burton, A. S.; Locke, D. R.; Lewis, E. K.

2017-01-01

Mars is an important target for Astrobiology. A key goal of the MSL mission was to determine whether Mars was habitable in the past, a que-tion that has now been definitely determined to be yes. Another key goal for Mars exploration is to understand the origin and distribution of organic material on Mars; this question is being addressed by the SAM instrument on MSL, and will also be informed by two upcoming Mars exploration missions, ExoMars and Mars 2020. These latter two missions have instrumentation capable of detecting and characterize organic molecules. Over the next decade, these missions will analyze organics in surface, near-surface and sub-surface samples. Each mission has the capability to analyze organics by different methods (pyrolysis gas chromatography-mass spectrometry [py-GC-MS]; laser desorption and thermal volatilization GC-MS; and Raman spectroscopy). Plausibly extraterrestrial organics were recently discovered by the Mars Science Laboratory (MSL), providing an important first step towards understanding the organic inventory on Mars [1]. The compounds detected were chlorobenzenes and chloroalkanes, but it was argued that chlorination of these compounds occurred during pyrolysis of samples containing unchlorinated organics in the presence of perchlorate. A recent report analyzed a suite of aromatic (benzene, toluene, benzoic acid, phthalic acid, and mellitic acid) and aliphatic (acetic acid, propane, propanol, and hexane) by pyrolysis under SAM-like conditions in the presence of perchlorate to attempt to constrain possible precursor molecules for the organic molecules detected on Mars. For aromatic compounds, the aromatic acids all readily produced SAM-relevant chlorobenzes, whereas benzene and toluene did not. This observation suggests that the chlorobenzene detected on Mars could have derived from compounds like mellitic acid, consistent with the previous hypothesis by Benner et al. [3]. Among the aliphatic molecules, it was shown that pyrolysis of alkanes and alcohols in the presence of perchlorates produced polychlorine containing chloro-alkanes similar to what was observed on Mars. Surpris-ingly, however, similar treatment of acetic acid pro-duced chloroketones, instead, and no chloroalkanes were reported. This suggests that the chloroalkanes detected in the Sheepbed mudstone were not derived from aliphatic carboxylic acids, but instead were from more reduced alcohols or even alkanes, or perhaps were degradation products of more complicated organic material. Because organics analyses on mars will rely heavily on py-GC-MS of perchlorate-containing samples over the next decade, it is important to understand the fate of organic molecules of biotic and abiotic origin under such conditions. In this work we begin a series of experiments to improve our understanding of products generated during py-GC-MS of increasingly complex organic molecules (esters, amides, peptides, nucleic acids, fatty acids) in the presence of perchlorate.

In Vitro and In Vivo Activities of Dicationic Diguanidino Compounds against Echinococcus multilocularis Metacestodes

PubMed Central

Küster, Tatiana; Kriegel, Nadja; Boykin, David W.; Stephens, Chad E.

2013-01-01

Alveolar echinococcosis (AE) is a disease predominantly affecting the liver, with metacestodes (larvae) of the tapeworm Echinococcus multilocularis proliferating and exhibiting tumor-like infiltrative growth. For many years, chemotherapeutical treatment against alveolar echinococcosis has relied on the benzimidazoles albendazole and mebendazole, which require long treatment durations and exhibit parasitostatic rather than parasiticidal efficacy. Although benzimidazoles have been and still are beneficial for the patients, there is clearly a demand for alternative and more efficient treatment options. Aromatic dications, more precisely a small panel of di-N-aryl-diguanidino compounds, were screened for efficacy against E. multilocularis metacestodes in vitro. Only those with a thiophene core group were active against metacestodes, while furans were not. The most active compound, DB1127, was further investigated in terms of in vivo efficacy in mice experimentally infected with E. multilocularis metacestodes. This diguanidino compound was effective against AE when administered intraperitoneally but not when applied orally. Thus, thiophene-diguanidino derivatives with improved bioavailability when administered orally could lead to treatment options against AE. PMID:23716058

Desulfurization of benzonaphthothiophenes and dibenzothiophene with a Raney nickel catalyst and its relationship to the. pi. -electron density

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

Nagai, M.; Urimoto, H.; Uetake, K.

The hydrodesulfurization of heavy petroleum feedstocks and coal-derived liquids requires the conversion of high molecular weight compounds like dibenzothiophene and benzonaphthothiophenes. There are several studies in the literature which deal with the mechanism of the hydrodesulfurization of multi-ring thiophenic compounds on cobalt or nickel molybdenum catalysts at high pressure. However, there are only a few studies which relate the chemical reactivity of these compounds to their electronic structure. The reactivity of a multi-ring sulfur-containing compound is not determined solely by the size of the molecule. In addition, others studied the relationship between the first step in the hydrotreating reaction ofmore » benzonaphthothiophene and the Coulombic interaction term of the compounds using the CNDO/S method. Because there is competition between the different processes (hydrogenation and desulfurization) during reaction, it is difficult to understand the relationship between desulfurization and the electronic properties of the compounds under reaction conditions. The calculation of electronic structures necessarily involves many sigma bonds of hydrogenated aromatic rings as well as many electrons of high molecular weight compounds. For this reason, it is best to select a catalyst and reaction conditions under which desulfurization takes place without hydrogenation.« less

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.

Synthesis of magnetically recyclable MnFe2O4@SiO2@Ag nanocatalyst: Its high catalytic performances for azo dyes and nitro compounds reduction

NASA Astrophysics Data System (ADS)

Kurtan, U.; Amir, Md.; Yıldız, A.; Baykal, A.

2016-07-01

In this study, magnetically recycable MnFe2O4@SiO2@Ag nanocatalyst (MnFe2O4@SiO2@Ag MRCs) has been synthesized through co-precipition and chemical reduction method. XRD analysis confirmed the synthesis of single phase nanoproduct with crystallite size of 10 nm. VSM measurements showed the superparamagnetic property of the product. Catalytic studies showed that MnFe2O4@SiO2@Ag MRC could catalyze the reduction of the various azo compounds like methyl orange (MO), methylene blue (MB), eosin Y (EY), and rhodamine B (RhB) and also aromatic nitro compounds such as 4-nitrophenol (4-NP), 4-nitroaniline (4-NA) and 2-nitroaniline (2-NA). Moreover, the magnetic nanocatalyst showed an excellent reusability properties that remained unchanged after several cycles. Therefore, MnFe2O4@SiO2@Ag is the potential candidate for the application of organic pollutants for wastewater treatment.

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

Small-Molecule Inhibition and Activation-Loop Trans-Phosphorylation of the IGF1 Receptor

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

Wu,J.; Li, W.; Craddock, B.

2008-01-01

The insulin-like growth factor-1 receptor (IGF1R) is a receptor tyrosine kinase (RTK) that has a critical role in mitogenic signalling during embryogenesis and an antiapoptotic role in the survival and progression of many human tumours. Here, we present the crystal structure of the tyrosine kinase domain of IGF1R (IGF1RK), in its unphosphorylated state, in complex with a novel compound, cis-3-[3-(4-methyl-piperazin-l-yl)-cyclobutyl]-1-(2-phenyl-quinolin-7-yl)-imidazo[1, 5-a]pyrazin-8-ylamine (PQIP), which we show is a potent inhibitor of both the unphosphorylated (basal) and phosphorylated (activated) states of the kinase. PQIP interacts with residues in the ATP-binding pocket and in the activation loop, which confers specificity for IGF1RK andmore » the highly related insulin receptor (IR) kinase. In this crystal structure, the IGF1RK active site is occupied by Tyr1135 from the activation loop of an symmetry (two-fold)-related molecule. This dimeric arrangement affords, for the first time, a visualization of the initial trans-phosphorylation event in the activation loop of an RTK, and provides a molecular rationale for a naturally occurring mutation in the activation loop of the IR that causes type II diabetes mellitus.« less

Ice Radiation Chemistry as a Source of Potential False Biomarkers on the Surface of Europa

NASA Technical Reports Server (NTRS)

Bernstein, Max P.; Sandford, Scott A.; Allamandola, Louis J.

2004-01-01

If we find evidence of Life elsewhere in the Solar System it will probably be in form of chemical biomarkers, quintessentially biological molecules that indicate the presence of micro-organisms. While molecules such as amino acids and nucleo-bases might seem to be biomarkers, and alkyl substituted aromatics have been invoked as such, they are not necessarily. These molecules are present in some meteorites and are expected to be present on the surface of other planets even in the absence of life. Understanding the range of non-biological organic molecules which could act as false biomarkers in space is a prerequisite for any reasonable search for true biomarkers on other worlds. Our experiments have shown that some organic molecules in meteorites that appear biological in nature are formed by energetic processing of extraterrestrial ices can account for amino acids, quinones and other functionalized aromatic compounds. In the past, such molecules have been proposed as biomarkers. For example, alkylated aromatics were invoked as biomarkers in the Alan Hills 84001 'Martian meteorite.' When simple organics arrive at the surface of a body like Europa, either from below or from space, how long do they survive and what do they make? How can we distinguish these from real biomarkers?

Biosynthesis of cis,cis-muconic acid and its aromatic precursors, catechol and protocatechuic acid, from renewable feedstocks by Saccharomyces cerevisiae.

PubMed

Weber, Christian; Brückner, Christine; Weinreb, Sheila; Lehr, Claudia; Essl, Christine; Boles, Eckhard

2012-12-01

Adipic acid is a high-value compound used primarily as a precursor for the synthesis of nylon, coatings, and plastics. Today it is produced mainly in chemical processes from petrochemicals like benzene. Because of the strong environmental impact of the production processes and the dependence on fossil resources, biotechnological production processes would provide an interesting alternative. Here we describe the first engineered Saccharomyces cerevisiae strain expressing a heterologous biosynthetic pathway converting the intermediate 3-dehydroshikimate of the aromatic amino acid biosynthesis pathway via protocatechuic acid and catechol into cis,cis-muconic acid, which can be chemically dehydrogenated to adipic acid. The pathway consists of three heterologous microbial enzymes, 3-dehydroshikimate dehydratase, protocatechuic acid decarboxylase composed of three different subunits, and catechol 1,2-dioxygenase. For each heterologous reaction step, we analyzed several potential candidates for their expression and activity in yeast to compose a functional cis,cis-muconic acid synthesis pathway. Carbon flow into the heterologous pathway was optimized by increasing the flux through selected steps of the common aromatic amino acid biosynthesis pathway and by blocking the conversion of 3-dehydroshikimate into shikimate. The recombinant yeast cells finally produced about 1.56 mg/liter cis,cis-muconic acid.

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.

Formation of alkylated aromatic acids in groundwater by anaerobic degradation of alkylbenzenes.

PubMed

Martus, Peter; Püttmann, Wilhelm

2003-05-20

Evidence for the presence of previously unreported alkylated aromatic acids in anaerobic groundwater samples from a jet fuel-contaminated site is presented. The redox conditions are dominated by sulfate reduction. A gas chromatography/mass spectrometry screening showed a composition of aromatic hydrocarbons ranging from BTEX (C(0)-C(2)-substituted benzenes) up to C(7)-benzenes. Known metabolites like methylbenzoates (C(1)-BA), C(2)-BA, C(3)-BA as well as methylbenzylsuccinates (C(1)-BSA) were detected. Additionally, previously unreported metabolites of higher alkylated benzenes have been identified in the extracts: those are C(2)-BSA to C(5)-BSA as well as C(4)-BA to C(6)-BA, which were detected in the microg/l-concentration range. The formation of C(1)- and C(2)-BSA as well as the C(1)- and C(2)-BA can be linked to structurally corresponding parent contaminants like the xylene isomers and the trimethylbenzene isomers. The C(3)-BSA and C(3)-BA represent metabolites of C(4)-benzenes. The occurrence of C(4)-C(5)-BSA and C(4)-C(6)-BA is attributed to C(5)-C(7)-benzenes acting as parent compounds. The concentration of total aromatic contaminants decreased along the plume centre line. In contrast, benzoates and benzylsuccinates (BA and BSA) showed constant concentrations over a distance of 84 m. BA concentrations were up to 162 times higher compared to BSA, as indicated by the ratio f(BA/BSA). A pronounced transient behaviour of BSA or an overall persistent behaviour of BA can explain this. Hence, along the plume centre line, f(BA/BSA) was constant over a distance of 128 m. The degradation products detected in a monitoring well are not necessarily tied to contaminants detected in that well. Therefore, the metabolite plume is partly located in front of the contaminant plume, but does not significantly migrate downstream the plume toe.

Aromatic hydrocarbons at urban, sub-urban, rural (8°52'N; 67°19'W) and remote sites in Venezuela

NASA Astrophysics Data System (ADS)

Holzinger, R.; Kleiss, B.; Donoso, L.; Sanhueza, E.

Using the novel on-line proton transfer reaction mass spectrometry (PTR-MS) technique, atmospheric concentrations of benzene, toluene, xylenes, and C 9-benzenes were measured in Caracas (urban), Altos de Pipe (sub-urban), Calabozo (rural) and Parupa (remote), during various campaigns in 1999 and 2000. Average daytime mixing ratios measured in Caracas are 1.1, 3.2, 3.7, and 2.7 nmol/mol for benzene, toluene, xylenes, and C 9-benzenes. At the sub-urban site, located only few km from Caracas, relatively low levels (˜20% of the levels measured in Caracas) of these aromatic hydrocarbons were observed. At the rural site during the dry season, higher concentrations of benzene (0.15 nmol/mol) were recorded, whereas those of toluene (0.08 nmol/mol) were lower during that time. The aromatic hydrocarbon ratios in the wet season (benzene: 0.08 nmol/mol; toluene: 0.09 nmol/mol) are consistent with an aged urban plume, whereas biomass burning emissions dominate during the dry season. From rural and urban [benzene]/[toluene] ratios a mean HO concentration of 2.6×10 6 molecules/cm 3 was estimated during the wet season. This value must be considered an overestimate because it does not account for background concentrations which are likely for benzene and toluene. At the remote "La Gran Sabana" region (Parupa) very low mixing ratios (0.031 and 0.015 nmol/mol for benzene and toluene) are showing the pristine region to be unaffected by local sources. From the [benzene]/[toluene] ratio we deduced, that "urban" air arriving from the coastline (350 km) is likely mixed with air containing some background of benzene and toluene. Urban emissions (automobiles) should be the major source of aromatic compounds, however, during the dry season biomass burning seems to make an important contribution.

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

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.

Putative identification of new p-coumaroyl glycoside flavonoids in grape by ultra-high performance liquid chromatography/high-resolution mass spectrometry.

PubMed

Panighel, Annarita; De Rosso, Mirko; Dalla Vedova, Antonio; Flamini, Riccardo

2015-02-28

Grape polyphenols are antioxidant compounds, markers in vine chemotaxonomy, and involved in color stabilization of red wines. Sugar acylation usually confers higher stability on glycoside derivatives and this effect is enhanced by an aromatic substituent such as p-coumaric acid. Until now, only p-coumaroyl anthocyanins have been found in grape. A method of 'suspect screening analysis' by ultra-high-performance liquid chromatography/high-resolution mass spectrometry (UHPLC/QTOFMS) has recently been developed to study grape metabolomics. In the present study, this approach was used to identify new polyphenols in grape by accurate mass measurement, MS/MS fragmentation, and study of correlations between fragments observed and putative structures. Three putative p-coumaroyl flavonoids were identified in Raboso Piave grape extract: a dihydrokaempferide-3-O-p-coumaroylhexoside-like flavanone, isorhamnetin-3-O-p-coumaroylglucoside, and a chrysoeriol-p-coumaroylhexoside-like flavone. Accurate MS provided structural characterization of functional groups, and literature data indicates their probable position in the molecule. A fragmentation scheme is proposed for each compound. Compounds were identified by overlapping various analytical methods according to recommendations in the MS-based metabolomics literature. Stereochemistry and the definitive position of substituents in the molecule can only be confirmed by isolation and characterization or synthesis of each compound. These findings suggest addressing research of acylated polyphenol glycosides to other grape varieties. Copyright © 2015 John Wiley & Sons, Ltd.

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.

Large-Scale Selection and Breeding To Generate Industrial Yeasts with Superior Aroma Production

PubMed Central

Steensels, Jan; Meersman, Esther; Snoek, Tim; Saels, Veerle

2014-01-01

The concentrations and relative ratios of various aroma compounds produced by fermenting yeast cells are essential for the sensory quality of many fermented foods, including beer, bread, wine, and sake. Since the production of these aroma-active compounds varies highly among different yeast strains, careful selection of variants with optimal aromatic profiles is of crucial importance for a high-quality end product. This study evaluates the production of different aroma-active compounds in 301 different Saccharomyces cerevisiae, Saccharomyces paradoxus, and Saccharomyces pastorianus yeast strains. Our results show that the production of key aroma compounds like isoamyl acetate and ethyl acetate varies by an order of magnitude between natural yeasts, with the concentrations of some compounds showing significant positive correlation, whereas others vary independently. Targeted hybridization of some of the best aroma-producing strains yielded 46 intraspecific hybrids, of which some show a distinct heterosis (hybrid vigor) effect and produce up to 45% more isoamyl acetate than the best parental strains while retaining their overall fermentation performance. Together, our results demonstrate the potential of large-scale outbreeding to obtain superior industrial yeasts that are directly applicable for commercial use. PMID:25192996

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.

Identification of Novel Synthetic Toll-like Receptor 2 Agonists by High Throughput Screening*

PubMed Central

Guan, Yue; Omueti-Ayoade, Katherine; Mutha, Sarita K.; Hergenrother, Paul J.; Tapping, Richard I.

2010-01-01

Toll-like receptors (TLRs) play a central role in host defense by inducing inflammatory and adaptive immune responses following infection. Drugs that target TLRs are of considerable interest as potential inflammatory regulators, vaccine adjuvants, and novel immunotherapeutics. TLR2, in cooperation with either TLR1 or TLR6, mediates responses to a wide variety of microbial products as well as products of host tissue damage. In an effort to understand the structural basis of TLR2 recognition and uncover novel TLR2 agonists, a synthetic chemical library of 24,000 compounds was screened using an IL-8-driven luciferase reporter in cells expressing these human receptors. The screening yielded several novel TLR2-dependent activators that utilize TLR1, TLR6, or both as co-receptors. These novel small molecule compounds are aromatic in nature and structurally unrelated to any known TLR2 agonists. The three most potent compounds do not exhibit synergistic activity, nor do they act as pseudoantagonists toward natural TLR2 activators. Interestingly, two of the compounds exhibit species specificity and are inactive toward murine peritoneal macrophages. Mutational analysis reveals that although the central extracellular region of TLR1 is required for stimulation, there are subtle differences in the mechanism of stimulation mediated by the synthetic compounds in comparison with natural lipoprotein agonists. The three most potent compounds activate cells in the nanomolar range and stimulate cytokine production from human peripheral blood monocytes. Our results confirm the utility of high throughput screens to uncover novel synthetic TLR2 agonists that may be of therapeutic benefit. PMID:20504771

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...

Aromatic Ring Currents Illustrated--NMR Spectra of Tin(IV) Porphyrin Complexes. An Advanced Undergraduate Experiment.

ERIC Educational Resources Information Center

Arnold, Dennis P.

1988-01-01

Attempts to show that in the closed loops of cyclic structures the protons situated in conic regions above and below the ring will be shielded. Uses the diamagnetic and air stable octahedral tin(IV) complexes of porphyrins for study. Notes complexes crystallize easily and offer spectacular purple colors. (MVL)