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Sample records for non-aromatic heterocyclic amines

  1. Metabolism and Biomarkers of Heterocyclic Aromatic Amines in Molecular Epidemiology Studies: Lessons Learned from Aromatic Amines

    Science.gov (United States)

    2011-01-01

    Aromatic amines and heterocyclic aromatic amines (HAAs) are structurally related classes of carcinogens that are formed during the combustion of tobacco or during the high-temperature cooking of meats. Both classes of procarcinogens undergo metabolic activation by N-hydroxylation of the exocyclic amine group, to produce a common proposed intermediate, the arylnitrenium ion, which is the critical metabolite implicated in toxicity and DNA damage. However, the biochemistry and chemical properties of these compounds are distinct and different biomarkers of aromatic amines and HAAs have been developed for human biomonitoring studies. Hemoglobin adducts have been extensively used as biomarkers to monitor occupational and environmental exposures to a number of aromatic amines; however, HAAs do not form hemoglobin adducts at appreciable levels and other biomarkers have been sought. A number of epidemiologic studies that have investigated dietary consumption of well-done meat in relation to various tumor sites reported a positive association between cancer risk and well-done meat consumption, although some studies have shown no associations between well-done meat and cancer risk. A major limiting factor in most epidemiological studies is the uncertainty in quantitative estimates of chronic exposure to HAAs and, thus, the association of HAAs formed in cooked meat and cancer risk has been difficult to establish. There is a critical need to establish long-term biomarkers of HAAs that can be implemented in molecular epidemioIogy studies. In this review article, we highlight and contrast the biochemistry of several prototypical carcinogenic aromatic amines and HAAs to which humans are chronically exposed. The biochemical properties and the impact of polymorphisms of the major xenobiotic-metabolizing enzymes on the biological effects of these chemicals are examined. Lastly, the analytical approaches that have been successfully employed to biomonitor aromatic amines and HAAs, and

  2. Inhibitory effects of pomegranate seed extract on the formation of heterocyclic aromatic amines in beef and chicken meatballs after cooking by four different methods.

    Science.gov (United States)

    Keşkekoğlu, Hasan; Uren, Ali

    2014-04-01

    Beef and chicken meatballs with a 0.5% (w/w) pomegranate seed extract were cooked using four different cooking methods (oven roasting, pan cooking, charcoal-barbecue, and deep-fat frying) and six heterocyclic aromatic amines; IQ, MeIQx, 4,8-DiMeIQx, PhIP, norharman, and harman were observed. In the beef meatballs, the highest inhibitory effects of pomegranate seed extract on heterocyclic aromatic amines formation were 68% for PhIP, 24% for norharman, 18% for harman, 45% for IQ, and 57% for MeIQx. Total heterocyclic aromatic amine formation was reduced by 39% and 46% in beef meatballs cooked by charcoal-barbecue and deep-fat frying, respectively. In the chicken meatballs, the highest inhibitory effects were 75% for PhIP, 57% for norharman, 28% for harman, 46% for IQ, and 49% for MeIQx. When the pomegranate seed extract was added to the chicken meatballs cooked by deep-fat frying, the total heterocyclic aromatic amine formation was inhibited by 49%, in contrast the total heterocyclic aromatic amine contents after oven roasting increased by 70%. Copyright © 2013 Elsevier Ltd. All rights reserved.

  3. Bacterial degradation of monocyclic aromatic amines

    Directory of Open Access Journals (Sweden)

    Pankaj Kumar Arora

    2015-08-01

    Full Text Available Aromatic amines are an important group of industrial chemicals, which are widely used for manufacturing of dyes, pesticides, drugs, pigments, and other industrial products. These compounds have been considered highly toxic to human beings due to their carcinogenic nature. Three groups of aromatic amines have been recognized: monocyclic, polycyclic and heterocyclic aromatic amines. Bacterial degradation of several monocyclic aromatic compounds has been studied in a variety of bacteria, which utilizes monocyclic aromatic amines as their sole source of carbon and energy. Several degradation pathways have been proposed and the related enzymes and genes have also been characterized. Many reviews have been reviewed toxicity of monocyclic aromatic amines; however, there is lack of review on biodegradation of monocyclic aromatic amines. The aim of this review is to summarize bacterial degradation of monocyclic aromatic amines. This review will increase our current understanding of biochemical and molecular basis of bacterial degradation of monocyclic aromatic amines.

  4. Content of heterocyclic amines and polycyclic aromatic hydrocarbons in pork, beef and chicken barbecued at home by Danish consumers

    DEFF Research Database (Denmark)

    Aaslyng, Margit D.; Duedahl-Olesen, Lene; Jensen, Kirsten

    2013-01-01

    It is a well-known fact that, when meat is barbecued, several harmful components, including heterocyclic amines (HCA) and polycyclic aromatic hydrocarbons (PAH), may be formed. The aim of this study was to determine the HCA and PAH content in meat (pork, chicken and beef) when barbecued at home...

  5. Application of micro-solid-phase extraction for the on-site extraction of heterocyclic aromatic amines in seawater.

    Science.gov (United States)

    Basheer, Chanbasha

    2018-04-01

    An efficient on-site extraction technique to determine carcinogenic heterocyclic aromatic amines in seawater has been reported. A micro-solid-phase extraction device placed inside a portable battery-operated pump was used for the on-site extraction of seawater samples. Before on-site applications, parameters that influence the extraction efficiency (extraction time, type of sorbent materials, suitable desorption solvent, desorption time, and sample volume) were investigated and optimized in the laboratory. The developed method was then used for the on-site sampling of heterocyclic aromatic amines determination in seawater samples close to distillation plant. Once the on-site extraction completed, the small extraction device with the analytes was brought back to the laboratory for analysis using high-performance liquid chromatography with fluorescence detection. Based on the optimized conditions, the calibration curves were linear over the concentration range of 0.05-20 μg/L with correlation coefficients up to 0.996. The limits of detection were 0.004-0.026 μg/L, and the reproducibility values were between 1.3 and 7.5%. To evaluate the extraction efficiency, a comparison was made with conventional solid-phase extraction and it was applied to various fortified real seawater samples. The average relative recoveries obtained from the spiked seawater samples varied in the range 79.9-95.2%. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Diazotisation of Weakly Basic Aromatic and Heterocyclic Amines in Strongly Acid Media

    Science.gov (United States)

    Godovikova, Tamara I.; Rakitin, Oleg A.; Khmel'nitskii, Lenor I.

    1983-05-01

    The review is devoted to the diazotisation of weakly basic aromatic amines. The methods of synthesis of diazonium salts based on these amines by non-traditional methods are examined. Data on the mechanism of the diazotisation reaction in strongly acid media are surveyed. Reactions of diazonium salts leading to the synthesis of new compounds are presented. The bibliography includes 75 references.

  7. Induction of micronuclei in V79 cells after combined treatments with heterocyclic aromatic amines.

    Science.gov (United States)

    Perez, C; Lopez de Cerain, A; Bello, J

    2002-10-01

    Heterocyclic aromatic amines (HAs) appear in foods rich in proteins when subjected to different cooking processes. These amines have been demonstrated to be mutagenic in bacteria; in eucaryotic cells, controversial results have been referred. The objective of this study is to evaluate the clastogenic and/or aneugenic capacity of three HAs--2-amino-3-methylimidazo[4,5-f]quinoline (IQ), 2-amino-3-methylimidazo[4,5-f]quinoxaline (IQx), and 2-amino-3-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP)--in isolated as well as in combined treatments. The micronucleus test in vitro was used on V79 cells in the presence and absence of metabolic activation. The duration of the treatment was 2 h, and cytochalasin B was added for 21 h to stop cytokinesis; then, micronuclei (MN) were counted in binucleated cells. In the presence of metabolic activation, the three amines showed a significant increase in the number of MN with respect to the negative control. The PhIP amine presented the highest values and it also resulted slightly active in the absence of metabolic activation, although these differences have not been considered to be significant. The combined treatments of these amines have shown that the effects attributed to them when administered together are those that are expected for a possible additive effect; the effect attributed to each HA separately is not potentiated nor inhibited.

  8. Heterocyclic aromatic amines in domestically prepared chicken and fish from Singapore Chinese households.

    Science.gov (United States)

    Salmon, C P; Knize, M G; Felton, J S; Zhao, B; Seow, A

    2006-04-01

    Chicken and fish samples prepared by 42 Singapore Chinese in their homes were obtained. Researchers were present to collect data on raw sample weight, cooking time, maximum cooking surface temperature, and cooked sample weight. Each participant prepared one pan-fried fish sample and two pan-fried chicken samples, one marinated, one not marinated. The cooked samples were analyzed for five heterocyclic aromatic amine (HAA) mutagens, including MeIQx (2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline); 4,8-DiMeIQx (2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline); 7,8-DiMeIQx (2-amino-3,7,8-trimethylimidazo[4,5-f]quinoxaline); PhIP (2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine), and IFP (2-amino-(1,6-dimethylfuro[3,2-e]imidazo[4,5-b])pyridine). A paired Student's t-test showed that marinated chicken had lower concentrations of PhIP (pchicken, and also that weight loss due to cooking was less in marinated chicken than in non-marinated chicken (pchicken (pchicken (pchicken (pchicken (pchicken (p<0.05). This study provides new information on HAA content in the Singapore Chinese diet.

  9. N-heterocyclic carbene copper(I) catalysed N-methylation of amines using CO2

    KAUST Repository

    Santoro, Orlando

    2015-09-30

    The N-methylation of amines using CO2 and PhSiH3 as source of CH3 was efficiently performed using a N-heterocyclic carbene copper(I) complex. The methodology was found compatible with aromatic and aliphatic primary and secondary amines. Synthetic and computational studies have been carried out to support the proposed reaction mechanism for this transformation.

  10. N-heterocyclic carbene copper(I) catalysed N-methylation of amines using CO2

    KAUST Repository

    Santoro, Orlando; Lazreg, Faï ma; Minenkov, Yury; Cavallo, Luigi; Cazin, Catherine S. J.

    2015-01-01

    The N-methylation of amines using CO2 and PhSiH3 as source of CH3 was efficiently performed using a N-heterocyclic carbene copper(I) complex. The methodology was found compatible with aromatic and aliphatic primary and secondary amines. Synthetic and computational studies have been carried out to support the proposed reaction mechanism for this transformation.

  11. Influence of beer marinades on the reduction of carcinogenic heterocyclic aromatic amines in charcoal-grilled pork meat.

    Science.gov (United States)

    Viegas, Olga; Moreira, Patrícia S; Ferreira, Isabel M P L V O

    2015-01-01

    The effect of beer marinades on the formation of heterocyclic aromatic amines (HAs) was examined in charcoal-grilled pork. Pilsner, non-alcoholic pilsner and black beers (coded respectively as PB, P0B and BB) were assayed and unmarinated samples cooked under similar conditions provided reference HAs levels. Two thermic (PhIP and 4,8-DiMeIQx) and three pyrolytic HAs (Trp-P-1, AαC, MeAαC) were quantified in unmarinated meat samples. Marinating meat in beer resulted in a significant decrease of PhIP, Trp-P-1 and AαC (p beers reduced total HA formation in charcoal-grilled pork, black beer being the most efficient with a level of 90% inhibition. A strong positive correlation was observed between the inhibitory effect of beer on total HA formation and their antioxidant activity. Beer marinades mitigate the impact of consumption of well-done grilled pork meat reducing the formation of cooking carcinogens.

  12. Heterocyclic aromatic amine content in chicken burgers and chicken nuggets sold in fast food restaurants and effects of green tea extract and microwave thawing on their formation

    Science.gov (United States)

    The aims of the current study were to investigate the presence of carcinogenic and mutagenic heterocyclic aromatic amines (HAAs) in chicken burgers (CBs) and chicken nuggets (CNs) purchased from fast food restaurants and the effects of green tea extract addition (GTE) to the covering material as wel...

  13. Polar and non-polar heterocyclic amines in cooked fish and meat products and their corresponding pan residues.

    Science.gov (United States)

    Skog, K; Augustsson, K; Steineck, G; Stenberg, M; Jägerstad, M

    1997-06-01

    Fourteen cooked dishes with their corresponding pan residues were analysed for polar and non-polar heterocyclic amines using HPLC. The choice of foods, including beef, pork, poultry, game, fish, egg and sausages, was based on an investigation of an elderly population in Stockholm participating in an analytical epidemiological case-control study on cancer risks after intake of heterocyclic amines. The food items were prepared using normal household cooking practices, and to reflect the wide range of surface browning of the cooked dishes that would be encountered in this population, four cooking temperatures were used in the range 150-225 degrees C. For all food samples, the total amount of heterocyclic amines formed at 150 degrees C was less than 1 ng/g cooked product, and at 175 degrees C less than 2 ng/g. The highest concentrations of heterocyclic amines were detected in fillet of pork, reindeer meat and chicken breast fried at 200 and 225 degrees C and their corresponding pan residues. The total sum of 2-amino-3,8-dimethylimidazo-[4,5-f]quinoxaline, 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline and 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine was about 1 microgram per 100 g portion (including pan residues) for reindeer meat and chicken breast, and between 1.9 and 6.3 micrograms per 100-g portion for fillet of pork. PhIP was the most abundant heterocyclic amine, identified in 73 of 84 samples, and the highest concentration of PhIP, 32.0 ng/g, was found in the pan residue from fillet of pork cooked at 225 degrees C. The non-polar heterocyclic amines 3-amino-1,4-dimethyl-5H-pyrido[4,3-b]indole and 3-amino-1-methyl-5H-pyrido[4,3-b]indole were detected in the range of 0.5-7.4 ng/g in most foods cooked at 225 degrees C, and also in meat sauce prepared at 200 and 175 degrees C. The other heterocyclic amines tested for: 2-amino-3-methylimidazo-[4,5-f]quinoline, 2-amino-3,4-dimethylimidazo[4,5-f]quinoline, 2-amino-6-methyl-pyrido-[1,2-a:3',2'-d]-imidazole and 2

  14. Fusing porphyrins with polycyclic aromatic hydrocarbons and heterocycles for optoelectronic applications

    Science.gov (United States)

    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.

  15. Reduction of Aromatic and Heterocyclic Aromatic N-Hydroxylamines by Human Cytochrome P450 2S1

    Science.gov (United States)

    Wang, Kai; Guengerich, F. Peter

    2013-01-01

    Many aromatic amines and heterocyclic aromatic amines (HAAs) are known carcinogens for animals and there is also strong evidence for some in human cancer. The activation of these compounds, including some arylamine drugs, involves N-hydroxylation, usually by cytochrome P450 enzymes (P450) in Family 1 (1A2, 1A1, and 1B1). We previously demonstrated that the bioactivation product of the anti-cancer agent 2-(4-amino-3-methylphenyl)-5-fluorobenzothiazole (5F 203), an N-hydroxylamine, can be reduced by P450 2S1 to its amine precursor under anaerobic conditions and, to a lesser extent, under aerobic conditions (Wang, K., and Guengerich, F. P. (2012) Chem. Res. Toxicol. 25, 1740–1751). In the present study, we tested the hypothesis that P450 2S1 is involved in the reductive biotransformation of known carcinogenic aromatic amines and HAAs. The N-hydroxylamines of 4-aminobiphenyl (4-ABP), 2-naphthylamine (2-NA), and 2-aminofluorene (2-AF) were synthesized and found to be reduced by P450 2S1 under both anaerobic and aerobic conditions. The formation of amines due to P450 2S1 reduction also occurred under aerobic conditions but was less apparent because the competitive disproportionation reactions (of the N-hydroxylamines) also yielded amines. Further, some nitroso and nitro derivatives of the arylamines could also be reduced by P450 2S1. None of the amines tested were oxidized by P450 2S1. These results suggest that P450 2S1 may be involved in the reductive detoxication of several of the activated products of carcinogenic aromatic amines and HAAs. PMID:23682735

  16. Blue Chitin columns for the extraction of heterocyclic amines from urine samples

    DEFF Research Database (Denmark)

    Bang, J.; Frandsen, Henrik Lauritz; Skog, K.

    2004-01-01

    During normal cooking of meat, a class of mutagenic/carcinogenic compounds called heterocyclic amines is formed. Heterocyclic amines are rapidly absorbed and metabolised in the human body, and for estimation of the intake of heterocyclic amines, it is useful to determinate their levels in the uri...

  17. Methemoglobin Formation and Characterization of Hemoglobin Adducts of Carcinogenic Aromatic Amines and Heterocyclic Aromatic Amines.

    Science.gov (United States)

    Pathak, Khyatiben V; Chiu, Ting-Lan; Amin, Elizabeth Ambrose; Turesky, Robert J

    2016-03-21

    Arylamines (AAs) and heterocyclic aromatic amines (HAAs) are structurally related carcinogens formed during the combustion of tobacco or cooking of meat. They undergo cytochrome P450 mediated N-hydroxylation to form metabolites which bind to DNA and lead to mutations. The N-hydroxylated metabolites of many AAs also can undergo a co-oxidation reaction with oxy-hemolgobin (HbO2) to form methemoglobin (met-Hb) and the arylnitroso intermediates, which react with the β-Cys(93) chain of Hb to form Hb-arylsulfinamide adducts. The biochemistry of arylamine metabolism has been exploited to biomonitor certain AAs through their Hb arylsulfinamide adducts in humans. We examined the reactivity of HbO2 with the N-hydroxylated metabolites of 4-aminobiphenyl (ABP, HONH-ABP), aniline (ANL, HONH-ANL), and the HAAs 2-amino-9H-pyrido[2,3-b]indole (AαC, HONH-AαC), 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP, HONH-PhIP), and 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx, HONH-MeIQx). HONH-ABP, HO-ANL, and HONH-AαC induced methemoglobinemia and formed Hb sulfinamide adducts. However, HONH-MeIQx and HONH-PhIP did not react with the oxy-heme complex, and met-Hb formation and chemical modification of the β-Cys(93) residue were negligible. Molecular modeling studies showed that the distances between the H-ON-AA or H-ON-HAA substrates and the oxy-heme complex of HbO2 were too far away to induce methemoglobinemia. Different conformational changes in flexible helical and loop regions around the heme pocket induced by the H-ON-AA or H-ON-HAAs may explain the different proclivities of these chemicals to induce methemoglobinemia. Hb-Cys(93β) sulfinamide and sulfonamide adducts of ABP, ANL, and AαC were identified, by Orbitrap MS, following the proteolysis of Hb with trypsin, Glu-C, or Lys-C. Hb sulfinamide and sulfonamide adducts of ABP were identified in the blood of mice exposed to ABP, by Orbitrap MS. This is the first report of the identification of intact Hb

  18. Effect of oven cooking method on formation of heterocyclic amines and quality characteristics of chicken patties: steam-assisted hybrid oven versus convection ovens.

    Science.gov (United States)

    Isleroglu, Hilal; Kemerli, Tansel; Özdestan, Özgül; Uren, Ali; Kaymak-Ertekin, Figen

    2014-09-01

    The aim of this study was to evaluate effect of steam-assisted hybrid oven cooking method in comparison with convection ovens (natural and forced) on quality characteristics (color, hardness, cooking loss, soluble protein content, fat retention, and formation of heterocyclic aromatic amines) of chicken patties. The cooking experiments of chicken patties (n = 648) were conducted at oven temperatures of 180, 210, and 240°C until 3 different end point temperatures (75, 90, and 100°C) were reached. Steam-assisted hybrid oven cooking enabled faster cooking than convection ovens and resulted in chicken patties having lower a* and higher L* value, lower hardness, lower fat, and soluble protein content (P cooking loss than convection ovens. Steam-assisted hybrid oven could reduce the formation of heterocyclic aromatic amines that have mutagenic and carcinogenic effects on humans. © 2014 Poultry Science Association Inc.

  19. Influence of cooking methods and storage time on lipid and protein oxidation and heterocyclic aromatic amines production in bacon.

    Science.gov (United States)

    Soladoye, O P; Shand, P; Dugan, M E R; Gariépy, C; Aalhus, J L; Estévez, M; Juárez, M

    2017-09-01

    This study aimed to examine the influence of cooking methods and pre-determined refrigerated storage days on the production of lipid oxidation (TBARS), protein oxidation (PROTOX) and heterocyclic aromatic amines (HAA) in bacon. Forty-four pork bellies selected from pigs varying in breed, sex and diets to introduce variability in composition were processed as bacon. Sliced-bacon was stored at 4°C either for 2 or 28days and these storage groups were cooked either with microwave or frying pan. Microwave led to significantly higher PROTOX (P0.05) by the cooking methods and storage times. Similarly, the fatty acid composition of pork belly did not significantly influence the production of HAA, TBARS and PROTOX produced in bacon during cooking. Overall, microwave cooking had lesser impact on the production of carcinogenic compounds in bacon with only minor impact on sensory attributes. Copyright © 2017. Published by Elsevier Ltd.

  20. Simultaneous determination of 9 heterocyclic aromatic amines in pork products by liquid chromatography coupled with triple quadrupole tandem mass spectrometry

    Science.gov (United States)

    Shen, X. C.; Zhang, Y. L.; Cui, Y. Q.; Xu, L. Y.; Li, X.; Qi, J. H.

    2017-07-01

    Heterocyclic aromatic amines (HAAs) are potent mutagens that formed at high temperature in cooked, protein-rich food. Owing to their frequent intake, an accurate method is essential to access human health risk of HAAs exposure through detecting these compounds in various heat-treated meat products. In this study, a liquid chromatography-electrospray tandem mass spectrometry (LC--ESI-MS/MS) method was developed to perform the determination of 9 mutagenic heterocyclic amines (HAAs) in meat samples with multiple reaction monitoring (MRM) mode. Ultrasound assisted extraction and diatomaceous earth was employed to extract HAAs from food samples, and the analytes were purified and enriched using tandem solid phase extraction, with propyl sulfonic acid coupled to a C18 cartridge. Two parameters, extraction time and eluent, were carefully optimized to improve the extraction and purification efficiency. The LC separation was carried out using a Zorbax SB-C18 (3.5 μm particle size, 2.1 × 150 mm i.d.) column and optimized some parameters, such as pH, concentration and volume. Under the optimal experimental conditions, recoveries ranged from 52.97% to 97.11% with good quality parameters: limit of detection values between 0.02 and 0.24 ng mL-1, linearity (R2>0.998), and run-to-run and day-to-day precisions lower than 9.81% achieved. To evaluate the performance of the method in high throughput analysis of complex meat samples, the LC-MS/MS method was applied to the analysis of HAAs in three food samples, and the results demonstrated that the method can be used for the trace determination of HAAs in pork samples.

  1. Reducing effect of artichoke extract on heterocyclic aromatic amine formation in beef and chicken breast meat.

    Science.gov (United States)

    Tengilimoglu-Metin, Mercan Merve; Kizil, Mevlude

    2017-12-01

    The aim of this study was to investigate the inhibitory effect of different levels of artichoke extract (0, 0.5, and 1.0%) on the formation of heterocyclic aromatic amines (HAAs) in beef and chicken breast meat cooked by either pan-frying or oven-roasting. All meat samples were cooked at three different temperatures (150, 200, and 250°C) and the levels of 12 HAAs (IQ, IQx, MeIQ, MeIQx, 4,8-DiMeIQx, 7,8-DiMeIQx, PhIP, harman, norharman, AαC, MeAαC, and Trp-P-2) were assessed. The total HAA content in beef and chicken breast ranged from not detectable to 49.26ng/g, and not detectable to 83.06ng/g, respectively. The inhibitory effects of 0.5 and 1.0% artichoke extracts on total HAAs levels were found to be 6-46% and 25-98% in beef, and 5-97% and 14-95% in chicken breast, respectively. The present study showed that artichoke extracts could mitigate HAA formation especially in oven-roasted beef and chicken breast meat. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Dietary exposure to heterocyclic amines in high-temperature cooked meat and fish in Malaysia.

    Science.gov (United States)

    Jahurul, M H A; Jinap, S; Ang, S J; Abdul-Hamid, A; Hajeb, P; Lioe, H N; Zaidul, I S M

    2010-08-01

    The intake of heterocyclic amines is influenced by the amount and type of meat and fish ingested, frequency of consumption, cooking methods, cooking temperature, and duration of cooking. In this study, the dietary intake of heterocyclic amines in Malaysia and their main sources were investigated. Forty-two samples of meat and fish were analysed by high-performance liquid chromatography with photodiode array detector to determine the concentration of the six predominant heterocyclic amines, namely: 2-amino-3-methylimidazo[4,5-f] quinoline (IQ), 2-amino-3,4-dimethylimidazo[4,5-f] quinoline(MeIQ), 2-amino-3,8-dimethylimidazo[4,5-f] quinoxaline (MeIQx), 2-amino-3,4,8-trimethylimidazo[4,5-f] quinoxaline (4,8-DiMeIQx), 2-amino-3,7,8-trimethylimidazo[4,5-f] quinoxaline (7,8-DiMeIQx), and 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP). Dietary intake data were obtained using a food-frequency questionnaire when interviewing 600 Malaysian respondents. The level of total heterocyclic amines in food samples studies ranged from not detected to 38.7 ng g(-1). The average daily intake level of heterocyclic amine was 553.7 ng per capita day(-1). The intake of PhIP was the highest, followed by MeIQx and MeIQ. The results reveal that fried and grilled chicken were the major dietary source of heterocyclic amines in Malaysia. However, the heterocyclic amine intake by the Malaysian population was lower than those reported from other regions.

  3. Nitrite and hypochlorite treatments in determination of the contributions of IQ-type and non-IQ-type heterocyclic amines to the mutagenicities in crude pyrolyzed materials

    Energy Technology Data Exchange (ETDEWEB)

    Tsuda, M.; Negishi, C.; Makino, R.; Sato, S.; Yamaizumi, Z.; Hirayama, T.; Sugimura, T.

    1985-12-01

    The mutagenic heterocyclic amines Glu-P-2, MeA alpha C and Phe-P-1, which possess a 2-aminopyridine structure in their molecule (non-IQ-type mutagens), were found to be inactivated by nitrite treatment under acidic conditions, as observed previously with Trp-P-1, Trp-P-2, Glu-P-1 and A alpha C. In contrast, MeIQx, 4,8- and 7,8-DiMeIQx, which were originally isolated from fried beef or heated model mixtures of creatinine, amino acids and glucose, and which have a 2-aminoimidazole moiety in their molecules (IQ-type mutagens), were very resistant to nitrite treatment like IQ and MeIQ. Both types of mutagenic heterocyclic amines were completely inactivated by treatment with hypochlorite. This differential inactivation of mutagenic heterocyclic amines by nitrite and hypochlorite was used in determination of the contributions of IQ-type and non-IQ-type mutagens to the total mutagenicities of various pyrolyzed materials. The percentage contributions of IQ-type mutagens to the mutagenicities of broiled sardine, fried beef, broiled horse mackerel, cigarette smoke condensate and albumin tar were 88, 75, 48, 6 and 4, respectively.

  4. Infrared Spectroscopy of Matrix-Isolated Polycyclic Aromatic Nitrogen Heterocycles (PANHs)

    Science.gov (United States)

    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.

  5. Investigations on organogermanium compounds; III. N-tributylgermyl-substituted aliphatic and heterocyclic amines

    NARCIS (Netherlands)

    Rijkens, F.; Janssen, M.J.; Kerk, G.J.M. van der

    1965-01-01

    A series of new organogermanium compounds containing a germanium‐nitrogen bond, in many of which the nitrogen atom forms part of an heterocyclic ring, are prepared, in some cases by new methods: transamination reactions and reactions of germoxanes with heterocyclic amines. Striking differences in

  6. Quantitation of heterocyclic aromatic amines in ready to eat meatballs by ultra fast liquid chromatography.

    Science.gov (United States)

    Oz, Fatih

    2011-06-15

    Heterocyclic aromatic amines (HCAs) in meatballs ready to eat and sold in restaurants in Turkey were determined. A solid phase extraction method was used to isolate HCAs from meatballs. Various HCAs analysed by ultra fast liquid chromatography (UFLC) were varying levels of 2-amino-3-methylimidazo[4,5-f]quinoline (IQ) (up to 1.59ng/g), 2-amino-3-methylimidazo[4,5-f]quinoxaline (IQx) (up to 3.81ng/g), 2-amino-3,4-dimethylimidazo[4,5-f]quinoline (MeIQ) (up to 0.66ng/g), 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx) (not detected or not quantified), 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline (4,8-DiMeIQx) (not detected or not quantified), 2-amino-3,7,8-trimethylimidazo[4,5-f]quinoxaline (7,8-DiMeIQx) (up to 0.43ng/g), 2-amino-1-methyl-6-phenylimidazo[4,5-b] pyridine (PhIP) (up to 1.93ng/g), 2-amino-9H-pyrido[2,3-b]indole (AαC) (up to 0.35ng/g), and 2-amino-3-methyl-9H-pyrido[2,3-b]indole (MeAαC) (up to 0.43ng/g) in cooked meatballs which are consumed in Turkey. Overall average of total HCA amount was 5.54ng/g. The present study is to prove that HCAs can be isolated in a very short time (5min) by using UFLC. Copyright © 2010 Elsevier Ltd. All rights reserved.

  7. Effects of varying degrees of doneness on the formation of heterocyclic aromatic amines in chicken and beef satay.

    Science.gov (United States)

    Jinap, S; Mohd-Mokhtar, M S; Farhadian, A; Hasnol, N D S; Jaafar, S N; Hajeb, P

    2013-06-01

    The study was carried out to determine the effect of cooking method on Heterocyclic Aromatic Amines (HAs) concentration in grilled chicken and beef (satay). Six common HAs were investigated: 2-amino-3-methylimidazo[4,5-f]quinolone (IQ), 2amino 3,4dimethylimidazo [4,5f]quinoline (MeIQ), 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx), 2-amino-3,4,8 trimethylimidazo[4,5-f]quinoxaline (4,8-DiMeIQx), 2-amino-3,7,8trimethylimidazo [4,5-f]quinoxaline (7,8-DiMeIQx), and 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP). Chicken and beef satay samples were grilled to medium and well done level of doneness. Charcoal grilled (treatment A), microwave pre-treatment prior to grilling (treatment B), and microwave-deep fried (treatment C) were applied to beef and chicken satay samples. The satay samples which were microwaved prior to grilling (B) showed significantly (pcooked beef and chicken satay samples that were microwaved and deep fried (C) as an alternative method to grilling were proven to produce significantly lesser HAs as compared to charcoal-grilled (A) and microwaved prior to grilling (B). Copyright © 2013 Elsevier Ltd. All rights reserved.

  8. Impact of environmental exposures on the mutagenicity/carcinogenicity of heterocyclic amines

    Energy Technology Data Exchange (ETDEWEB)

    Felton, James S; Knize, Mark G; Bennett, L Michelle; Malfatti, Michael A; Colvin, Michael E; Kulp, Kristen S

    2004-05-20

    Carcinogenic heterocyclic amines are produced from overcooked foods and are highly mutagenic in most short-term test systems. One of the most abundant of these amines, 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), induces breast, colon and prostate tumors in rats. Human dietary epidemiology studies suggest a strong correlation between either meat consumption or well-done muscle meat consumption and cancers of the colon, breast, stomach, lung and esophagus. For over 20 years our laboratory has helped define the human exposure to these dietary carcinogens. In this report we describe how various environmental exposures may modulate the risk from exposure to heterocyclic amines, especially PhIP. To assess the impact of foods on PhIP metabolism in humans, we developed an LC/MS/MS method to analyze the four major PhIP urinary metabolites following the consumption of a single portion of grilled chicken. Adding broccoli to the volunteers' diet altered the kinetics of PhIP metabolism. At the cellular level we have found that PhIP itself stimulates a significant estrogenic response in MCF-7 cells, but even more interestingly, co-incubation of the cells with herbal teas appear to enhance the response. Numerous environmental chemicals found in food or the atmosphere can impact the exposure, metabolism, and cell proliferation response of heterocyclic amines.

  9. Impact of environmental exposures on the mutagenicity/carcinogenicity of heterocyclic amines

    International Nuclear Information System (INIS)

    Felton, James S.; Knize, Mark G.; Bennett, L. Michelle; Malfatti, Michael A.; Colvin, Michael E.; Kulp, Kristen S.

    2004-01-01

    Carcinogenic heterocyclic amines are produced from overcooked foods and are highly mutagenic in most short-term test systems. One of the most abundant of these amines, 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), induces breast, colon and prostate tumors in rats. Human dietary epidemiology studies suggest a strong correlation between either meat consumption or well-done muscle meat consumption and cancers of the colon, breast, stomach, lung and esophagus. For over 20 years our laboratory has helped define the human exposure to these dietary carcinogens. In this report we describe how various environmental exposures may modulate the risk from exposure to heterocyclic amines, especially PhIP. To assess the impact of foods on PhIP metabolism in humans, we developed an LC/MS/MS method to analyze the four major PhIP urinary metabolites following the consumption of a single portion of grilled chicken. Adding broccoli to the volunteers' diet altered the kinetics of PhIP metabolism. At the cellular level we have found that PhIP itself stimulates a significant estrogenic response in MCF-7 cells, but even more interestingly, co-incubation of the cells with herbal teas appear to enhance the response. Numerous environmental chemicals found in food or the atmosphere can impact the exposure, metabolism, and cell proliferation response of heterocyclic amines

  10. Synthesis and bioelectrochemical behavior of aromatic amines.

    Science.gov (United States)

    Shabbir, Muhammad; Akhter, Zareen; Ahmad, Iqbal; Ahmed, Safeer; Bolte, Michael; McKee, Vickie

    2017-12-01

    Four aromatic amines 1-amino-4-phenoxybenzene (A 1 ), 4-(4-aminophenyloxy) biphenyl (A 2 ), 1-(4-aminophenoxy) naphthalene (A 3 ) and 2-(4-aminophenoxy) naphthalene (A 4 ) were synthesized and characterized by elemental, spectroscopic (FTIR, NMR), mass spectrometric and single crystal X-ray diffraction methods. The compounds crystallized in monoclinic crystal system with space group P2 1 . Intermolecular hydrogen bonds were observed between the amine group and amine/ether acceptors of neighboring molecules. Electrochemical investigations were done using cyclic voltammetry (CV), square wave voltammetry (SWV) and differential pulse voltammetry (DPV). CV studies showed that oxidation of aromatic amines takes place at about 0.9 V (vs. Ag/AgCl) and the electron transfer (ET) process has irreversible nature. After first scan reactive intermediate were generated electrochemically and some other cathodic and anodic peaks also appeared in the succeeding scans. DPV study revealed that ET process is accompanied by one electron. DNA binding study of aromatic amines was performed by CV and UV-visible spectroscopy. These investigations revealed groove binding mode of interaction of aromatic amines with DNA. Copyright © 2017 Elsevier Inc. All rights reserved.

  11. Polymorphisms in heterocyclic aromatic amines metabolism-related genes are associated with colorectal adenoma risk.

    Science.gov (United States)

    Eichholzer, Monika; Rohrmann, Sabine; Barbir, Aline; Hermann, Silke; Teucher, Birgit; Kaaks, Rudolf; Linseisen, Jakob

    2012-01-01

    Colorectal adenoma (CRA) and colorectal cancer (CRC) risks have been linked to the intake of red and processed meat. Heterocyclic aromatic amines (HCA) formed herein during high temperature cooking, are metabolized by a variety of enzymes, and allelic variation in the coding genes could influence individual CRA risk. Associations of polymorphisms in NAT1, NAT2, GSTA1, SULT1A1, CYP1A2, UGT1A7, UGT1A9, GSTP1 genes with colorectal adenoma risk were investigated in a nested case-control study of the EPIC-Heidelberg cohort including 428 cases matched by age, sex and year of recruitment with one or two controls (n=828) with negative colonoscopy per case. Genoyping was preformed with the Sequenom MassArray system and the LightCycler 480. Conditional logistic regression was used to compute odds ratios (OR) and corresponding 95% confidence intervals (CI). For rs15561 (NAT1) and rs1057126 (NAT1), the rarer allel was significantly inversely associated with adenoma risk OR=0.80 (95% CI 0.65-0.97) and (OR=0.81 (95% CI 0.65-0.99) and, respectively). For the combined NAT2 alleles encoding for enzymes with medium (versus slow) activity we also observed a significantly inverse association with adenoma risk (OR=0.75; 95% CI 0.85-0.97). In addition, homozygous carriers of the A allele of rs3957357 (GSTA1), i.e., those with a decreased enzyme activity, had a decreased risk of colorectal adenoma with an OR of 0.68 (95% CI 0.50-0.92; AA versus GG/GA). Polymorphisms in the other tested genes did not modify the risk of colorectal adenomas. In conclusion, polymorphisms in NAT1, NAT2, and GSTA1 are related to colorectal adenoma risk in this German cohort.

  12. Lactoperoxidase, an Antimicrobial Milk Protein, as a Potential Activator of Carcinogenic Heterocyclic Amines in Breast Cancer.

    Science.gov (United States)

    Sheikh, Ishfaq Ahmad; Jiffri, Essam Hussain; Kamal, Mohammad Amjad; Ashraf, Ghulam Md; Beg, Mohd Amin

    2017-11-01

    Lactoperoxidase (LPO) is an antimicrobial protein secreted from mammary, salivary and other mucosal glands. It is an important member of heme peroxidase enzymes and the primary peroxidase enzyme present in breast tissues. In addition to the antimicrobial properties, LPO has been shown to be associated with breast cancer etiology. Heterocyclic amines, an important class of environmental and dietary carcinogens, have been increasingly associated with breast cancer etiology. Heterocyclic amines undergo activation in breast tissue as a result of oxidation by LPO. The current study includes three important heterocyclic amines, 2-amino-3-methylimidazo[4,5-f]quinoline (IQ), 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx) and 2-amino-1-methy-6-phenylimidazo[4,5-b]-pyridine (PhIP), that have carcinogenic activity. The structural binding characterization of IQ, MeIQx and PhIP with LPO was done using in silico approaches. Their binding pattern and interactions with LPO amino acid residues were analyzed. The three compounds bound in the distal heme cavity of LPO without replacing the important water molecule required for oxidation of substrate compounds. PhIP displayed lesser binding affinity for LPO in comparison to IQ and MeIQx. The binding mode of heterocyclic amines in distal heme cavity of LPO resembled to that of substrate binding pattern. The three heterocyclic amines are suggested to act as LPO substrate. The undisturbed water molecule present in distal heme cavity of the LPO is expected to facilitate the oxidation and activation of the three heterocyclic amines. These activated compounds may potentially bind with DNA in breast tissues forming DNA adducts and may subsequently lead to breast cancer initiation. Copyright© 2017, International Institute of Anticancer Research (Dr. George J. Delinasios), All rights reserved.

  13. Screening of molecular cell targets for carcinogenic heterocyclic aromatic amines by using CALUX® reporter gene assays.

    Science.gov (United States)

    Steinberg, Pablo; Behnisch, Peter A; Besselink, Harrie; Brouwer, Abraham A

    2017-06-01

    Heterocyclic aromatic amines (HCAs) are compounds formed when meat or fish are cooked at high temperatures for a long time or over an open fire. To determine which pathways of toxicity are activated by HCAs, nine out of the ten HCAs known to be carcinogenic in rodents (2-amino-9H-pyrido[2,3-b]indole (AαC), 2-aminodipyrido[1,2-a:3',2-d]imidazole (Glu-P-2), 2-amino-3-methylimidazo[4,5-f]quinoline (IQ), 2-amino-3-methyl-9H-pyrido[2,3-b]indole (MeAαC), 2-amino-3,4-dimethylimidazo[4,5-f]quinoline (MeIQ), 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx), 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), 3-amino-1,4-dimethyl-5H-pyrido[4,3-b]indole (Trp-P-1), and 3-amino-1-methyl-5H-pyrido[4,3-b]indole (Trp-P-2)) were tested in the estrogen receptor α (ERα), androgen receptor (AR), glucocorticoid receptor (GR), peroxisome proliferator-activated receptor γ2 (PPARγ2), polycyclic aromatic hydrocarbons (PAH), Nrf2, and p53 CALUX® reporter gene assays. Trp-P-1 was the only HCA that led to a positive response in the ERα, PPARγ2, and Nrf2 CALUX® assays. In the PAH CALUX® assay, Trp-P-2, MeAαC, and AαC induced luciferase activity to a greater extent than MeIQ and PhIP. In the p53 CALUX® assay without a coupled metabolic activation, only Trp-P-1 and Trp-P-2 enhanced luciferase expression; when a metabolic activation step was coupled to the p53 CALUX® assay, Trp-P-1, Glu-P-2, MeIQ, MeIQx, and PhIP induced a positive response. No HCA was positive in the AR and GR CALUX® assays. Taken together, the results obtained show that the battery of CALUX® assays performed in the present study can successfully be used to screen for molecular cell targets of carcinogenic compounds such as HCAs.

  14. Bioinspired aerobic oxidation of secondary amines and nitrogen heterocycles with a bifunctional quinone catalyst.

    Science.gov (United States)

    Wendlandt, Alison E; Stahl, Shannon S

    2014-01-08

    Copper amine oxidases are a family of enzymes with quinone cofactors that oxidize primary amines to aldehydes. The native mechanism proceeds via an iminoquinone intermediate that promotes high selectivity for reactions with primary amines, thereby constraining the scope of potential biomimetic synthetic applications. Here we report a novel bioinspired quinone catalyst system consisting of 1,10-phenanthroline-5,6-dione/ZnI2 that bypasses these constraints via an abiological pathway involving a hemiaminal intermediate. Efficient aerobic dehydrogenation of non-native secondary amine substrates, including pharmaceutically relevant nitrogen heterocycles, is demonstrated. The ZnI2 cocatalyst activates the quinone toward amine oxidation and provides a source of iodide, which plays an important redox-mediator role to promote aerobic catalytic turnover. These findings provide a valuable foundation for broader development of aerobic oxidation reactions employing quinone-based catalysts.

  15. Breast cancer, heterocyclic aromatic amines from meat and N-acetyltransferase 2 genotype.

    Science.gov (United States)

    Delfino, R J; Sinha, R; Smith, C; West, J; White, E; Lin, H J; Liao, S Y; Gim, J S; Ma, H L; Butler, J; Anton-Culver, H

    2000-04-01

    Breast cancer risk has been hypothesized to increase with exposure to heterocyclic aromatic amines (HAAs) formed from cooking meat at high temperature. HAAs require enzymatic activation to bind to DNA and initiate carcinogenesis. N-acetyltransferase 2 (NAT2) enzyme activity may play a role, its rate determined by a polymorphic gene. We examined the effect of NAT2 genetic polymorphisms on breast cancer risk from exposure to meat by cooking method, doneness and estimated HAA [2-amino-1-methyl-6-phenylimidazole[4,5-b]pyridine (PhIP), 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx) and 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline (DiMeIQx)] intake. Women were recruited with suspicious breast masses and questionnaire data were collected prior to biopsy to blind subjects and interviewers to diagnoses. For 114 cases with breast cancer and 280 controls with benign breast disease, NAT2 genotype was determined using allele-specific PCR amplification to detect slow acetylator mutations. HAAs were estimated from interview data on meat type, cooking method and doneness, combined with a quantitative HAA database. Logistic regression models controlled for known risk factors, first including all controls, then 108 with no or low risk (normal breast or no hyperplasia) and finally 149 with high risk (hyperplasia, atypical hyperplasia, complex fibroadenomas). Meat effects were examined within NAT2 strata to assess interactions. We found no association between NAT2 and breast cancer. These Californian women ate more white than red meat (control median 46 versus 8 g/day). There were no significant associations of breast cancer with red meat for any doneness. White meat was significantly protective (>67 versus chicken, including well done, pan fried and barbecued chicken. MeIQx and DiMeIQx were not associated with breast cancer. A protective effect of PhIP was confounded after controlling for well done chicken. Results were unchanged using low or high risk controls or dropping

  16. Effect of cooking methods on the formation of heterocyclic aromatic amines in chicken and duck breast.

    Science.gov (United States)

    Liao, G Z; Wang, G Y; Xu, X L; Zhou, G H

    2010-05-01

    Heterocyclic aromatic amines (HAAs), potent mutagens/carcinogens, are pyrolysis formed during the cooking of meat and fish. In the present study, the effects of various cooking methods, pan-frying, deep-frying, charcoal grilling and roasting on the formation of HAAs in chicken breast and duck breast were studied. The various HAAs formed during cooking were isolated by solid-phase extraction and analyzed by high-performance liquid chromatography (HPLC). Results showed that chicken breast cooked by charcoal grilling contained the highest content of total HAAs, as high as 112 ng/g, followed by pan-fried duck breast (53.3 ng/g), charcoal grilled duck breast (32 ng/g), pan-fried chicken breast (27.4 ng/g), deep-fried chicken breast (21.3 ng/g), deep-fried duck breast (14 ng/g), roasted duck breast (7 ng/g) and roasted chicken breast (4 ng/g). For individual HAA, the most abundant HAA was 9H-pyrido-[4,3-b]indole (Norharman), which was detected in charcoal grilled chicken breast at content as high as 32.2 ng/g, followed by 1-methyl-9H-pyrido[4,3-b] indole (Harman) and 2-amino-1-methyl-6-phenylimidazo[4,5-f]pyridine(PhIP) at 32 and 31.1 ng/g in charcoal grilled chicken breast, respectively. The content of PhIP in pan-fried duck and chicken breast were 22 and 18.3 ng/g, respectively. Generally, the type and content of HAAs in cooked poultry meat varies with cooking method and cooking conditions. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

  17. Photometabolism of Heterocyclic Aromatic Compounds by Rhodopseudomonas palustris OU 11

    Science.gov (United States)

    Sasikala, C.; Ramana, C. V.; Rao, P. Raghuveer

    1994-01-01

    Rhodopseudomonas palustris OU 11 (ATCC 51186; DSM 7375) isolated from a pond of chemical industry effluent could anaerobically photometabolize heterocyclic aromatic compounds belonging to the pyridine and pyrazine groups only after a period of adaptation on pyrazinoic acid of 5 to 6 weeks. Growth on heterocyclic compounds was light dependent. The effects of various concentrations of heterocyclic compounds on growth suggest that higher concentrations of these compounds inhibit growth and are toxic. PMID:16349307

  18. A nanocomposite disk prepared from reduced graphene oxide and gold nanoparticles for the preconcentration of heterocyclic aromatic amines prior to their determination by HPLC

    International Nuclear Information System (INIS)

    Tan, Connieal; Wang, Yiru; Deng, Zhuo; Xu, Na; Song, Xinhong; Liu, Haihong; Rong, Mingcong; Chen, Xi

    2014-01-01

    We report on a preconcentration disk for the determination of trace amounts of heterocyclic aromatic amines (HAAs) in the groups of quinoline and quinoxaline congeners as possible human carcinogens. The disk is based on nanocomposite (NC) prepared from graphene oxide as the precursor and from gold nanoparticles that act as building blocks to form a three-dimensional NC. If deposited in the sampling valve of a HPLC system, the material displays excellent extraction capability for HAAs owing to its large surface and π-π stacking interaction. Following an optimization of the extraction parameters, the method was successfully applied to the simultaneous determination of polar HAAs in meat samples with detection limit of 0.09 to 0.16 ng g −1 and recoveries of 69.5 to 122.7 %. The disk was used in more than 150 subsequent preconcentration cycles without obvious loss of the absorption capability. The results reveal that this new NC represents an excellent sorbent for purposes of preconcentration. (author)

  19. Two-dimensional inorganic–organic hybrid semiconductors composed of double-layered ZnS and monoamines with aromatic and heterocyclic aliphatic rings: Syntheses, structures, and properties

    International Nuclear Information System (INIS)

    Wang, Sujing; Li, Jing

    2015-01-01

    As an addition to the II–VI based inorganic–organic hybrid semiconductor family, five new two-dimensional (2D) double-layered structures have been synthesized employing monoamines with different aromatic or heterocyclic aliphatic rings. Zn 2 S 2 (bza) (1), Zn 2 S 2 (mbza) (2), Zn 2 S 2 (fbza) (3), Zn 2 S 2 (pca) (4), and Zn 2 S 2 (thfa) (5) (bza=benzylamine, mbza=4-methoxybenzylamine, fbza=4-flurobenzylamine, pca=3-picolylamine, and thfa=tetrahydrofurfurylamine) are prepared by solvothermal reactions and characterized by different analytical methods, including powder X-ray diffraction, optical diffuse reflection, thermogravimetric analysis and photoluminescence spectroscopy. The powder X-ray diffraction patterns show that all five compounds adopt 2D double-layered structures. Optical diffuse reflectance spectra of these compounds suggest that they have notably lower band gaps than those of the similar compounds composed of aliphatic alkyl amines. Their photoluminescence properties and thermal stability are also analyzed. - Graphical abstract: Five new members of two-dimensional double-layered 2D-Zn 2 S 2 (L) (L=Ligand) structures employing monoamines with different aromatic or heterocyclic aliphatic rings have been designed, synthesized, and characterized. - Highlights: • A new sub-family of II-VI based hybrid semiconductors are designed, synthesized, and structurally characterized using amines with aromatic or aliphatic cyclic rings. • These compounds have notably lower band gaps than those made of aliphatic alkyl amines, greatly broadening the range of band gaps of this material family. • They emit strongly with systematically tunable emission intensity and energy

  20. [Distribution and sources of oxygen and sulfur heterocyclic aromatic compounds in surface soil of Beijing, China].

    Science.gov (United States)

    He, Guang-Xiu; Zhang, Zhi-Huan; Peng, Xu-Yang; Zhu, Lei; Lu, Ling

    2011-11-01

    62 surface soil samples were collected from different environmental function zones in Beijing. Sulfur and oxygen heterocyclic aromatic compounds were detected by GC/MS. The objectives of this study were to identify the composition and distribution of these compounds, and discuss their sources. The results showed that the oxygen and sulfur heterocyclic aromatic compounds in the surface soils mainly contained dibenzofuran, methyl- and C2-dibenzofuran series, dibenzothiophene, methyl-, C2- and C3-dibenzothiophene series and benzonaphthothiophene series. The composition and distribution of the oxygen and sulfur heterocyclic aromatic compounds in the surface soil samples varied in the different environmental function zones, of which some factories and the urban area received oxygen and sulfur heterocyclic aromatic compounds most seriously. In Beijing, the degree of contamination by oxygen and sulfur heterocyclic aromatic compounds in the north surface soil was higher than that in the south. There were preferable linear correlations between the concentration of dibenzofuran series and fluorene series, as well as the concentration of dibenzothiophene series and dibenzofuran series. The oxygen and sulfur heterocyclic aromatic compounds in the surface soil were mainly derived from combustion products of oil and coal and direct input of mineral oil, etc. There were some variations in pollution sources of different environmental function zones.

  1. Differential toxicity of heterocyclic aromatic amines and their mixture in metabolically competent HepaRG cells

    International Nuclear Information System (INIS)

    Dumont, Julie; Josse, Rozenn; Lambert, Carine; Antherieu, Sebastien; Le Hegarat, Ludovic; Aninat, Caroline; Robin, Marie-Anne; Guguen-Guillouzo, Christiane

    2010-01-01

    Human exposure to heterocyclic aromatic amines (HAA) usually occurs through mixtures rather than individual compounds. However, the toxic effects and related mechanisms of co-exposure to HAA in humans remain unknown. We compared the effects of two of the most common HAA, 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) and 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx), individually or in combination, in the metabolically competent human hepatoma HepaRG cells. Various endpoints were measured including cytotoxicity, apoptosis, oxidative stress and DNA damage by the comet assay. Moreover, the effects of PhIP and/or MeIQx on mRNA expression and activities of enzymes involved in their activation and detoxification pathways were evaluated. After a 24 h treatment, PhIP and MeIQx, individually and in combination, exerted differential effects on apoptosis, oxidative stress, DNA damage and cytochrome P450 (CYP) activities. Only PhIP induced DNA damage. It was also a stronger inducer of CYP1A1 and CYP1B1 expression and activity than MeIQx. In contrast, only MeIQx exposure resulted in a significant induction of CYP1A2 activity. The combination of PhIP with MeIQx induced an oxidative stress and showed synergistic effects on apoptosis. However, PhIP-induced genotoxicity was abolished by a co-exposure with MeIQx. Such an inhibitory effect could be explained by a significant decrease in CYP1A2 activity which is responsible for PhIP genotoxicity. Our findings highlight the need to investigate interactions between HAA when assessing risks for human health and provide new insights in the mechanisms of interaction between PhIP and MeIQx.

  2. Genetically modified CHO cells for studying the genotoxicity of heterocyclic amines from cooked foods

    International Nuclear Information System (INIS)

    Thompson, L.H.; Wu, R.W.; Felton, J.S.

    1995-07-01

    We have developed metabolically competent CHO cells to evaluate the genotoxicity associated with heterocyclic amines, such as those that are present in cooked foods. Into repair-deficient UV5 cells we introduced cDNAs for expressing cytochrome P450IA2 and acetyltransferases. We then genetically reverted these transformed lines to obtain matched metabolically competent repair-deficient/proficient lines. For a high mutagenic response, we find a requirement for acetyltransferase with IQ but not with PhIP. This system allows for both quantifying mutagenesis and analyzing the mutational spectra produced by heterocyclic amines

  3. One-Pot Two-Step Multicomponent Process of Indole and Other Nitrogenous Heterocycles or Amines toward α-Oxo-acetamidines.

    Science.gov (United States)

    Martinez-Ariza, Guillermo; McConnell, Nicholas; Hulme, Christopher

    2016-04-15

    A cesium carbonate promoted three-component reaction of N-H containing heterocycles, primary or secondary amines, arylglyoxaldehydes, and anilines is reported. The key step involves a tandem sequence of N-1 addition of a heterocycle or an amine to preformed α-iminoketones, followed by an air- or oxygen-mediated oxidation to form α-oxo-acetamidines. The scope of the reaction is enticingly broad, and this novel methodology is applied toward the synthesis of various polycyclic heterocycles.

  4. Trace Analysis of Mutagenic Heterocyclic Aromatic Amines in Cigarette Smoke Condensate and its Base Fractions via Silylation-GC-MS

    Directory of Open Access Journals (Sweden)

    Liu S

    2014-12-01

    Full Text Available Among the more than 5000 chemicals reported in cigarette smoke condensate (CSC, heterocyclic aromatic amines (HAAs are considered to be a contributor to observed biological activity. HAAs are non-volatile and are reported at ppb levels in CSC. A new method for HAA analysis at the trace level is reported here. N, O-Bis(trimethylsilyl trifluoroacetamide (BSTFA containing 1% trimethylchlorosilane was employed to derivatize amino groups by heating the reagent containing a sample of CSC at 80 °C for 30 min followed by analysis employing gas chromatography-mass spectroscopy (GC-MS in the selected-ion-monitoring (SIM mode. This derivatization method afforded symmetrical peak shapes on a ZB-50 stationary phase and achieved instrumental limits of quantification (LOQ at 10:1 S/N from -1 ng/mL for AαC to120 ng/mL for Glu-P-1. The chemical identity of each derivative was confirmed by comparison of retention time and mass spectra of standards. The latter were characterized by the following ions: M·+ or [M-1]+, [M-15]+, and m/z 73 (i.e., trimethylsilyl. CSC and its base sub-fractions were studied using the GC-MS method. Ten HAAs were screened and five were quantified in cigarette smoke condensate, while 2-5 HAAs were quantified in each of three base sub-fractions. Values obtained with the new procedure agree well with values reported in the literature and with results obtained from a commercial laboratory via a different analytical method. The potential contribution of each HAA to the overall mutagenic activity observed for CSC and its base fractions is discussed. When considered together, HAAs account for only a small portion (-7.8% of the observed mutagenicity of the CSC.

  5. Fluorescence method for enzyme analysis which couples aromatic amines with aromatic aldehydes

    Science.gov (United States)

    Smith, R.E.; Dolbeare, F.A.

    1980-10-21

    Analysis of proteinases is accomplished using conventional amino acid containing aromatic amine substrates. Aromatic amines such as 4-methoxy-2-naphthylamine (4M2NA), 2-naphthylamine, aminoisophthalic acid dimethyl ester, p-nitroaniline, 4-methoxy-1-aminofluorene and coumarin derivatives resulting from enzymatic hydrolysis of the substrate couples with aromatic aldehydes such as 5-nitrosalicylaldehyde (5-NSA), benzaldehyde and p-nitrobenzaldehyde to produce Schiff-base complexes which are water insoluble. Certain Schiff-base complexes produce a shift from blue to orange-red (visible) fluorescence. Such complexes are useful in the assay of enzymes. No Drawings

  6. Two-dimensional inorganic–organic hybrid semiconductors composed of double-layered ZnS and monoamines with aromatic and heterocyclic aliphatic rings: Syntheses, structures, and properties

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Sujing; Li, Jing, E-mail: jingli@rutgers.edu

    2015-04-15

    As an addition to the II–VI based inorganic–organic hybrid semiconductor family, five new two-dimensional (2D) double-layered structures have been synthesized employing monoamines with different aromatic or heterocyclic aliphatic rings. Zn{sub 2}S{sub 2}(bza) (1), Zn{sub 2}S{sub 2}(mbza) (2), Zn{sub 2}S{sub 2}(fbza) (3), Zn{sub 2}S{sub 2}(pca) (4), and Zn{sub 2}S{sub 2}(thfa) (5) (bza=benzylamine, mbza=4-methoxybenzylamine, fbza=4-flurobenzylamine, pca=3-picolylamine, and thfa=tetrahydrofurfurylamine) are prepared by solvothermal reactions and characterized by different analytical methods, including powder X-ray diffraction, optical diffuse reflection, thermogravimetric analysis and photoluminescence spectroscopy. The powder X-ray diffraction patterns show that all five compounds adopt 2D double-layered structures. Optical diffuse reflectance spectra of these compounds suggest that they have notably lower band gaps than those of the similar compounds composed of aliphatic alkyl amines. Their photoluminescence properties and thermal stability are also analyzed. - Graphical abstract: Five new members of two-dimensional double-layered 2D-Zn{sub 2}S{sub 2}(L) (L=Ligand) structures employing monoamines with different aromatic or heterocyclic aliphatic rings have been designed, synthesized, and characterized. - Highlights: • A new sub-family of II-VI based hybrid semiconductors are designed, synthesized, and structurally characterized using amines with aromatic or aliphatic cyclic rings. • These compounds have notably lower band gaps than those made of aliphatic alkyl amines, greatly broadening the range of band gaps of this material family. • They emit strongly with systematically tunable emission intensity and energy.

  7. SEDIMENT-ASSOCIATED REACTIONS OF AROMATIC AMINES. 2. QSAR DEVELOPMENT

    Science.gov (United States)

    The fate of aromatic amines in soils and sediments is dominated by irreversible binding through nucleophilic addition and oxidative radical coupling. Despite the common occurrence of the aromatic amine functional group in organic chemicals, the molecular properties useful for pr...

  8. Physicochemical Mechanisms of Synergistic Biological Action of Combinations of Aromatic Heterocyclic Compounds

    OpenAIRE

    Evstigneev, Maxim P.

    2013-01-01

    The mechanisms of synergistic biological effects observed in the simultaneous use of aromatic heterocyclic compounds in combination are reviewed, and the specific biological role of heteroassociation of aromatic molecules is discussed.

  9. Nucleobases in Space: Laboratory Studies of Polycyclic Aromatic Nitrogen Heterocycles

    Science.gov (United States)

    Elsila, Jamie; Mattioda, Andy; Bernstein, Max; Sandford, Scott; Hudgins, Doug

    2005-01-01

    Polycyclic Aromatic Nitrogen Heterocycles (PANHs) are heterocyclic aromatics Le., PAHs with carbon atoms replaced by a nitrogen atom. These molecules have been detected in meteorite extracts, and in general these nitrogen heterocycles are of astrobiological interest since this class of molecules include nucleobases, basic components of our nucleic acids. These compounds are predicted to be present in the interstellar medium and in Titan tholin, but have received relatively little attention. We will present spectra and reactions of PANHs, frozen in solid H2O at 12 K, conditions germane to astronomical observations. In contrast to simple PAHs, that do not interact strongly with solid H2O, the nitrogen atoms in PANHs are potentially capable of hydrogen bonding with H20 changing their spectra, complicating their remote detection on the surfaces of icy bodies. Moreover, we have studied the photo-chemistry of these interesting compounds under astrophysical conditions and will use our lab studies to assess a potential interstellar heritage of these compounds in carbonaceous chondrites.

  10. Effect of cooking time and temperature on the heterocyclic amine content of fried beef patties.

    Science.gov (United States)

    Knize, M G; Dolbeare, F A; Carroll, K L; Moore, D H; Felton, J S

    1994-07-01

    The mutagenic heterocyclic amines 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx), 2-amino-3-methylimidazo[4,5-f]quinoline (IQ), 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) and 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline (DiMeIQx) were measured in ground-beef patties fried at 150, 190 and 230 degrees C for 2-10 min on each side. Heterocyclic amines were purified using solid-phase extraction and analysed by HPLC. Recovery-corrected amounts of each heterocyclic amine were determined by the method of standard addition based on spiked samples with recoveries ranging from 40 to 70%. Mutagenic activity measured by the Ames/Salmonella test was determined for each sample. The amounts of MeIQx, PhIP, DiMeIQx and IQ increased with time and temperature of cooking. 3-Amino-1,4-dimethyl-5H-pyrido[4,3-b]indole (Trp-P-1), 3-amino-1-methyl-5H-pyrido[4,3-b]indole (Trp-P-2) and 2-amino-9H-pyrido[2,3-b]indole (A alpha C) were not detected in any sample. The mutagenic activity response measured for the meat extracts (TA98 revertants) was similar to the mutagenic activity calculated from the mass of heterocyclic amines present. The rate of formation of PhIP in a model system containing creatinine and phenylalanine heated in 80% diethylene glycol was compared with PhIP formation during meat frying. The apparent heats of activation were 6.5 kcal/mol in the model system compared with 6.0 kcal/mol in the fried meat patties. The increase in PhIP and MeIQx formation fitted an exponential function over the range 0 to 11 min and from 150 to 230 degrees C. This report shows clearly that increases in cooking temperature and time can have a profound effect on the amounts of heterocyclic amines generated and subsequently consumed in the diet.

  11. Two food-borne heterocyclic amines: Metabolism and DNA adduct formation of amino-alpha-carbolines

    DEFF Research Database (Denmark)

    Frederiksen, Hanne

    2005-01-01

    or proteins of animal or vegetable origin, furthermore they are found in many cooked foods, such as fish, meat, and chicken. The specific mutagenicity of the amino-a-carbolines are lower in the Ames Salmonella assay than other heterocyclic amines, but in rodent studies the carcinogenicity of the aminoa, alpha......The amino-alpha-carbolines 2-amino-9H-pyrido[2,3-b]indole (A alpha C) and 2-amino-3-methyl-9H-pyrido-[2,3-b]indole (MeA alpha C) are two mutagenic and carcinogenic heterocyclic amines formed during ordinary cooking. Amino-alpha-carbolines can be formed in model systems by pyrolyzing tryptophan...

  12. Sodium Perborate Oxidation of an Aromatic Amine

    Science.gov (United States)

    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)

  13. Analysis of heterocyclic amines in hair by on-line in-tube solid-phase microextraction coupled with liquid chromatography−tandem mass spectrometry

    International Nuclear Information System (INIS)

    Kataoka, Hiroyuki; Inoue, Tsutomu; Saito, Keita; Kato, Hisato; Masuda, Kazufumi

    2013-01-01

    Graphical abstract: Mutagenic and carcinogenic heterocyclic amines are accumulated in the hair of smoker. -- Highlights: •On-line in-tube solid-phase microextraction of heterocyclic amines was optimized. •Fourteen heterocyclic amines were simultaneously determined by LC–MS/MS. •Pico gram levels of heterocyclic amines could be easily analyzed within 15 min. •Heterocyclic amines could be quantitatively analyzed from several milligrams of hair. •The method is useful for the assessment of long-term exposure to heterocyclic amines. -- Abstract: Mutagenic and carcinogenic heterocyclic amines (HCAs) are formed during heating of various proteinaceous foods, but human exposure to HCAs has not yet been elucidated in detail. To assess long-term exposure to HCAs, we developed a simple and sensitive method for measuring HCAs in hair by automated on-line in-tube solid-phase microextraction (SPME) coupled with liquid chromatography–tandem mass spectrometry (LC–MS/MS). Using a Zorbax Eclipse XDB-C8 column, 16 HCAs were analyzed within 15 min. The optimum in-tube SPME conditions were 20 draw/eject cycles of 40 μL sample at a flow rate of 200 μL min −1 using a Supel-Q PLOT capillary column as an extraction device. The extracted HCAs were easily desorbed from the column by passage of the mobile phase, with no carryover observed. This in-tube SPME LC–MS/MS method showed good linearity for HCAs in the range of 10–2000 pg mL −1 , with correlation coefficients above 0.9989 (n = 18), using stable isotope-labeled HCA internal standards. The detection limits (S/N = 3) of 14 HCAs except for MeAαC and Glu-P-1 were 0.10–0.79 pg mL −1 . This method was successfully utilized to analyze 14 HCAs in hair samples without any interference peaks, with quantitative limits (S/N = 10) of about 0.17–1.32 pg mg −1 hair. Using this method, we evaluated the exposure to HCAs in cigarette smoke and the suitability of using hair HCAs as exposure biomarkers

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

    Science.gov (United States)

    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.

  15. Synthesis and Characterization of a New Heterocyclic Azo Pigment

    International Nuclear Information System (INIS)

    Asniza, M.; Issam, A.M.; Khalil, H.P.S.A.

    2011-01-01

    A new heterocyclic coupling agent has been produced from the reaction of maleic anhydride and p-aminophenol, namely N-(4-hexahydrophenol)maleimide. The coupling agent underwent azo coupling reaction with aromatic amine, which is p-aminophenol to produce a new heterocyclic azo pigment. The pigment was then subjected to solubility, hiding power and light fastness test. Fourier Transform Infrared Spectroscopy (FTIR), Ultraviolet/ Visible (UV/Vis) Spectroscopy, and Nuclear Magnetic Resonance Spectroscopy ( 1 H-NMR, 13 C-NMR) were used to obtain the characteristics and structural features of the pigment. (author)

  16. Structural and spectral comparisons between isomeric benzisothiazole and benzothiazole based aromatic heterocyclic dyes

    Science.gov (United States)

    Wang, Yin-Ge; Wang, Yue-Hua; Tao, Tao; Qian, Hui-Fen; Huang, Wei

    2015-09-01

    A pair of isomeric heterocyclic compounds, namely 3-amino-5-nitro-[2,1]-benzisothiazole and 2-amino-6-nitrobenzothiazole, are used as the diazonium components to couple with two N-substituted 4-aminobenzene derivatives. As a result, two pairs of isomeric aromatic heterocyclic azo dyes have been produced and they are structurally and spectrally characterized and compared including single-crystal structures, electronic spectra, solvatochromism and reversible acid-base discoloration, thermal stability and theoretically calculations. It is concluded that both benzisothiazole and benzothiazole based dyes show planar molecular structures and offset π-π stacking interactions, solvatochromism and reversible acid-base discoloration. Furthermore, benzisothiazole based aromatic heterocyclic dyes exhibit higher thermal stability, larger solvatochromic effects and maximum absorption wavelengths than corresponding benzothiazole based ones, which can be explained successfully by the differences of their calculated isomerization energy, dipole moment and molecular band gaps.

  17. Complexes of uranyl with N-oxides of heterocyclic amines. Electron-vibrational absorption spectra

    International Nuclear Information System (INIS)

    Jezowska-Trzebiatowska, B.; Wieczorek, M.

    1977-01-01

    A number of coordination compounds formed by uranyl chloride and nitrate with N-oxides of heterocyclic amines have been prepared and characterized by spectral measurements in the absorption region 20000-50000 cm -1 . The electrons and vibronic transitions have been determined and discussed. (author)

  18. The effects of different spices and fat types on the formation of heterocyclic aromatic amines in barbecued sucuk.

    Science.gov (United States)

    Unal, Kubra; Karakaya, Mustafa; Oz, Fatih

    2018-01-01

    Sucuk is one of the popular traditional Turkish meat products. The aim of this research was to evaluate the effects of different spices (clove, 0.2%; cinnamon, 0.5%) and animal fat types (beef fat, tallow, subcutaneous and tail fat) on the formation of heterocyclic aromatic amine (HCA) in barbecued sucuk. Although 2-amino-3-methyl-9H-pyrido[2,3-b]indole (MeAαC) could not be detected in the any of the samples, 2-amino-3-methylimidazo[4,5-f]quinoxaline (IQx) (up to 0.54 ng g -1 ), 2-amino-3-methylimidazo[4,5-f]quinoline (IQ) (up to 5.96 ng g -1 ), 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx) (up to 0.21 ng g -1 ), 2-amino-3,4-dimethylimidazo[4,5-f]quinoline (MeIQ) (up to 0.34 ng g -1 ), 2-amino-3,7,8-trimethylimidazo[4,5-f]quinoxaline (7,8-DiMeIQx) (up to 0.32 ng g -1 ), 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline (4,8-DiMeIQx) (up to 0.19 ng g -1 ), 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) (up to 1.94 ng g -1 ) and 2-amino-9H-pyrido[2,3-b]indole (AαC) (up to 0.98 ng g -1 ) were found in the barbecued sucuk samples. The results of the current study have shown that HCAs could be formed in barbecued sucuk. Total HCA can be affected by adding different fat types; however, adding clove and cinnamon decreased the total HCA content in the subcutaneous fat group of sucuk samples. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

  19. Role of certain plant natural products or gamma radiation in the control of mutagenic activity of some heterocyclic amines

    International Nuclear Information System (INIS)

    Abu Ghadeer, A.R.M.; El-Sedeek, A.B.A.; Salem, A.M.; Abu Zaid, M.M.

    1999-01-01

    The present study was designed to use ames test to evaluate the antimutagenic effect of some natural products on the lever microsomes extracted from rats and incubated with some chemical mutagens (heterocyclic compounds). Male swiss albino rats (120-140 g) were used as the source of liver microsomes. Three natural products (Nigella extract, garlic powder and sesame oil) were used to evaluate their antimutagenic activities on six heterocyclic amines. All the tested natural products exhibited their antimutagenic activities when added to the investigated heterocyclic compounds and the most effective product was nigella sativa. another group of rats was exposed to gamma-radiation (6.5 Gy) for testing the validity of ames test in quantitating mutagenicity using liver microsomes of irradiated rats. Liver microsomes from irradiated rats showed to lose ability for metabolic activation needed for heterocyclic amines to exert their mutagenic effect on salmonella typhimurium

  20. Mechanistic Investigation of the Ruthenium–N-Heterocyclic-Carbene-Catalyzed Amidation of Alcohols and Amines

    DEFF Research Database (Denmark)

    Makarov, Ilya; Fristrup, Peter; Madsen, Robert

    2012-01-01

    The mechanism of the ruthenium–N-heterocyclic-carbene-catalyzed formation of amides from alcohols and amines was investigated by experimental techniques (Hammett studies, kinetic isotope effects) and by a computational study by using dispersion-corrected density functional theory (DFT/ M06...

  1. Evaluation and application of microwave-assisted extraction and dispersive liquid-liquid microextraction followed by high-performance liquid chromatography for the determination of polar heterocyclic aromatic amines in hamburger patties.

    Science.gov (United States)

    Aeenehvand, Saeed; Toudehrousta, Zahra; Kamankesh, Marzieh; Mashayekh, Morteza; Tavakoli, Hamid Reza; Mohammadi, Abdorreza

    2016-01-01

    This study developed an analytical method based on microwave-assisted extraction and dispersive liquid-liquid microextraction followed by high-performance liquid chromatography for the determination of three polar heterocyclic aromatic amines from hamburger patties. Effective parameters controlling the performance of the microextraction process, such as the type and volume of extraction and disperser solvents, microwave time, nature of alkaline aqueous solution, pH and salt amount, were optimized. The calibration graphs were linear in the range of 1-200 ng g(-1), with a coefficient of determination (R(2)) better than 0.9993. The relative standard deviations (RSD) for seven analyses were between 3.2% and 6.5%. The recoveries of those compounds in hamburger patties were from 90% to 105%. Detection limits were between 0.06 and 0.21 ng g(-1). A comparison of the proposed method with the existing literature demonstrates that it is a simple, rapid, highly selective and sensitive, and it gives good enrichment factors and detection limits for determining HAAs in real hamburger patties samples. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

    Science.gov (United States)

    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).

  3. Effects of phenotypes in heterocyclic aromatic amine (HCA) metabolism-related genes on the association of HCA intake with the risk of colorectal adenomas.

    Science.gov (United States)

    Barbir, Aline; Linseisen, Jakob; Hermann, Silke; Kaaks, Rudolf; Teucher, Birgit; Eichholzer, Monika; Rohrmann, Sabine

    2012-09-01

    Heterocyclic aromatic amines (HCA), formed by high-temperature cooking of meat, are well-known risk factors for colorectal cancer (CRC). Enzymes metabolizing HCAs may influence the risk of CRC depending on the enzyme activity level. We aimed to assess effect modification by polymorphisms in the HCA-metabolizing genes on the association of HCA intake with colorectal adenoma (CRA) risk, which are precursors of CRC. A case-control study nested in the EPIC-Heidelberg cohort was conducted. Between 1994 and 2005, 413 adenoma cases were identified and 796 controls were matched to cases. Genotypes were determined and used to predict phenotypes (i.e., enzyme activities). Odds ratios (OR) and corresponding 95 % confidence intervals (CI) were calculated by logistic regression analysis. CRA risk was positively associated with PhIP, MeIQx, and DiMeIQx (p trend = 0.006, 0.022, and 0.045, respectively) intake. SULT1A1 phenotypes modified the effect of MeIQx on CRA risk (p (Interaction) > 0.01) such that the association of MeIQx intake with CRA was stronger for slow than for normal phenotypes. Other modifying effects by phenotypes did not reach statistical significance. HCA intake is positively associated with CRA risk, regardless of phenotypes involved in the metabolizing process. Due to the number of comparisons made in the analysis, the modifying effect of SULT1A1 on the association of HCA intake with CRA risk may be due to chance.

  4. Mixed ligand complexes of uranyl lactate with some simple and heterocyclic amines

    International Nuclear Information System (INIS)

    Jaiswal, S.R.; Rupainwar, D.C.

    1984-01-01

    Mixed ligand complexes of uranyl lactate with simple and heterocyclic amines having a general formula UO 2 (C 3 H 5 O 3 ).nL.xH 2 O, were prepared, where n=1 and x=1 for L=ethylenediamine (En), dimethyl aniline (DMAn), diethyl amine (DEA), orthophenylenediamine (OPDA), pyridine (Py), 2-picoline(2-Pic), 3-picoline(3-Pic), 4-Picoline(4-Pic), piperidine (Pipy), 2,4-lutidine (2,4 Lut), 2-Aminopyridine (2 APy), quinoline (Quin), isoquinoline (Isoquin) but x=0 for the ligands 2,2'-bipyrldyl (Bipy) and 1,10-phenenthroline (Phen). All the compounds are bright yellow coloured with high decomposition temp. (>200deg) and were characterized by electronic and infrared spectral data. (author)

  5. Quantum-chemical investigation of the 1,2-proton shift in protonated five-membered aromatic heterocycles

    International Nuclear Information System (INIS)

    Abronin, I.A.; Gorb, L.G.; Litvinov, V.P.

    1985-01-01

    Calculations of the energetics of the 1,2-proton shift in protonated five-membered aromatic heterocycles - pyrrole, furan, and thiophene - have been carried out by the SCF MO LCAO method in the MINDO/3 approximation and nonempirically on the OST-3GF (OST-3GF) basis. The general features of this process, and also the influence of solvation and of taking into account the vacant d-AOs of the sulfur atom in the protonated form of thiophene on the results of the calculation are considered. The results obtained have been used for a discussion of the activity and selectivity of the heterocycles considered in aromatic electrophilic substitution reactions

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

    International Nuclear Information System (INIS)

    Salter-Blanc, Alexandra J.; Lyon, Molly A.; Science University, Portland, OR; Ness, Stuart C.; Science University, Portland, OR; Tratnyek, Paul G.; Science University, Portland, OR

    2016-01-01

    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 [Hammett σ constants (σ − ), pK a s 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).

  7. Adsorption and Oxidation of Aromatic Amines on Metal(II Hexacyanocobaltate(III Complexes: Implication for Oligomerization of Exotic Aromatic Compounds

    Directory of Open Access Journals (Sweden)

    Rachana Sharma

    2017-03-01

    Full Text Available Based on the hypothesis on the presence of double metal cyanides in the primordial oceans, a series of nano-sized metal(II hexacyanocobaltate(III (MHCCo with the general formula: M3[Co(CN6]2•xH2O (where M = Zn, Fe, Ni and Mn has been synthesized. Surface interaction of aromatic amines, namely aniline, 4-chloroaniline, 4-methylaniline and 4-methoxyaniline with MHCCo particles has been carried out at the concentration range of 100–400 μM at pH~7.0. The percentage binding of aromatic amines on MHCCo surface was found to be in the range of 84%–44%. The trend in adsorption was in accordance to the relative basicity of the studied amines. At the experimental pH, amines reacted rapidly with the surface of the iron(II hexacyanocobaltate, producing colored products that were analyzed by Gas Chromatography Mass Spectroscopy (GC-MS. GC-MS analysis of the colored products demonstrated the formation of dimers of the studied aromatic amines. Surface interaction of aromatic amines with MHCCo was studied by Fourier Transform Infrared (FT-IR spectroscopy and Field Emission Scanning Electron Microscopy (FE-SEM. The change in amine characteristic frequencies, as observed by FT-IR, suggests that interaction took place through the NH2 group on amines with metal ions of hexacyanocobaltate complexes. FE-SEM studies revealed the adherence of 4-methoxyaniline on zinc hexacyanocobaltate particles surface. We proposed that MHCCo might have been formed under the conditions on primitive Earth and may be regarded as an important candidate for concentrating organic molecules through the adsorption process.

  8. Heterocyclic amines content of meat and fish cooked by Brazilian methods

    OpenAIRE

    Iwasaki, Motoki; Kataoka, Hiroyuki; Ishihara, Junko; Takachi, Ribeka; Hamada, Gerson Shigeaki; Sharma, Sangita; Le Marchand, Loïc; Tsugane, Shoichiro

    2010-01-01

    Heterocyclic amine (HCA) concentrations were measured in meat and fish samples cooked by pan-frying, grilling and churrasco (Brazilian barbecue) to various levels of doneness in accordance with the cooking methods most commonly used in Brazil. HCAs were extracted by the Blue-rayon absorption method and measured by liquid chromatography–mass spectrometry. 2-Amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx), and 2-amino-3,4,8-trimethylim...

  9. Quantitation of 13 heterocyclic aromatic amines in cooked beef, pork, and chicken by liquid chromatography-electrospray ionization/tandem mass spectrometry.

    Science.gov (United States)

    Ni, Weijuan; McNaughton, Lynn; LeMaster, David M; Sinha, Rashmi; Turesky, Robert J

    2008-01-09

    The concentrations of heterocyclic aromatic amines (HAAs) were determined, by liquid chromatography-electrospray ionization/tandem mass spectrometry (LC-ESI-MS/MS), in 26 samples of beef, pork, and chicken cooked to various levels of doneness. The HAAs identified were 2-amino-3-methylimidazo[4,5- f]quinoline, 2-amino-1-methylimidazo[4,5- b]quinoline, 2-amino-1-methylimidazo[4,5- g]quinoxaline (I gQx), 2-amino-3-methylimidazo[4,5- f]quinoxaline, 2-amino-1,7-dimethylimidazo[4,5- g]quinoxaline (7-MeI gQx), 2-amino-3,8-dimethylimidazo[4,5- f]quinoxaline, 2-amino-1,6-dimethyl-furo[3,2- e]imidazo[4,5- b]pyridine, 2-amino-1,6,7-trimethylimidazo[4,5- g]quinoxaline, 2-amino-3,4,8-trimethylimidazo[4,5- f]quinoxaline, 2-amino-1,7,9-trimethylimidazo[4,5- g]quinoxaline, 2-amino-1-methyl-6-phenylimidazo[4,5- b]pyridine (PhIP), 2-amino-9 H-pyrido[2,3- b]indole, and 2-amino-3-methyl-9 H-pyrido[2,3- b]indole. The concentrations of these compounds ranged from chicken (up to 305 microg/kg), broiled bacon (16 microg/kg), and pan-fried bacon (4.9 microg/kg). 7-MeI gQx was the most abundant HAA formed in very well done pan-fried beef and steak, and in beef gravy, at concentrations up to 30 microg/kg. Several other linear tricyclic ring HAAs containing the I gQx skeleton are formed at concentrations in cooked meats that are relatively high in comparison to the concentrations of their angular tricyclic ring isomers, the latter of which are known experimental animal carcinogens and potential human carcinogens. The toxicological properties of these recently discovered I gQx derivatives warrant further investigation and assessment.

  10. Normal-phase liquid chromatography retention behavior of polycyclic aromatic sulfur heterocycles and alkyl-substituted polycyclic aromatic sulfur heterocycle isomers on an aminopropyl stationary phase.

    Science.gov (United States)

    Wilson, Walter B; Hayes, Hugh V; Sander, Lane C; Campiglia, Andres D; Wise, Stephen A

    2018-02-01

    Retention indices for 67 polycyclic aromatic sulfur heterocycles (PASHs) and 80 alkyl-substituted PASHs were determined using normal-phase liquid chromatography (NPLC) on an aminopropyl (NH 2 ) stationary phase. The retention behavior of PASH on the NH 2 phase is correlated with the number of aromatic carbon atoms and two structural characteristics have a significant influence on their retention: non-planarity (thickness, T) and the position of the sulfur atom in the bay-region of the structure. Correlations between solute retention on the NH 2 phase and T of PASHs were investigated for three cata-condensed (cata-) PASH isomer groups: (a) 13 four-ring molecular mass (MM) 234 Da cata-PASHs, (b) 20 five-ring MM 284 Da cata-PASHs, and (c) 12 six-ring MM 334 Da cata-PASHs. Correlation coefficients ranged from r = -0.49 (MM 234 Da) to r = -0.65 (MM 334 Da), which were significantly lower than structurally similar PAH isomer groups (r = -0.70 to r = -0.99). The NPLC retention behavior of the PASHs are compared to similar results for PAHs.

  11. Meat Consumption, Heterocyclic Amines, and Colorectal Cancer Risk: The Multiethnic Cohort Study

    OpenAIRE

    Ollberding, Nicholas J.; Wilkens, Lynne R.; Henderson, Brian E.; Kolonel, Laurence N.; Le Marchand, Loïc

    2012-01-01

    Greater consumption of red and processed meat has been associated with an increased risk of colorectal cancer in several recent meta-analyses. Heterocyclic amines (HCAs) have been hypothesized to underlie this association. In this prospective analysis conducted within the Multiethnic Cohort Study, we examined whether greater consumption of total, red, or processed meat was associated with the risk of colorectal cancer among 165,717 participants who completed a detailed food frequency question...

  12. Amide Synthesis from Alcohols and Amines Catalyzed by Ruthenium N-Heterocyclic Carbene Complexes

    DEFF Research Database (Denmark)

    Dam, Johan Hygum; Osztrovszky, Gyorgyi; Nordstrøm, Lars Ulrik Rubæk

    2010-01-01

    The direct synthesis of amides from alcohols and amines is described with the simultaneous liberation of dihydrogen. The reaction does not require any stoichiometric additives or hydrogen acceptors and is catalyzed by ruthenium N-heterocyclic carbene complexes. Three different catalyst systems...... are presented that all employ 1,3-diisopropylimidazol-2-ylidene (IiPr) as the carbene ligand. In addition, potassium tert-butoxide and a tricycloalkylphosphine are required for the amidation to proceed. In the first system, the active catalyst is generated in situ from [RuCl2(cod)] (cod = 1,5-cyclooctadiene), 1...... chloride and base. A range of different primary alcohols and amines have been coupled in the presence of the three catalyst systems to afford the corresponding amides in moderate to excellent yields. The best results are obtained with sterically unhindered alcohols and amines. The three catalyst systems do...

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

    Science.gov (United States)

    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.

  14. Genotoxicity and induction of DNA damage responsive genes by food-borne heterocyclic aromatic amines in human hepatoma HepG2 cells.

    Science.gov (United States)

    Pezdirc, Marko; Žegura, Bojana; Filipič, Metka

    2013-09-01

    Heterocyclic aromatic amines (HAAs) are potential human carcinogens formed in well-done meats and fish. The most abundant are 2-Amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), 2-Amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx), 2-Amino-3,4,8-trimethyl-3H-imidazo[4,5-f]quinoxaline (4,8-DiMeIQx) and 2-Amino-3-methyl-3H-imidazo[4,5-f]quinoline (IQ). HAAs exert genotoxic activity after metabolic transformation by CYP1A enzymes, that is well characterized, however the genomic and intervening responses are not well explored. We have examined cellular and genomic responses of human hepatoma HepG2 cells after 24h exposure to HAAs. Comet assay revealed increase in formation of DNA strand breaks by PhIP, MeIQx and IQ but not 4,8-DiMeIQx, whereas increased formation of micronuclei was not observed. The four HAAs up-regulated expression of genes encoding metabolic enzymes CYP1A1, CYP1A2 and UGT1A1 and expression of TP53 and its downstream regulated genes CDKN1A, GADD45α and BAX. Consistent with the up-regulation of CDKN1A and GADD45α the cell-cycle analysis showed arrest in S-phase by PhIP and IQ, and in G1-phase by 4,8-DiMeIQx and MeIQx. The results indicate that upon exposure to HAAs the cells respond with the cell-cycle arrest, which enables cells to repair the damage or eliminate them by apoptosis. However, elevated expression of BCL2 and down-regulation of BAX may indicate that HAAs could suppress apoptosis meaning higher probability of damaged cells to survive and mutate. Copyright © 2013 Elsevier Ltd. All rights reserved.

  15. Degradation of aromatic amines in textile-dyeing sludge by combining the ultrasound technique with potassium permanganate treatment.

    Science.gov (United States)

    Liang, Jieying; Ning, Xun-An; An, Taicheng; Sun, Jian; Zhang, Yaping; Wang, Yujie

    2016-08-15

    This paper reports, for the first time, a combined technique of ultrasound (US) with KMnO4 degradation of aromatic amines in a textile-dyeing sludge. The reaction mechanisms and the degradation kinetics of aromatic amines at various operating parameters (KMnO4 dosage, US power density and pH) were systematically examined by the combined system of US-KMnO4. The results indicated that there was a synergistic effect between US and KMnO4, as US greatly enhanced KMnO4 in the degradation of aromatic amines and exhibited apparent sludge disintegration and separated pollutants from the sludge. In addition to accelerating the Mn(VII) reaction with pollutants in the filtrate, US also caused Mn(VII) to enter the porous sludge and sufficiently facilitated the reaction of the strongly absorbed aromatic amines. The combined treatment of US-KMnO4 was effective in the degradation of aromatic amines in textile-dyeing sludge. On average, 58.7% of monocyclic anilines, 88.3% of other forms of aromatic amines, and 24.0% of TOC were removed under the optimal operating conditions of a KMnO4 dosage of 12mM, an US power density of 1.80W/cm(3) and pH 5. The present study proposed US-KMnO4 treatment as a practical method for the disposal of aromatic amines in textile-dyeing sludge. Copyright © 2016 Elsevier B.V. All rights reserved.

  16. Heterocyclic amines in meat and meat products

    Directory of Open Access Journals (Sweden)

    Aliye BULGAN

    2013-06-01

    Full Text Available Heterocyclic amines (HA are the mutagenic/carcinogenic compounds which generate as a result of cooking of red meat, poultry meat and fish fillets at high temperatures. Up to 20 different HAs were detected and classified in the researches that conducted on these types of meats cooked at high temperatures. HAs are the products of Maillard reactions and the Strecker degredation of main precursors such as creatine/creatinine, aminoacid and the polysaccharides. Many physical and chemical factors effect the formation of HAs. Thus, it was reported by many researchers that utilizing coating and marination processes in addition to using natural and synthetic antioxidants and seasonings-plant extracts were effective on inhibiting/decreasing the formation of HAs. Additionally, boiling/steaming and microwave cooking methodologies were recommended instead of barbecuing, grilling or frying to inhibit/decrease the formation of HAs. The HAs formed in meat and meat products and the factors which have effects on the formation of HAs are presented in this review.

  17. Basic deuteroexchange in transition metal complexes with nitrogen-containing aromatic heterocycles

    International Nuclear Information System (INIS)

    Tupitsyn, I.F.

    1986-01-01

    Kinetics of deuteroexchange in the methyl group of nitrate complexes of a metal - nickel (2) - with different methyl-substituted aromatic heterocycles and isostructural complexes of a ligand - 2 - methyl quinoline - with different central metal atoms (Mn(2), Ni(2), Cu(2), Zn(2)) is studied. Series for influence of ligand structure on deuteroexchange rate in complexes doesn't correspond qualitatively to series for deuteroexchange rate increase in noncoordinated ligands. Deuteroexchange rate is weakly subjected to influence of exchange in metal-complexing agent. Deuteroexchange mechanism is suggested and discussed. According to this mechanism the structure developed in the course of the exchange process with electron density transfer from the heterocyclic ligand to a metal ion is a transition state of the reaction

  18. Selective fluorescence quenching of nitrogen-containing polycyclic aromatic hydrocarbons by aliphatic amines

    International Nuclear Information System (INIS)

    Li Xiaoping; McGuffin, Victoria L.

    2004-01-01

    In this investigation, primary, secondary, and tertiary amines are evaluated for their efficiency and selectivity as fluorescence quenchers for polycyclic aromatic hydrocarbons (PAHs) and nitrogen-containing polycyclic aromatic hydrocarbons (N-PAHs). In general, the quenching efficiency tends to increase from primary to tertiary amine due to a greater number of alkyl groups that increase the electron-donating ability. However, the selectivity decreases from primary to tertiary amine. The effect of low concentrations of water is also examined. Because water can form hydrogen bonds with amines, the nonbonding electron pair is not available for interaction with the fluorophore, thus the quenching constant is decreased. These aliphatic amines are then applied to PAHs and N-PAHs and some interesting trends are observed. Whereas amino-PAHs remain virtually unquenched by different amines, aza-PAHs are all quenched well. The selectivity between aza-PAHs and amino-PAHs is as high as several hundred. This trend provides an easy and effective method to discriminate between these classes of N-PAHs. Moreover, the alternant aza-PAHs are quenched more than their corresponding alternant PAHs

  19. Metabolism and genotoxicity of aromatic amines in aquatic organisms

    International Nuclear Information System (INIS)

    Knezovich, J.P.; Krauter, P.W.; Lawton, M.P.; Harrison, F.L.

    1987-01-01

    Marine mussels (Mytilus edulis) and bullfrog tadpoles (Rana catesbeiana) were used to investigate the comparative metabolism and genotoxicity of aromatic amines in vivo. These organisms were selected because they possess distinctly different metabolic capabilities: mussels lack an active mixed-function-oxidase enzyme system that is present in most other organisms, including amphibians. Using 14 C-labeled chemical probes (o- and p-toluidine, 2-aminofluorene (2-AF), and 2-acetylaminofluorene (2-AAF)), mussels and tadpoles well dosed with individual compounds by direct immersion in aqueous solutions. The identities of metabolites were then determined by HPLC and GC/MS methods. Results indicate that the N-conjugating pathways used by mussels result primarily in the detoxification of aromatic amines by limiting the amount of primary amine available for activation. The tadpoles excreted a number of 2-AAF metabolites but did form DNA and protein adducts in the liver. Induction of micronuclei in the peripheral red blood cells was also demonstrated. The tadpole was shown to be a sensitive biological indicator of pollution in aquatic ecosystems

  20. Precursors to radiopharmaceutical agents for tissue imaging

    International Nuclear Information System (INIS)

    Srivastava, P.C.; Knapp, F.F. Jr.

    1988-01-01

    A compound is described comprising: a heterocyclic moiety wherein the hetero member of the heterocyclic moiety is nitrogen; the heterocyclic moiety being quaternary and capable of being reduced to a dihydrogenated form; the heterocyclic moiety having a carbonyl group attached to a carbon of the ring of the heterocyclic moiety; the heterocyclic moiety being coupled at the carbonyl carbon with the amino nitrogen of an aromatic or aromatic alkyl amine; the aromatic or aromatic alkyl amine having attached to a carbon of the aromatic ring a moiety that is readily replaced by a radiohalide selected from the group a substituted triazene, mercuric acetate and a boron moiety

  1. Inhibitory effect of cellulose fibers on the formation of heterocyclic aromatic amines in grilled beef patties.

    Science.gov (United States)

    Gibis, Monika; Weiss, Jochen

    2017-08-15

    Microcrystalline cellulose (MCC) or carboxymethyl cellulose (CMC) can be used as fat replacers; both are nondigestible fibers. As water-holding compounds, the impact of added CMC or MCC was studied concerning the formation of heterocyclic amines (HAAs). Low-fat patties with 0.5-3% MCC/CMC were prepared using 90% of beef and 10% of an aqueous fiber dispersion and were determined for HAA-levels after grilling. The HAAs in patties containing CMC(MCC) were found in the following concentrations; MeIQx (2-Amino-3,8-dimethylimidazo[4,5-f]quinoxaline) 0.6-2.7 (0.9-3.3)ng/g, 4,8-DiMeIQx (2-Amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline) n.d.-1.5 (n.d.-2.2)ng/g and PhIP (2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine) 0.03-0.3 (0.06-0.2)ng/g. The patties clearly contained lower HAA-levels with increasing addition of CMC or MCC. A continuous increase of the concentrations of comutagenic harman was observed (CMC: 1.2-13.2; MCC: 5.2-11.4ng/g) for increasing levels of fibers and a slight decrease of the content of norharman for MCC (0.5-1.6ng/g). No clear tendency was found for norharman using CMC (0.3-1.1ng/g). Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Regularities of synthesis and mechanism of polycondensation of aromatic amines

    International Nuclear Information System (INIS)

    Matnishyan, Hagob

    2002-01-01

    Full text.Aniline polymers and its derivatives are widely used in modern electronics, electrical engineering and manufacturing of various appliances. They are used for production of electrical power sources, probes and sensors, composite materials absorbing high frequency radiations, anticorrosion coatings, nonlinear optical devices-such as lasers, cathode ray tubes, photodiodes etc. Such a wide usage of aromatic amine polymers brings up new demands to their structure and properties, which is dependent on conditions of synthesis and forming of the hard phase. The presented article describes regularities and mechanisms of oxidative polycondensation of aromatic amines. Several types of polymers have been synthesized by chemical and electrochemical oxidation of aniline and its chlor-, brom-, iodo-, nitro-, p-substituted derivatives; diphenylamine, benzidine and phenylenediamines in nonwater media. On the basis of kinetic and electrochemical studies and literature analysis we suggested a mechanism of polycondensation of aromatic amines. According to it, oxidation of amines starts with the electron transfer with cation-radical formation on the first stage, which stabilizes in acid environments due to complex formation with initial amine. Dimer formation and further growth of chain takes place upon another electron transfer from formed complex, which results in forming of macromolecules. We also suggested a scheme for obtaining of structures defect in media assisting in deprotonizing of cation radicals and formation of arylamine radical centers. Those processes lead to formation of azo- and diphenyl fragments in the main chain of the polymer and predetermine the possibility of chain disruption. We also considered reactions leading to formation of branched polymers and cyclic structures, such as phenazine in particular. The peculiarity of electrochemical process lies in regulation of concentration of active centres on the positive electrode surface

  3. Dietary exposure to heterocyclic amines in a Chinese population.

    Science.gov (United States)

    Wong, Kin-Yoke; Su, Jin; Knize, Mark G; Koh, Woon-Puay; Seow, Adeline

    2005-01-01

    Heterocyclic aromatic amines (HAAs) formed in meat during high-temperature cooking have been associated with risk of colorectal and breast cancer. Incidence of these cancers is increasing in Singapore, a country with 77% ethnic Chinese. The purpose of this study was to estimate HAA levels in the Chinese diet and individual levels of exposure to these compounds because little is known. Twenty-five samples (each pooled from three sources) of meat and fish, cooked as commonly consumed, were analyzed by high-performance liquid chromatography for concentrations (ng/g) of 2-amino-3-methylimidazo[4,5-f]quinoline, 2-amino-3, 4-dimethylimidazo[4,5-f]quinoline (MeIQ), 2-amino-3,8- dimethylimidazo[4,5-f]quinoxaline (MeIQx), 2-amino-3, 4,8-trimethylimidazo[4,5-f]quinoxaline (4,8-DiMeIQx), 2- amino-3,7,8-trimethylimidazo[4,5-f]quinoxaline, 2-amino -1,6-dimethylfuro[3,2-e]imidazo[4,5-b]pyridine, and 2- amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP). Dietary meat consumption data (g/day), including meat type and cooking method, were gathered from food-frequency questionnaires completed by 497 randomly sampled Chinese men and women aged 20-59 yr. PhIP, MeIQx, and 4,8-DiMeIQx were the most abundant HAAs detected. Total HAA concentrations ranged from roasted pork had the highest levels. The estimated mean daily exposure to HAA was 49.95 ng/day (P10 14.0 ng/day, P90 95.8 ng/day); this was 50% higher among younger (20-39 yr) compared with older individuals. Seven specific meat-cooking method combinations contributed 90.1% of this intake, namely, pan-fried fish, pork, and chicken, deep-fried chicken as well as fish, roasted/barbecued pork, and grilled minced beef.

  4. Synthesis, characterization and applications of some novel mordent and heterocyclic disperse dyes on polyester and wool fibers

    Directory of Open Access Journals (Sweden)

    Hitendra Mangubhai Patel

    2012-10-01

    Full Text Available The novel mordent and disperse heterocyclic dyes were prepared by coupling of various diazo solution of aromatic amines with 1-[(2-butyl-2,3-dihydrobenzofuran-3-yl]-1-(4-hydroxyphenylmethanone. The resultant mordent and disperse heterocyclic dyes were characterized by elemental analyses, IR and 1H-NMR and 13C-NMR spectral studies. The UV-visible spectral data have also been discussed in terms of structural property relationship. The dyeing assessment of all the mordent and disperse heterocyclic dyes was evaluated on wool and polyester textile fibers. The results of antibacterial studies of chrome pretreated fabrics revealed that the toxicity of mordented dyes against Escherichia coli, Staphylococcus aureus, Salmonella typhi, Bacillus subtilis bacteria was fairly good.

  5. Petroleum geochemistry of the Potwar Basin, Pakistan: II – Oil classification based on heterocyclic and polycyclic aromatic hydrocarbons

    International Nuclear Information System (INIS)

    Asif, Muhammad; Fazeelat, Tahira

    2012-01-01

    In a previous study, oils in the Potwar Basin (Upper Indus) of Pakistan were correlated based on the dissimilarity of source and depositional environment of organic matter (OM) using biomarkers and bulk stable isotopes. This study is aimed at supporting the classification of Potwar Basin oils into three groups (A, B and C) using the distribution of alkylnaphthalenes, alkylphenanthrenes, alkyldibenzothiophenes, alkyldibenzofurans, alkylfluorenes, alkylbiphenyls, triaromatic steroids, methyl triaromatic steroids, retene, methyl retenes and cadalene. The higher relative abundance of specific methyl isomers of naphthalene and phenanthrene and the presence of diagnostic aromatic biomarkers clearly indicate the terrigenous and oxic depositional environment of OM for group A oil. Group B and C oils are of marine origin and the aforementioned heterocyclic and polycyclic aromatic hydrocarbons (HCs) differentiate them clearly into two different groups. The relative percentages of heterocyclic aromatic HCs reveal that the distribution of these compounds is controlled by the depositional environment of the OM. Sulfur-containing heterocyclic aromatic HCs are higher in crude oils generated from source rocks deposited in suboxic depositional environments, while oxygen-containing heterocyclic aromatic HCs in combination with alkylfluorenes are higher in marine oxic and deltaic oils. Biomarker and aromatic HC parameters do not indicate significant differences in the thermal maturity of Potwar Basin oils. Triaromatic and methyl triaromatic steroids support the division of Potwar Basin oils into the three groups and their relative abundances are related to source OM rather than thermal maturity. Significantly higher amounts of C 20 and C 21 triaromtic steroids and the presence or absence of long chain triaromatic steroids (C 25 , C 26 , C 27 , and C 28 ) indicates that these compounds are probably formed from different biological precursors in each group. Different isomers of methyl

  6. Preferential induction of the AhR gene battery in HepaRG cells after a single or repeated exposure to heterocyclic aromatic amines

    International Nuclear Information System (INIS)

    Dumont, Julie; Josse, Rozenn; Lambert, Carine; Antherieu, Sebastien; Laurent, Veronique; Loyer, Pascal; Robin, Marie-Anne; Guillouzo, Andre

    2010-01-01

    2-Amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) and 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx) are two of the most common heterocyclic aromatic amines (HAA) produced during cooking of meat, fish and poultry. Both HAA produce different tumor profiles in rodents and are suspected to be carcinogenic in humans. In order to better understand the molecular basis of HAA toxicity, we have analyzed gene expression profiles in the metabolically competent human HepaRG cells using pangenomic oligonucleotide microarrays, after either a single (24-h) or a repeated (28-day) exposure to 10 μM PhIP or MeIQx. The most responsive genes to both HAA were downstream targets of the arylhydrocarbon receptor (AhR): CYP1A1 and CYP1A2 after both time points and CYP1B1 and ALDH3A1 after 28 days. Accordingly, CYP1A1/1A2 induction in HAA-treated HepaRG cells was prevented by chemical inhibition or small interference RNA-mediated down-regulation of the AhR. Consistently, HAA induced activity of the CYP1A1 promoter, which contains a consensus AhR-related xenobiotic-responsive element (XRE). In addition, several other genes exhibited both time-dependent and compound-specific expression changes with, however, a smaller magnitude than previously reported for the prototypical AhR target genes. These changes concerned genes mainly related to cell growth and proliferation, apoptosis, and cancer. In conclusion, these results identify the AhR gene battery as the preferential target of PhIP and MeIQx in HepaRG cells and further support the hypothesis that intake of HAA in diet might increase human cancer risk.

  7. MACROMOLECULAR ADDUCT FORMATION AND METABOLISM OF HETEROCYCLIC AMINES IN HUMANS AND RODENTS AT LOW DOSES. (R825280)

    Science.gov (United States)

    Abstract2-Amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx) and 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) are heterocyclic amines formed during the cooking of meat and fish. Both are genotoxic in a number of test systems and are carcinogen...

  8. Can creatine supplementation form carcinogenic heterocyclic amines in humans?

    Science.gov (United States)

    Pereira, Renato Tavares dos Santos; Dörr, Felipe Augusto; Pinto, Ernani; Solis, Marina Yazigi; Artioli, Guilherme Giannini; Fernandes, Alan Lins; Murai, Igor Hisashi; Dantas, Wagner Silva; Seguro, Antônio Carlos; Santinho, Mirela Aparecida Rodrigues; Roschel, Hamilton; Carpentier, Alain; Poortmans, Jacques Remi; Gualano, Bruno

    2015-01-01

    Abstract Creatine supplementation has been associated with increased cancer risk. In fact, there is evidence indicating that creatine and/or creatinine are important precursors of carcinogenic heterocyclic amines (HCAs). The present study aimed to investigate the acute and chronic effects of low- and high-dose creatine supplementation on the production of HCAs in healthy humans (i.e. 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (8-MeIQx),  2-amino-(1,6-dimethylfuro[3,2-e]imidazo[4,5-b])pyridine (IFP) and 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline (4,8-DiMeIQx)). This was a non-counterbalanced single-blind crossover study divided into two phases, in which low- and high-dose creatine protocols were tested. After acute (1 day) and chronic supplementation (30 days), the HCAs PhIP, 8-MeIQx, IFP and 4,8-DiMeIQx were assessed through a newly developed HPLC–MS/MS method. Dietary HCA intake and blood and urinary creatinine were also evaluated. Out of 576 assessments performed (from 149 urine samples), only nine (3 from creatine and 6 from placebo) showed quantifiable levels of HCAs (8-MeIQx: n = 3; 4,8-DiMeIQx: n = 2; PhIP: n = 4). Individual analyses revealed that diet rather than creatine supplementation was the main responsible factor for HCA formation in these cases. This study provides compelling evidence that both low and high doses of creatine supplementation, given either acutely or chronically, did not cause increases in the carcinogenic HCAs PhIP, 8-MeIQx, IFP and 4,8-DiMeIQx in healthy subjects. These findings challenge the long-existing notion that creatine supplementation could potentially increase the risk of cancer by stimulating the formation of these mutagens. Key points There is a long-standing concern that creatine supplementation could be associated with cancer, possibly by facilitating the formation of carcinogenic heterocyclic amines (HCAs). This study provides compelling evidence

  9. Dehydrogenative Synthesis of Imines from Alcohols and Amines Catalyzed by a Ruthenium N-Heterocyclic Carbene Complex

    DEFF Research Database (Denmark)

    Maggi, Agnese; Madsen, Robert

    2012-01-01

    A new method for the direct synthesis of imines from alcohols and amines is described where hydrogen gas is liberated. The reaction is catalyzed by the ruthenium N-heterocyclic carbene complex [RuCl2(IiPr)(p-cymene)] in the presence of the ligand DABCO and molecular sieves. The imination can...... be applied to a variety of primary alcohols and amines and can be combined with a subsequent addition reaction. A deuterium labeling experiment indicates that the catalytically active species is a ruthenium dihydride. The reaction is believed to proceed by initial dehydrogenation of the alcohol...

  10. Adsorption Characteristics of DNA Nucleobases, Aromatic Amino Acids and Heterocyclic Molecules on Silicene and Germanene Monolayers

    KAUST Repository

    Hussain, Tanveer; Vovusha, Hakkim; Kaewmaraya, Thanayut; Amornkitbamrung, Vittaya; Ahuja, Rajeev

    2017-01-01

    Binding of DNA/RNA nucleobases, aromatic amino acids and heterocyclic molecules on two-dimensional silicene and germanene sheets have been investigated for the application of sensing of biomolecules using first principle density functional theory

  11. Catalytic oxidation of 2-aminophenols and ortho hydroxylation of aromatic amines by tyrosinase

    International Nuclear Information System (INIS)

    Toussaint, O.; Lerch, K.

    1987-01-01

    The usual substrates of tyrosinase, a copper-containing monooxygenase (EC 1.14.18.1), are monophenols and o-diphenols which are both converted to o-quinones. In this paper, the authors studied the reaction of this enzyme with two new classes of substrates: aromatic amines and o-aminophenols, structural analogues of monophenols and o-diphenols, respectively. They undergo the same catalytic reactions (ortho hydroxylation and oxidation), as documented by product analysis and kinetic studies. In the presence of tyrosinase, arylamines and o-aminophenols are converted to o-quinone imines, which are isolated as quinone anils or phenoxazones. As an example, in the presence of tyrosinase, 2-amino-3-hydroxybenzoic acid (an o-aminophenol) is converted to cinnabarinic acid, a well-known phenoxazone, while p-aminotoluene (an aromatic amine) gives rise to the formation of 5-amino-2-methyl-1,4-benzoquinone 1-(4-methylanil). Kinetic studies using an oxygen electrode show that arylamines and the corresponding monophenols exhibit similar Michaelis constants. In contrast, the reaction rates observed for aromatic amines are relatively slow as compared to monophenols. The enzymatic conversion of arylamines by tryosinase is different from the typical ones: N-oxidation and ring hydroxylation without further oxidation. This difference originates from the regiospecific hydroxylation (ortho position) and subsequent oxidation of the intermediate o-aminophenol to the corresponding o-quinone imine. Finally, the well-know monooxygenase activity of tyrosinase was also confirmed for the aromatic amine p-aminotoluene, with 18 O 2

  12. Hemoglobin binding of aromatic amines: molecular dosimetry and quantitative structure-activity relationships for N-oxidation.

    Science.gov (United States)

    Sabbioni, G

    1993-01-01

    Aromatic amines are important intermediates in industrial manufacturing. N-Oxidation to N-hydroxyarylamines is a key step in determining the genotoxic properties of aromatic amines. N-Hydroxyarylamines can form adducts with DNA, with tissue proteins, and with the blood proteins albumin and hemoglobin in a dose-dependent manner. The determination of hemoglobin adducts is a useful tool for biomonitoring exposed populations. We have established the hemoglobin binding index (HBI) [(mmole compound/mole hemoglobin)/(mmole compound/kg body weight)] of several aromatic amines in female Wistar rats. Including the values from other researchers obtained in the same rat strain, the logarithm of hemoglobin binding (logHBI) was plotted against the following parameters: the sum of the Hammett constants(sigma sigma = sigma p + sigma m), pKa, logP (octanol/water), the half-wave oxidation potential (E1/2), and the electronic descriptors of the amines and their corresponding nitrenium ions obtained by semi-empirical calculations (MNDO, AMI, and PM3), such as atomic charge densities, energies of the highest occupied molecular orbit and lowest occupied molecular orbit and their coefficients, the bond order of C-N, the dipole moments, and the reaction enthalpy [MNDOHF, AM1HF or PM3HF = Hf(nitrenium) - Hf(amine)]. The correlation coefficients were determined from the plots of all parameters against log HBI for all amines by means of linear regression analysis. The amines were classified in three groups: group 1, all parasubstituted amines (maximum, n = 9); group 2, all amines with halogens (maximun, n = 11); and group 3, all amines with alkyl groups (maximum, n = 13).(ABSTRACT TRUNCATED AT 250 WORDS) PMID:8319626

  13. Synthesis, characterization and dyeing behavior of heterocyclic acid dyes and mordent acid dyes on wool and silk fabrics

    Directory of Open Access Journals (Sweden)

    Patel Hitendra M.

    2012-01-01

    Full Text Available Novel heterocyclic acid and mordent acid dyes were synthesized by the coupling of diazonium salt solution of different aromatic amines with 2- butyl-3-(4-hydroxybenzoylbenzofuran. The resulting heterocyclic acid dyes were characterized by spectral techniques, i.e., elemental analysis, IR, 1HNMR, 13C-NMR spectral studies and UV- visible spectroscopy. The dyeing performance of all the heterocyclic acid dyes was evaluated on wool and silk fabrics. The dyeing of chrome pre treated wool and silk fabrics showed better hues on mordented fabrics. Dyeing of wool and silk fabrics resulted in pinkish blue to red shades with very good depth and levelness. The dyed fabrics showed excellent to very good light, washing, perspiration, sublimation and rubbing fastness.

  14. Formation mechanism of NDMA from ranitidine, trimethylamine, and other tertiary amines during chloramination: a computational study.

    Science.gov (United States)

    Liu, Yong Dong; Selbes, Meric; Zeng, Chengchu; Zhong, Rugang; Karanfil, Tanju

    2014-01-01

    Chloramination of drinking waters has been associated with N-nitrosodimethylamine (NDMA) formation as a disinfection byproduct. NDMA is classified as a probable carcinogen and thus its formation during chloramination has recently become the focus of considerable research interest. In this study, the formation mechanisms of NDMA from ranitidine and trimethylamine (TMA), as models of tertiary amines, during chloramination were investigated by using density functional theory (DFT). A new four-step formation pathway of NDMA was proposed involving nucleophilic substitution by chloramine, oxidation, and dehydration followed by nitrosation. The results suggested that nitrosation reaction is the rate-limiting step and determines the NDMA yield for tertiary amines. When 45 other tertiary amines were examined, the proposed mechanism was found to be more applicable to aromatic tertiary amines, and there may be still some additional factors or pathways that need to be considered for aliphatic tertiary amines. The heterolytic ONN(Me)2-R(+) bond dissociation energy to release NDMA and carbocation R(+) was found to be a criterion for evaluating the reactivity of aromatic tertiary amines. A structure-activity study indicates that tertiary amines with benzyl, aromatic heterocyclic ring, and diene-substituted methenyl adjacent to the DMA moiety are potentially significant NDMA precursors. The findings of this study are helpful for understanding NDMA formation mechanism and predicting NDMA yield of a precursor.

  15. Solvent-free functionalization of fullerene C{sub 60} and pristine multi-walled carbon nanotubes with aromatic amines

    Energy Technology Data Exchange (ETDEWEB)

    Ramírez-Calera, Itzel J. [Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Circuito Exterior C. U., 04510, México, D.F. (Mexico); Meza-Laguna, Victor [Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, Circuito Exterior C. U., 04510 México, D.F. (Mexico); Gromovoy, Taras Yu. [O.O. Chuiko Institute of Surface Chemistry, National Academy of Sciences of the Ukraine, Gen. Naumova 17, 03164 Kiev (Ukraine); Chávez-Uribe, Ma. Isabel [Instituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior C. U., 04510 México, D.F. (Mexico); Basiuk, Vladimir A., E-mail: basiuk@nucleares.unam.mx [Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, Circuito Exterior C. U., 04510 México, D.F. (Mexico); Basiuk, Elena V., E-mail: elbg1111@gmail.com [Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Circuito Exterior C. U., 04510, México, D.F. (Mexico)

    2015-02-15

    Highlights: • Pristine multi-walled carbon nanotubes were functionalized with aromatic amines. • The amines add onto nanotube defects, likewise they add onto fullerene C{sub 60}. • The addition takes place at elevated temperature and without organic solvents. • Functionalized nanotubes were characterized by a number of instrumental techniques. - Abstract: We employed a direct one-step solvent-free covalent functionalization of solid fullerene C{sub 60} and pristine multi-walled carbon nanotubes (MWCNTs) with aromatic amines 1-aminopyrene (AP), 2-aminofluorene (AF) and 1,5-diaminonaphthalene (DAN). The reactions were carried out under moderate vacuum, in a wide temperature range of 180–250 °C, during relatively short time of about 2 h. To confirm successful amine attachment, a large number of analytical techniques were used (depending on the nanomaterial functionalized) such as Fourier transform infrared, Raman, X-ray photoelectron, {sup 13}C cross-polarization magic angle spinning NMR spectroscopy, thermogravimetric analysis, laser-desorption ionization time-of-flight mass spectrometry, temperature-programmed desorption with mass spectrometric detection, as well as scanning and transmission electron microscopy. The nucleophilic addition of the aromatic amines to C{sub 60} molecule was studied theoretically by using density functional theory (PBE GGA functional with Grimme dispersion correction in conjunction with the DNP basis set). In the case of crystalline C{sub 60}, the solvent-free technique has a limited applicability due to poor diffusion of vaporous aromatic amines into the bulk. Nevertheless, the approach proposed allows for a facile preparation of aromatic amine-functionalized pristine MWCNTs without contamination with other chemical reagents, detergents and solvents, which is especially important for a vast variety of nanotube applications spanning from nanoelectronics to nanomedicine.

  16. Basic deuteroexchange in complexes of transition metals with nitrogen-containing aromatic heterocycles

    International Nuclear Information System (INIS)

    Tupitsyn, I.F.

    1986-01-01

    A study was made of the kinetics of deuteroexchange in the methyl group in complexes of one metal [nickel(II)] with different methyl-substituted aromatic heterocycles and in isostructural complexes of one ligand (2-methylquinoline) with different central metal atoms (Mn 2+ , Ni 2+ , Cu 2+ , Zn 2+ ). The order in which the structures of the ligands influence the rate of deuteroexchange in the complexes does not correspond qualitatively with the order of increase in the rate of deuteroexchange in the noncoordinated ligands. The rate of deuteroexchange is only weakly influenced by change in the identity of the metal complex former. A deuteroexchange mechanism is proposed and discussed. A structure arising in the course of the exchange process with transfer of electron density from the heterocyclic ligand to the metal ion forms the transition state of the reaction

  17. Electrochemical degradation of aromatic amines on BDD electrodes

    International Nuclear Information System (INIS)

    Pacheco, M.J.; Santos, V.; Ciriaco, L.; Lopes, A.

    2011-01-01

    The electrochemical oxidation of four aromatic amines, with different substituent groups, 3-amino-4-hydroxy-5-nitrobenzenesulfonic acid (A1), 5-amino-2-methoxybenzenesulfonic acid (A2), 2,4-dihydroxyaniline hydrochloride (A3) and benzene-1,4-diamine (A4), was performed using as anode a boron-doped diamond electrode, commercially available at Adamant Technologies. Tests were run at room temperature with model solutions of the different amines, with concentrations of 200 ppm, using as electrolyte 0.035 M Na 2 SO 4 aqueous solutions, in a batch cell with recirculation, at different current densities (200 and 300 A m -2 ). The following analyses were performed with the samples collected during the assays: UV-Vis spectrophotometry, chemical oxygen demand (COD), total organic carbon (TOC), total Kjeldahl nitrogen, ammonia nitrogen, nitrates and HPLC. Results have shown a good electrodegradation of all the amines tested, with COD removals, after 6 h assays, higher than 90% and TOC removals between 60 and 80%. Combustion efficiency (η C ), which measures the tendency to convert organic carbon to CO 2 , was also determined for all the amines, being η CA1 CA2 CA3 CA4 = 0.99.

  18. Adsorption Characteristics of DNA Nucleobases, Aromatic Amino Acids and Heterocyclic Molecules on Silicene and Germanene Monolayers

    KAUST Repository

    Hussain, Tanveer

    2017-09-14

    Binding of DNA/RNA nucleobases, aromatic amino acids and heterocyclic molecules on two-dimensional silicene and germanene sheets have been investigated for the application of sensing of biomolecules using first principle density functional theory calculations. Binding energy range for nucleobases, amino acids and heterocyclic molecules with both the sheets have been found to be (0.43-1.16eV), (0.70-1.58eV) and (0.22-0.96eV) respectively, which along with the binding distances show that these molecules bind to both sheets by physisorption and chemisorption process. The exchange of electric charges between the monolayers and the incident molecules has been examined by means of Bader charge analysis. It has been observed that the introduction of DNA/RNA nucleobases, aromatic amino acids and heterocyclic molecules alters the electronic properties of both silicene and germanene nano sheets as studied by plotting the total (TDOS) and partial (PDOS) density of states. The DOS plots reveal the variation in the band gaps of both silicene and germanene caused by the introduction of studied molecules. Based on the obtained results we suggest that both silicene and germanene monolayers in their pristine form could be useful for sensing of biomolecules.

  19. Photocatalytic oxidation of aromatic amines using MnO2@g-C3N4

    Data.gov (United States)

    U.S. Environmental Protection Agency — 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...

  20. Analysis of primary aromatic amines using precolumn derivatization by HPLC fluorescence detection and online MS identification.

    Science.gov (United States)

    Zhao, Xianen; Suo, Yourui

    2008-03-01

    2-(2-phenyl-1H-phenanthro-[9,10-d]imidazole-1-yl)-acetic acid (PPIA) and 2-(9-acridone)-acetic acid (AAA), two novel precolumn fluorescent derivatization reagents, have been developed and compared for analysis of primary aromatic amines by high performance liquid chromatographic fluorescence detection coupled with online mass spectrometric identification. PPIA and AAA react rapidly and smoothly with the aromatic amines on the basis of a condensation reaction using 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC) as dehydrating catalyst to form stable derivatives with emission wavelengths at 380 and 440 nm, respectively. Taking six primary aromatic amines (aniline, 2-methylaniline, 2-methoxyaniline, 4-methylaniline, 4-chloroaniline, and 4-bromoaniline) as testing compounds, derivatization conditions such as coupling reagent, basic catalyst, reaction temperature and time, reaction solvent, and fluorescent labeling reagent concentration have also been investigated. With the better PPIA method, chromatographic separation of derivatized aromatic amines exhibited a good baseline resolution on an RP column. At the same time, by online mass spectrometric identification with atmospheric pressure chemical ionization (APCI) source in positive ion mode, the PPIA-labeled derivatives were characterized by easy-to-interpret mass spectra due to the prominent protonated molecular ion m/z [M + H](+) and specific fragment ions (MS/MS) m/z 335 and 295. The linear range is 24.41 fmol-200.0 pmol with correlation coefficients in the range of 0.9996-0.9999, and detection limits of PPIA-labeled aromatic amines are 0.12-0.21 nmol/L (S/N = 3). Method repeatability, precision, and recovery were evaluated and the results were excellent for the efficient HPLC analysis. The most important argument, however, was the high sensitivity and ease-of-handling of the PPIA method. Preliminary experiments with wastewater samples collected from the waterspout of a paper mill and its nearby soil where

  1. Stereochemical Basis for a Unified Structure Activity Theory of Aromatic and Heterocyclic Rings in Selected Opioids and Opioid Peptides

    Directory of Open Access Journals (Sweden)

    Joel S. Goldberg

    2010-02-01

    Full Text Available This paper presents a novel unified theory of the structure activity relationship of opioids and opioid peptides. It is hypothesized that a virtual or known heterocyclic ring exists in all opioids which have activity in humans, and this ring occupies relative to the aromatic ring of the drug, approximately the same plane in space as the piperidine ring of morphine. Since the rings of morphine are rigid, and the aromatic and piperidine rings are critical structural components for morphine’s analgesic properties, the rigid morphine molecule allows for approximations of the aromatic and heterocyclic relationships in subsequent drug models where bond rotations are common. This hypothesis and five propositions are supported by stereochemistry and experimental observations. Proposition #1 The structure of morphine provides a template. Proposition #2 Steric hindrance of some centric portion of the piperidine ring explains antagonist properties of naloxone, naltrexone and alvimopam. Proposition #3 Methadone has an active conformation which contains a virtual heterocyclic ring which explains its analgesic activity and racemic properties. Proposition #4 The piperidine ring of fentanyl can assume the morphine position under conditions of nitrogen inversion. Proposition #5 The first 3 amino acid sequences of beta endorphin (l-try-gly-gly and the active opioid dipeptide, l-tyr-pro, (as a result of a peptide turn and zwitterion bonding form a virtual piperazine-like ring which is similar in size, shape and location to the heterocyclic rings of morphine, meperidine, and methadone. Potential flaws in this theory are discussed. This theory could be important for future analgesic drug design.

  2. Hollow fibre-supported liquid membrane extraction and LC-MS/MS detection for the analysis of heterocyclic amines in urine samples

    DEFF Research Database (Denmark)

    Busquets, R.; Jonsson, J. A.; Frandsen, Henrik Lauritz

    2009-01-01

    Heterocyclic amines (HCAs) are potent mutagens/carcinogens to which humans are frequently exposed through the consumption of cooked meat and fish food. The effect of normal intake of HCAs and their role in the aetiology of human cancer is unknown. To some extent, limitations of the existing analy...

  3. Heterocyclic amines content of meat and fish cooked by Brazilian methods.

    Science.gov (United States)

    Iwasaki, Motoki; Kataoka, Hiroyuki; Ishihara, Junko; Takachi, Ribeka; Hamada, Gerson Shigeaki; Sharma, Sangita; Le Marchand, Loïc; Tsugane, Shoichiro

    2010-02-01

    Heterocyclic amine (HCA) concentrations were measured in meat and fish samples cooked by pan-frying, grilling and churrasco (Brazilian barbecue) to various levels of doneness in accordance with the cooking methods most commonly used in Brazil. HCAs were extracted by the Blue-rayon absorption method and measured by liquid chromatography-mass spectrometry. 2-Amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx), and 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline (4,8-DiMeIQx) were sharply increased in very well-done meats and fish. HCA levels varied somewhat across cooking methods: levels of PhIP (ng/g) in very well-done, non-marinated samples were particularly high for churrasco (31.8 in the exterior of the sample), compared to lower levels for grilled (16.3), and pan-fried beef (0.58). On comparison across foods, chicken contained higher HCA levels than other non-marinated samples. For example, PhIP levels (ng/g) in very well-done pan-fried foods were 34.6 for chicken with the skin, 0.58 for beef, 7.25 for pork, 2.28 for sardines, and 7.37 for salmon cooked with the skin. HCA levels were lower in marinated meats and fish than in non-marinated samples, except for pan-fried salmon. This study provides valuable information which will allow the estimation of dietary HCA exposure using an epidemiologic questionnaire and the investigation of the association of HCA intake with cancer risk in Brazil.

  4. A Catalyst-Enabled Diastereodivergent Aza-Diels-Alder Reaction: Complementarity of N-Heterocyclic Carbenes and Chiral Amines.

    Science.gov (United States)

    Rong, Zi-Qiang; Wang, Min; Chow, Chi Hao Eugene; Zhao, Yu

    2016-07-04

    Highly efficient and diastereodivergent aza-Diels-Alder reactions have been developed to access either diastereomeric series of benzofuran-fused δ-lactams and dihydropyridines in nearly perfect stereoselectivity (d.r. >20:1, >99 % ee for all examples). The complementarity of N-heterocyclic carbene and chiral amine as the catalyst was demonstrated for the first time, together with an excellent level of catalytic efficiency (1 mol % loading). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Efficient and Selective Reduction of Aromatic Nitro Compounds to Aromatic Amines by NbCl{sub 5}/Indium System

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Byung Woo; Kim, Duckil; Kim, Hyung Min; Kang, Sung Ho [Korea Univ., Seoul (Korea, Republic of)

    2012-09-15

    Aromatic amines find applicability in diverse fields including dyes, pharmaceuticals, agrochemicals, and photographic materials. To date, there are a variety of methods, which can be used to convert aromatic nitro compounds to their corresponding amines. Some of them include Cp{sub 2}TiCl{sub 2}/In, Al/NH{sub 4}Cl, (NH{sub 4}){sub 2}SO{sub 4}/NaBH{sub 4}, NiCl{sub 2}6H{sub 2}O/In, HI, Sm/I{sub 2}, In/NH{sub 4}Cl, B{sub 4}H{sub 10}/Pd/C, Co{sub 2}(CO){sub 8}/H{sub 2}O and In/HCl. However, most methods still lack the desired chemo-selectivity when other reducible functional groups are present in the nitroarene and often require long reaction times, or harsh reaction conditions. Consequently, efficient and selective methods for the reduction of aromatic nitro compounds continue to be developed. It has been reported that NbCl{sub 5}/Zn system is used as a reagent for reducing sulfoxides, epoxides, and amine N-oxides.12 Because of the close resemblance of indium to zinc in several respects, including first ionization potential, we considered that NbCl{sub 5}/In system can be an efficient reducing agent for the conversion of aromatic nitro compounds to the corresponding amines. Recently, indium metal has attracted much attention for its unique properties such as low toxicity and high stability in water and air compared with other metals. In continuation of our interest in exploring the utility of metal-metal salt system in organic synthesis, we would like to report an efficient and chemo-selective method for the reduction of various aromatic nitro compounds to the corresponding amines by treatment with NbCl{sub 5}/In system (eq. 1). The new reduction system was generated by the addition of indium powder to a stirred solution of niobium(V) chloride in THF under sonication. The generation of low-valent niobium species was examined at room temperature with an excess of indium metal. The observations suggest that this procedure can be applied for the chemo

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

    International Nuclear Information System (INIS)

    Hayon, E.; Rao, P.S.

    1975-01-01

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

  7. "Nanorust"-catalyzed benign oxidation of amines for selective synthesis of nitriles.

    Science.gov (United States)

    Jagadeesh, Rajenahally V; Junge, Henrik; Beller, Matthias

    2015-01-01

    Organic nitriles constitute key precursors and central intermediates in organic synthesis. In addition, nitriles represent a versatile motif found in numerous medicinally and biologically important compounds. Generally, these nitriles are synthesized by traditional cyanation procedures using toxic cyanides. Herein, we report the selective and environmentally benign oxidative conversion of primary amines for the synthesis of structurally diverse aromatic, aliphatic and heterocyclic nitriles using a reusable "nanorust" (nanoscale Fe2 O3 )-based catalysts applying molecular oxygen. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Monomers for thermosetting and toughening epoxy resins. [glycidyl amine derivatives, propargyl-containing amines, and mutagenic testing of aromatic diamines

    Science.gov (United States)

    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.

  9. Interaction of aromatic amines with iron oxides: implications for prebiotic chemistry.

    Science.gov (United States)

    Shanker, Uma; Singh, Gurinder; Kamaluddin

    2013-06-01

    The interaction of aromatic amines (aniline, p-chloroaniline, p-toludine and p-anisidine) with iron oxides (goethite, akaganeite and hematite) has been studied. Maximum uptake of amines was observed around pH 7. The adsorption data obtained at neutral pH were found to follow Langmuir adsorption. Anisidine was found to be a better adsorbate probably due to its higher basicity. In alkaline medium (pH > 8), amines reacted on goethite and akaganeite to give colored products. Analysis of the products by GC-MS showed benzoquinone and azobenzene as the reaction products of aniline while p-anisidine afforded a dimer. IR analysis of the amine-iron oxide hydroxide adduct suggests that the surface acidity of iron oxide hydroxides is responsible for the interaction. The present study suggests that iron oxide hydroxides might have played a role in the stabilization of organic molecules through their surface activity and in prebiotic condensation reactions.

  10. Pulse gas chromatographic study of adsorption of substituted aromatics and heterocyclic molecules on MIL-47 at zero coverage.

    Science.gov (United States)

    Duerinck, Tim; Couck, Sarah; Vermoortele, Frederik; De Vos, Dirk E; Baron, Gino V; Denayer, Joeri F M

    2012-10-02

    The low coverage adsorptive properties of the MIL-47 metal organic framework toward aromatic and heterocyclic molecules are reported in this paper. The effect of molecular functionality and size on Henry adsorption constants and adsorption enthalpies of alkyl and heteroatom functionalized benzene derivates and heterocyclic molecules was studied using pulse gas chromatography. By means of statistical analysis, experimental data was analyzed and modeled using principal component analysis and partial least-squares regression. Structure-property relationships were established, revealing and confirming several trends. Among the molecular properties governing the adsorption process, vapor pressure, mean polarizability, and dipole moment play a determining role.

  11. Occurrence of heterocyclic amines in cooked meat products.

    Science.gov (United States)

    Puangsombat, Kanithaporn; Gadgil, Priyadarshini; Houser, Terry A; Hunt, Melvin C; Smith, J Scott

    2012-03-01

    Heterocyclic amines (HCAs), potent mutagens and a risk factor for human cancers, are produced in meats cooked at high temperature. The aim of this study was to determine the HCA content in cooked meat products (beef, chicken, pork, fish) prepared by various cooking methods (pan frying, oven broiling, and oven baking at 170 to 230°C) that are preferred by U.S. meat consumers. The primary HCAs in these samples were PhIP (2-amino-1-methyl-6-phenylimidazo [4,5-b]pyridine) (1.49-10.89ng/g), MeIQx (2-amino-3,8-dimethylimidazo [4,5-f]quinoxaline) (not detected-4.0ng/g), and DiMeIQx (2-amino-3,4,8-trimethyl-imidazo [4,5-f]quinoxaline) (not detected-3.57ng/g). Type and content of HCAs in cooked meat samples were highly dependent on cooking conditions. The total HCA content in well-done meat was 3.5 times higher than that of medium-rare meat. Fried pork (13.91ng/g) had higher levels of total HCAs than fried beef (8.92ng/g) and fried chicken (7.00ng/g). Among the samples, fried bacon contained the highest total HCA content (17.59ng/g). Copyright © 2011 Elsevier Ltd. All rights reserved.

  12. Rapid determination of 9 aromatic amines in mainstream cigarette smoke by modified dispersive liquid liquid microextraction and ultraperformance convergence chromatography tandem mass spectrometry.

    Science.gov (United States)

    Deng, Huimin; Yang, Fei; Li, Zhonghao; Bian, Zhaoyang; Fan, Ziyan; Wang, Ying; Liu, Shanshan; Tang, Gangling

    2017-07-21

    Aromatic amines in mainstream cigarette smoke have long been monitored due to their carcinogenic toxicity. In this work, a reliable and rapid method was developed for the simultaneous determination of 9 aromatic amines in mainstream cigarette smoke by modified dispersive liquid liquid microextraction (DLLME) and ultraperformance convergence chromatography tandem mass spectrometry (UPC 2 -MS/MS). Briefly, the particulate phase of the cigarette smoke was captured by a Cambridge filter pad, and diluted hydrogen chloride aqueous solution is employed to extract the aromatic amines under mechanical shaking. After alkalization with sodium hydroxide solution, small amount of toluene was introduced to further extract and enrich aromatic amines by modified DLLME under vortexing. After centrifugation, toluene phase was purified by a universal QuEChERS cleanup kit and was finally analyzed by UPC 2 -MS/MS. Attributing to the superior performance of UPC 2 -MS/MS, this novel approach allowed the separation and determination of 9 aromatic amines within 5.0min with satisfactory resolution and sensitivity. The proposed method was finally validated using Kentucky reference cigarette 3R4F, and emission levels of targeted aromatic amines determined were comparable to previously reported methods At three different spiked levels, the recoveries of most analytes were ranged from 74.01% to 120.50% with relative standard deviation (RSD) less than 12%, except that the recovery of p-toluidine at low spiked level and 3-aminobiphenyl at medium spiked level was 62.77% and 69.37% respectively. Thus, this work provides a novel alternative method for the simultaneous analysis of 9 aromatic amines in mainstream cigarette smoke. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Peroxidase-mediated binding of aromatic amine carcinogens to tissue DNA

    International Nuclear Information System (INIS)

    Wise, R.W.; Lakshmi, V.M.; Zenser, T.V.; Davis, B.B.

    1986-01-01

    Benzidine is a aromatic amine bladder carcinogen in man and dog which requires endogenous metabolic activation. Dog bladder microsomes activate benzidine to bind glutathione and DNA by a peroxidatic but not a mixed-function oxidase mediated pathway. Prostaglandin H synthase was responsible for peroxidatic metabolism. This study was designed to assess benzidine metabolism in a whole cell system. Rabbit renal medullary slices (100 mg/ml) were incubated for 60 min. in Krebs-Ringer bicarbonate buffer containing 100 μM 3 H-benzidine and 250 μM arachidonic acid. Arachidonic acid increased 3-(glutathione-S-yL)-benzidine, a product of peroxidatically activated benzidine, (6-fold) and 3 H-benzidine binding to endogenous DNA (4-fold). Indomethacin (100 μM) completely inhibited arachidonic acid-mediated increases in conjugate formation and DNA binding. HPLC analysis of the media demonstrated benzidine (95% of total 3 H), 3-(glutathion-S-yL)-benzidine (1%) and two unidentified peaks (4%). These results are consistent with the hydroperoxidase activity of prostaglandin H synthase mediating metabolic activation of benzidine to bind tissue nucleophiles in a whole cell system. Inhibition of peroxidatic activation of aromatic amines to bind DNA may prevent initiation of bladder cancer

  14. Identification of metabolites in urine and feces from rats dosed with the heterocyclic amine, 2-amino-3-methyl-9H-pyrido[2,3-b]indole (MeA alpha C)

    DEFF Research Database (Denmark)

    Frederiksen, H; Frandsen, H

    2004-01-01

    2-Amino-3-methyl-9H-pyrido[2,3-b]indole (MeA alpha C) is a proximate mutagenic and carcinogenic heterocyclic amine formed during ordinary cooking. In model systems, MeA alpha C can be formed by pyrolyses of either tryptophan or proteins of animal or vegetable origin. In the present study, the in ......2-Amino-3-methyl-9H-pyrido[2,3-b]indole (MeA alpha C) is a proximate mutagenic and carcinogenic heterocyclic amine formed during ordinary cooking. In model systems, MeA alpha C can be formed by pyrolyses of either tryptophan or proteins of animal or vegetable origin. In the present study...

  15. Mild and Efficient Deoxygenation of Amine-N-Oxides with FeCl3·6H2O-Indium System under Ultrasonication

    International Nuclear Information System (INIS)

    Yoo, Byung Woo; Hwang, Sun Kyun; Kim, Dong Yoon; Choi, Jin Woo; Kang, Sang Ook; Yoo, Byoung Seung; Choi, Kyung Il; Kim, Joong Hyup

    2004-01-01

    We believe that the mild and efficient method described here will present an attractive alternative to the existing methods available for the reduction of amine-N-oxides to the corresponding amines. Further investigations of FeCl 3 ·6H 2 O/In system as reducing agent in organic synthesis are currently in progress. The deoxygenation of amine-N-oxides to amines in the presence of other functional groups is an important transformation in the synthesis of nitrogenous aromatic heterocycles. Many reagents have been employed for the deoxygenation of amine-N-oxides, including agents such as: low-valent titanium, phosphorous and sulphur compounds, tributyltin hydride, Pd/C, tetrathiomolybdate, SmI 2 , indium/NH 4 Cl. Recently we reported that Cp 2 TiCl 2 /In system could be used for the deoxygenation of various amine-N-oxides

  16. Alkynylation of heterocyclic compounds using hypervalent iodine reagent.

    Science.gov (United States)

    Kamlar, M; Císařová, I; Veselý, J

    2015-03-14

    The alkynylation of various nitrogen- and/or sulphur-containing heterocyclic compounds using hypervalent iodine TMS-EBX by utilization of tertiary amines under mild conditions is described. The developed metal-free methodology furnishes the corresponding alkynylated heterocycles bearing quaternary carbon in high yields.

  17. Comprehensive database of Manufactured Gas Plant tars. Part C. Heterocyclic and hydroxylated polycyclic aromatic hydrocarbons.

    Science.gov (United States)

    Gallacher, Christopher; Thomas, Russell; Lord, Richard; Kalin, Robert M; Taylor, Chris

    2017-08-15

    Coal tars are a mixture of organic and inorganic compounds that were by-products from the manufactured gas and coke making industries. The tar compositions varied depending on many factors such as the temperature of production and the type of retort used. For this reason a comprehensive database of the compounds found in different tar types is of value to understand both how their compositions differ and what potential chemical hazards are present. This study focuses on the heterocyclic and hydroxylated compounds present in a database produced from 16 different tars from five different production processes. Samples of coal tar were extracted using accelerated solvent extraction (ASE) and derivatized post-extraction using N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) with 1% trimethylchlorosilane (TMCS). The derivatized samples were analysed using two-dimensional gas chromatography combined with time-of-flight mass spectrometry (GCxGC/TOFMS). A total of 865 heterocyclic compounds and 359 hydroxylated polycyclic aromatic hydrocarbons (PAHs) were detected in 16 tar samples produced by five different processes. The contents of both heterocyclic and hydroxylated PAHs varied greatly with the production process used, with the heterocyclic compounds giving information about the feedstock used. Of the 359 hydroxylated PAHs detected the majority would not have been be detected without the use of derivatization. Coal tars produced using different production processes and feedstocks yielded tars with significantly different heterocyclic and hydroxylated contents. The concentrations of the individual heterocyclic compounds varied greatly even within the different production processes and provided information about the feedstock used to produce the tars. The hydroxylated PAH content of the samples provided important analytical information that would otherwise not have been obtained without the use of derivatization and GCxGC/TOFMS. Copyright © 2017 John Wiley & Sons, Ltd.

  18. Sacrificial spacer and non-covalent routes toward the molecular imprinting of 'poorly-functionalized' N-heterocycles

    International Nuclear Information System (INIS)

    Kirsch, N.; Alexander, C.; Davies, S.; Whitcombe, M.J.

    2004-01-01

    A comparison of three different methods for the imprinting of small aromatic heterocycles containing only a single nitrogen atom, for the preparation of specific analytical phases, was carried out. A conventional non-covalent approach to the imprinting of pyridine using methacrylic acid as the functional monomer was compared with two sacrificial spacer methods, in which heterocycles were imprinted as covalent template analogues. The results of binding experiments showed that discrimination based on ligand size was possible when polymers were prepared using a silyl ester-based template. The most selective polymer was able to bind pyridine in preference to quinoline or acridine which is opposite to the trend predicted by the pK HB values for the three ligands. Curve fitting of the isotherm for pyridine binding to this polymer to the Langmuir model gave an approximate K d of 1.1±0.1 mM and a binding site concentration of 57±2 mmol g -1 . Acridine binding did not show saturation behaviour and was non-specific and cooperative in nature

  19. Conformational switching of ethano-bridged Cu,H2-bis-porphyrin induced by aromatic amines.

    Science.gov (United States)

    Bettini, Simona; Maglie, Emanuela; Pagano, Rosanna; Borovkov, Victor; Inoue, Yoshihisa; Valli, Ludovico; Giancane, Gabriele

    2015-01-01

    Cu,H2-bis-porphyrin (Cu,H2-Por2), in which copper porphyrin and free-base porphyrin are linked together by an ethano-bridge, was dissolved in chloroform and spread at the air/liquid subphase interface of a Langmuir trough. The bis-porphyrin derivative, floating film was characterized by reflection spectroscopy and the surface pressure of the floating film was studied as a function of the mean area per molecule. When aromatic amines are dissolved in the subphase, an evident interaction between the bis-porphyrin host and the aromatic amine guest is observed. A clear-cut variation of the profile of surface pressure vs area per molecule curve is observed. Reflection spectroscopy highlights that the aromatic amines dissolved in the subphase are able to induce the syn-to-anti conformational switching in the bis-porphyrin derivative. The Langmuir-Schaefer technique has been used to transfer the floating bis-porphyrin film (when using pure water as a subphase) to a surface plasmon resonance (SPR) substrate and the resulting device was able to detect the presence of aniline at concentrations as low as 1 nM in aqueous solution. The high selectivity of the SPR sensing device has been verified by checking the spectral response of the active layer towards other analytes dissolved in the aqueous solutions.

  20. Conformational switching of ethano-bridged Cu,H2-bis-porphyrin induced by aromatic amines

    Directory of Open Access Journals (Sweden)

    Simona Bettini

    2015-11-01

    Full Text Available Cu,H2-bis-porphyrin (Cu,H2-Por2, in which copper porphyrin and free-base porphyrin are linked together by an ethano-bridge, was dissolved in chloroform and spread at the air/liquid subphase interface of a Langmuir trough. The bis-porphyrin derivative, floating film was characterized by reflection spectroscopy and the surface pressure of the floating film was studied as a function of the mean area per molecule. When aromatic amines are dissolved in the subphase, an evident interaction between the bis-porphyrin host and the aromatic amine guest is observed. A clear-cut variation of the profile of surface pressure vs area per molecule curve is observed. Reflection spectroscopy highlights that the aromatic amines dissolved in the subphase are able to induce the syn-to-anti conformational switching in the bis-porphyrin derivative. The Langmuir–Schaefer technique has been used to transfer the floating bis-porphyrin film (when using pure water as a subphase to a surface plasmon resonance (SPR substrate and the resulting device was able to detect the presence of aniline at concentrations as low as 1 nM in aqueous solution. The high selectivity of the SPR sensing device has been verified by checking the spectral response of the active layer towards other analytes dissolved in the aqueous solutions.

  1. PRESSURE EFFECTS IN POLYCYCLIC AROMATIC NITROGENATED HETEROCYCLES (PANHs): DIAGNOSTIC QUALITIES AND COSMOBAROMETRY POTENTIAL

    Energy Technology Data Exchange (ETDEWEB)

    Montgomery, Wren; Sephton, Mark A., E-mail: w.montgomery@imperial.ac.uk [Impacts and Astromaterials Research Centre, Department of Earth Science and Engineering, Imperial College London SW7 2AZ (United Kingdom)

    2016-03-01

    The influence of polycyclic aromatic nitrogen heterocycles (PANHs), which have been suggested as contributors to the interstellar IR emission bands, on interstellar emission features is difficult to constrain because their infrared characteristics are strongly similar to those for polycyclic aromatic hydrocarbons (PAHs). One possible solution is to seek a means of visualizing the presence of PANHs that provides information that is distinct from that for PAHs. Although PANHs and PAHs have similar infrared characteristics in many settings, this relationship may not be universally maintained. We have used in situ high-pressure synchrotron-source Fourier transform infrared spectroscopy to determine that the responses of two representative molecules, acridine and anthracene, differ at high pressures (>ca. 1 GPa). Because there are a number of high-pressure environments that can be remotely observed by infrared spectroscopy, they represent a potential to glimpse the distribution of PANHs across the cosmos.

  2. Mild and Efficient Deoxygenation of Amine-N-Oxides with FeCl{sub 3}·6H{sub 2}O-Indium System under Ultrasonication

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Byung Woo; Hwang, Sun Kyun; Kim, Dong Yoon; Choi, Jin Woo; Kang, Sang Ook [Korea University, Jochiwon (Korea, Republic of); Yoo, Byoung Seung [Dongguk University, Seoul (Korea, Republic of); Choi, Kyung Il; Kim, Joong Hyup [Korea Institute of Science and Technology, Seoul (Korea, Republic of)

    2004-11-15

    We believe that the mild and efficient method described here will present an attractive alternative to the existing methods available for the reduction of amine-N-oxides to the corresponding amines. Further investigations of FeCl{sub 3}·6H{sub 2}O/In system as reducing agent in organic synthesis are currently in progress. The deoxygenation of amine-N-oxides to amines in the presence of other functional groups is an important transformation in the synthesis of nitrogenous aromatic heterocycles. Many reagents have been employed for the deoxygenation of amine-N-oxides, including agents such as: low-valent titanium, phosphorous and sulphur compounds, tributyltin hydride, Pd/C, tetrathiomolybdate, SmI{sub 2}, indium/NH{sub 4}Cl. Recently we reported that Cp{sub 2}TiCl{sub 2}/In system could be used for the deoxygenation of various amine-N-oxides.

  3. Removal of polycyclic aromatic hydrocarbons in soil spiked with model mixtures of petroleum hydrocarbons and heterocycles using biosurfactants from Rhodococcus ruber IEGM 231.

    Science.gov (United States)

    Ivshina, Irina; Kostina, Ludmila; Krivoruchko, Anastasiya; Kuyukina, Maria; Peshkur, Tatyana; Anderson, Peter; Cunningham, Colin

    2016-07-15

    Removal of polycyclic aromatic hydrocarbons (PAHs) in soil using biosurfactants (BS) produced by Rhodococcus ruber IEGM 231 was studied in soil columns spiked with model mixtures of major petroleum constituents. A crystalline mixture of single PAHs (0.63g/kg), a crystalline mixture of PAHs (0.63g/kg) and polycyclic aromatic sulfur heterocycles (PASHs), and an artificially synthesized non-aqueous phase liquid (NAPL) containing PAHs (3.00g/kg) dissolved in alkanes C10-C19 were used for spiking. Percentage of PAH removal with BS varied from 16 to 69%. Washing activities of BS were 2.5 times greater than those of synthetic surfactant Tween 60 in NAPL-spiked soil and similar to Tween 60 in crystalline-spiked soil. At the same time, amounts of removed PAHs were equal and consisted of 0.3-0.5g/kg dry soil regardless the chemical pattern of a model mixture of petroleum hydrocarbons and heterocycles used for spiking. UV spectra for soil before and after BS treatment were obtained and their applicability for differentiated analysis of PAH and PASH concentration changes in remediated soil was shown. The ratios A254nm/A288nm revealed that BS increased biotreatability of PAH-contaminated soils. Copyright © 2016 Elsevier B.V. All rights reserved.

  4. Determination of Aromatic Amines in Cigarette Mainstream Smoke - The CORESTA 2007 Joint Experiment

    Directory of Open Access Journals (Sweden)

    Intorp M

    2014-12-01

    Full Text Available CORESTA joint experiment work in 2006 had compared data on a wide range of smoke constituents obtained from Kentucky reference cigarettes (1R5F and 2R4F, according to the existing methods used by participants. This work had identified that the methods used to determine aromatic amine yields in mainstream smoke would particularly benefit from further study to investigate the main weaknesses and influencing factors in their yield variability before progressing to full method standardisation. This report describes the output from a 2007 joint experiment to address these issues. Participating laboratories carried out experiments to investigate several factors that had been identified in the methodology as potential sources of variability. These were the amine derivative type, the derivatisation time and the point at which the addition of the internal standard for calibration occurred. A statistical assessment was made of their possible influence on aromatic amine smoke yields and yield reproducibility across different laboratories. Results showed that aromatic amines again had poor between-laboratory yield reproducibility. The stage at which the internal standard was added to the smoke sample had the most significant effect on yields. The least variable data were obtained when it was added directly after extraction from the filter pad rather than later in the process. It also appeared beneficial to use at least two calibration standards (i.e., an aminonaphthalene and an aminobiphenyl to minimise yield differences although this recommendation was not supported by statistically significant data. Large differences in yields were not found when comparing the two studied derivatising agents especially when compared against the greater overall between-laboratory variability. Any differences between laboratories in total particulate matter and puff count at the smoke collection stage did not appear to significantly contribute to betweenlaboratory

  5. Selective N-alkylation of amines using nitriles under hydrogenation conditions: facile synthesis of secondary and tertiary amines.

    Science.gov (United States)

    Ikawa, Takashi; Fujita, Yuki; Mizusaki, Tomoteru; Betsuin, Sae; Takamatsu, Haruki; Maegawa, Tomohiro; Monguchi, Yasunari; Sajiki, Hironao

    2012-01-14

    Nitriles were found to be highly effective alkylating reagents for the selective N-alkylation of amines under catalytic hydrogenation conditions. For the aromatic primary amines, the corresponding secondary amines were selectively obtained under Pd/C-catalyzed hydrogenation conditions. Although the use of electron poor aromatic amines or bulky nitriles showed a lower reactivity toward the reductive alkylation, the addition of NH(4)OAc enhanced the reactivity to give secondary aromatic amines in good to excellent yields. Under the same reaction conditions, aromatic nitro compounds instead of the aromatic primary amines could be directly transformed into secondary amines via a domino reaction involving the one-pot hydrogenation of the nitro group and the reductive alkylation of the amines. While aliphatic amines were effectively converted to the corresponding tertiary amines under Pd/C-catalyzed conditions, Rh/C was a highly effective catalyst for the N-monoalkylation of aliphatic primary amines without over-alkylation to the tertiary amines. Furthermore, the combination of the Rh/C-catalyzed N-monoalkylation of the aliphatic primary amines and additional Pd/C-catalyzed alkylation of the resulting secondary aliphatic amines could selectively prepare aliphatic tertiary amines possessing three different alkyl groups. According to the mechanistic studies, it seems reasonable to conclude that nitriles were reduced to aldimines before the nucleophilic attack of the amine during the first step of the reaction.

  6. Catalytic oxidation of o-aminophenols and aromatic amines by mushroom tyrosinase.

    Science.gov (United States)

    Muñoz-Muñoz, Jose Luis; Garcia-Molina, Francisco; Garcia-Ruiz, Pedro Antonio; Varon, Ramon; Tudela, Jose; Rodriguez-Lopez, Jose N; Garcia-Canovas, Francisco

    2011-12-01

    The kinetics of tyrosinase acting on o-aminophenols and aromatic amines as substrates was studied. The catalytic constants of aromatic monoamines and o-diamines were both low, these results are consistent with our previous mechanism in which the slow step is the transfer of a proton by a hydroxyl to the peroxide in oxy-tyrosinase (Fenoll et al., Biochem. J. 380 (2004) 643-650). In the case of o-aminophenols, the hydroxyl group indirectly cooperates in the transfer of the proton and consequently the catalytic constants in the action of tyrosinase on these compounds are higher. In the case of aromatic monoamines, the Michaelis constants are of the same order of magnitude than for monophenols, which suggests that the monophenols bind better (higher binding constant) to the enzyme to facilitate the π-π interactions between the aromatic ring and a possible histidine of the active site. In the case of aromatic o-diamines, both the catalytic and Michaelis constants are low, the values of the catalytic constants being lower than those of the corresponding o-diphenols. The values of the Michaelis constants of the aromatic o-diamines are slightly lower than those of their corresponding o-diphenols, confirming that the aromatic o-diamines bind less well (lower binding constant) to the enzyme. Copyright © 2011 Elsevier B.V. All rights reserved.

  7. Phenols and aromatic amines as thermal stabilizers in polyolefin processing

    Czech Academy of Sciences Publication Activity Database

    Pospíšil, Jan; Habicher, W. D.; Al-Malaika, S.; Zweifel, H.; Nešpůrek, Stanislav

    2001-01-01

    Roč. 176, - (2001), s. 55-63 ISSN 1022-1360. [International Conference on Polymer Modification, Degradation and Stabilization /1./. Palermo , 03.09.2000-07.09.2000] R&D Projects: GA AV ČR IAA1050901; GA MŠk ME 184; GA MŠk ME 372; GA AV ČR KSK4050111 Institutional research plan: CEZ:AV0Z4050913 Keywords : thermal stabilizers * phenols * aromatic amines Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.634, year: 2001

  8. A sensitive method using SPME pre-concentration for the quantification of aromatic amines in indoor air.

    Science.gov (United States)

    Lucaire, Vincent; Schwartz, Jean-Jacques; Delhomme, Olivier; Ocampo-Torres, Ruben; Millet, Maurice

    2018-03-01

    Monitoring the levels of aliphatic and aromatic amines (AA) in indoor air is important to protect human health because of exposure to these compounds through diet and inhalation. A sampling and analytical method using XAD-2 cartridges and gas chromatography coupled to mass spectrometry used for assessing 25 AA in different smoking and non-smoking indoor environment was developed. After sampling and delivering 1 m 3 of air (6-8 h sampling), an adsorbent was ultrasonically extracted with acetonitrile, concentrated to 1 mL and diluted in 25 mL of water (pH = 9; 5% NaCl), and then extracted for 40 min at 80 °C using a divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber and injected in a GC/MS system. With this method, 22 of the 25 AA can be analyzed with detection limits up to five times lower than that of classic liquid injection. Benzylamine, 3-aminophenol, and 4-aminophenol were not detected with the solid-phase micro-extraction (SPME) method. It can be assumed that aminophenols required a derivatization step for their analysis by GC as these molecules were not detected regardless of the injection mode used. Graphical abstract Analysis of aromatic amines in indoor air by SPME-GC/MS.

  9. Infrared Spectroscopy of Matrix-Isolated Polycyclic Aromatic Compounds and Their Ions. 7; Phenazine, a Dual Substituted Polycyclic Aromatic Nitrogen Heterocycle

    Science.gov (United States)

    Mattioda, A. L.; Hudgins, D. M.; Bauschlicher, C. W., Jr.; Allamandola, L. J.

    2004-01-01

    The matrix-isolation technique has been employed to measure the mid-infrared spectra of phenazine (C12H8N2), a dual substituted Polycyclic Aromatic Nitrogen Heterocycle (PANH), in the neutral, cationic and anionic forms. The experimentally measured band frequencies and intensities are tabulated and compared with their calculated values as well as those of the non-substituted parent molecule, anthracene. The theoretical band positions and intensities were calculated using both the 3-31 G as well as the larger 6-3lG* Basis Sets. A comparison of the results can be found in the tables. The spectroscopic properties of phenazine and its cation are similar to those observed in mono-substituted PANHs, with one exception. The presence of a second nitrogen atom results in an additional enhancement of the cation's total integrated intensity, for the 1500-1000 cm(sup -1) (6.7 to 10 micron) region, over that observed for a mono-substituted PANH cation. The significance of this enhancement and the astrobiological implications of these results are discussed.

  10. Aromatic/heterocyclic amino acids and the simulated sunlight-ultraviolet inactivation of the Heliothis/Helicoverpa baculovirus

    International Nuclear Information System (INIS)

    Ignoffo, C.M.; Garcia, C.

    1995-01-01

    Tryptophan, of five aromatic/heterocyclic amino acids (tyrosine, phenylalanine, proline, histidine) provided significant protection of the Heliothis baculovirus (HzSNPV) from inactivation by simulated ultraviolet (SUV). Fifty percent of SUV protection of HzSNPV with tryptophan or tyrosine was obtained at 0.03 mg/ml and 0.5 mg/ml, respectively. Rates as high as 100.0 mg/ml of phenylalanine, histidine, or proline provided <50% protection. The extent of tryptophan protection was correlated with its absorption in the sunlight UV-B spectra. 16 refs., 2 tabs

  11. Study of interaction and adsorption of aromatic amines by manganese oxides and their role in chemical evolution

    Science.gov (United States)

    Bhushan, Brij; Nayak, Arunima; Kamaluddin

    2017-04-01

    The role of manganese oxides in concentrating organic moieties and offering catalytic activity for prebiotic reactions is investigated by studying their interaction with different aromatic amines such as aniline, p-chloroaniline, p-toluidine and p-anisidine. For all amines, metal oxides showed highest adsorption at neutral pH. The order of their adsorption capacity and affinity as revealed by the Langmuir constants was found to be manganosite (MnO) > bixbyite (Mn2O3) > hausmannite (Mn3O4) > and pyrolusite (MnO2). At alkaline pH, these manganese oxides offered their surfaces for oxidation of amines to form coloured oligomers. Analysis of the oxidation products by gas chromatography-mass spectrometry showed the formation of a dimer from p-anisidine and p-chloroaniline, while a trimer and tetramer is formed from p-toluidine and aniline, respectively. A reaction mechanism is proposed for the formation of the oligomers. While field-emission scanning electron microscopic studies confirm the binding phenomenon, the Fourier transform infrared spectroscopy analysis suggests that the mechanism of binding of amines on the manganese oxides was primarily electrostatic. The adsorption behaviour of the studied aromatic amines followed the order: p-anisidine > p-toluidine > aniline > p-chloroaniline, which is related to the basicities and structure of the amines. Our studies confirmed the significance of the role of manganese oxides in prebiotic chemistry.

  12. Acrolein contributes strongly to antimicrobial and heterocyclic amine transformation activities of reuterin.

    Science.gov (United States)

    Engels, Christina; Schwab, Clarissa; Zhang, Jianbo; Stevens, Marc J A; Bieri, Corinne; Ebert, Marc-Olivier; McNeill, Kristopher; Sturla, Shana J; Lacroix, Christophe

    2016-11-07

    Glycerol/diol dehydratases catalyze the conversion of glycerol to 3-hydroxypropionaldehyde (3-HPA), the basis of a multi-component system called reuterin. Reuterin has antimicrobial properties and undergoes chemical conjugation with dietary heterocyclic amines (HCAs). In aqueous solution reuterin is in dynamic equilibrium with the toxicant acrolein. It was the aim of this study to investigate the extent of acrolein formation at various physiological conditions and to determine its role in biological and chemical activities. The application of a combined novel analytical approach including IC-PAD, LC-MS and NMR together with specific acrolein scavengers suggested for the first time that acrolein, and not 3-HPA, is the active compound responsible for HCA conjugation and antimicrobial activity attributed to reuterin. As formation of the HCA conjugate was observed in vivo, our results imply that acrolein is formed in the human gut with implications on detoxification of HCAs. We propose to re-define the term reuterin to include acrolein.

  13. Sacrificial spacer and non-covalent routes toward the molecular imprinting of 'poorly-functionalized' N-heterocycles

    Energy Technology Data Exchange (ETDEWEB)

    Kirsch, N.; Alexander, C.; Davies, S.; Whitcombe, M.J

    2004-02-16

    A comparison of three different methods for the imprinting of small aromatic heterocycles containing only a single nitrogen atom, for the preparation of specific analytical phases, was carried out. A conventional non-covalent approach to the imprinting of pyridine using methacrylic acid as the functional monomer was compared with two sacrificial spacer methods, in which heterocycles were imprinted as covalent template analogues. The results of binding experiments showed that discrimination based on ligand size was possible when polymers were prepared using a silyl ester-based template. The most selective polymer was able to bind pyridine in preference to quinoline or acridine which is opposite to the trend predicted by the pK{sub HB} values for the three ligands. Curve fitting of the isotherm for pyridine binding to this polymer to the Langmuir model gave an approximate K{sub d} of 1.1{+-}0.1 mM and a binding site concentration of 57{+-}2 mmol g{sup -1}. Acridine binding did not show saturation behaviour and was non-specific and cooperative in nature.

  14. Plant extracts, spices, and essential oils inactivate E. coli O157:H7 pathogens and reduce formation of potentially carcinogenic heterocyclic amines in grilled beef patties

    Science.gov (United States)

    Meats need to be sufficiently heated to inactivate foodborne pathogens such as Escherichia coli O157:H7. High-temperature heat treatment used to prepare well-done meats could, however, increase the formation of potentially carcinogenic heterocyclic amines (HCAs). The objective of this study was to ...

  15. Laboratory Infrared Spectra of Polycyclic Aromatic Nitrogen Heterocycles: Quinoline, and Phenanthridine in Solid Argon and H2O

    Science.gov (United States)

    Bernstein, M. P.; Mattioda, A. L.; Sandford, S. A.; Hudgins, D. M.

    2004-01-01

    Polycyclic aromatic hydrocarbons (PAHs) are common throughout the universe. Their detection and identification are based on telescopic infrared (IR) spectra compared with laboratory data. Polycyclic Aromatic Nitrogen Heterocycles (PANHs) are heterocyclic aromatics i.e., PAHs with carbon atoms replaced by a nitrogen atom. These molecules should be present in the interstellar medium, but have received relatively little attention. We present mid-IR spectra of two PANHs, quinoline (C9H7N), and phenanthridine (C13H9N) isolated in solid argon and frozen in solid H2O at 12 K, conditions yielding data directly comparable to astronomical observations. In contrast to simple PAHs, that do not interact strongly with solid H2O, the nitrogen atoms in PANHs are potentially capable of hydrogen bonding with H2O. Whereas the IR spectrum of phenanthridine in H2O is similar to that of the same compound isolated in an argon matrix, quinoline absorptions shift up to 16 cm(sup -1) (0.072 mm) between argon and H2O. Thus, astronomers will not always be able to rely on IR band positions of matrix isolated PANHs to correctly interpret the absorptions of PANHs frozen in H2O ice grains. Furthermore, our data suggest that relative band areas also vary, so determining column densities to better than a factor of 3 will require knowledge of the matrix in which the PANH is embedded and laboratory studies of relevant samples.

  16. Occurrence of heterocyclic amines in several home-cooked meat dishes of the Spanish diet.

    Science.gov (United States)

    Busquets, R; Bordas, M; Toribio, F; Puignou, L; Galceran, M T

    2004-03-25

    Heterocyclic amines (HAs) were determined in several of the most frequently eaten meat dishes in Spain such as fried beef hamburger, fried pork loin, fried chicken breast, fried pork sausages, griddled chicken breast, griddled lamb steak and griddled beef steak. All of the products tested were household cooked. The HAs were analysed in the selected meat dishes using an analytical method based on solid-phase extraction followed by liquid chromatography coupled to tandem mass spectrometry. DMIP, MeIQx, 4,8-DiMeIQx, Norharman, Harman, PhIP, Trp-P-1, AalphaC and MeAalphaC were the amines most frequently found at concentrations of up to 47 ng g(-1) of cooked meat. Glu-P-2, IQ, MeIQ, Glu-P-1, 7,8-DiMeIQx and Trp-P-2 were only found in a few of the meat dishes and their concentrations were lower than 1 ng g(-1) of cooked meat. The highest amounts of HAs, especially PhIP and DMIP, were formed in fried chicken breast and the lowest were formed in fried beef hamburger and in fried pork sausages. Daily intake of HAs in Spain was estimated at 606 ng of mutagenic HAs per capita and day, DMIP and PhIP being the main contributors.

  17. An etiologic prediction model incorporating biomarkers to predict the bladder cancer risk associated with occupational exposure to aromatic amines: a pilot study

    OpenAIRE

    Mastrangelo, Giuseppe; Carta, Angela; Arici, Cecilia; Pavanello, Sofia; Porru, Stefano

    2017-01-01

    Background No etiological prediction model incorporating biomarkers is available to predict bladder cancer risk associated with occupational exposure to aromatic amines. Methods Cases were 199 bladder cancer patients. Clinical, laboratory and genetic data were predictors in logistic regression models (full and short) in which the dependent variable was 1 for 15 patients with aromatic amines related bladder cancer and 0 otherwise. The receiver operating characteristics approach was adopted; th...

  18. Metabolic activation of polycyclic and heterocyclic aromatic hydrocarbons and DNA damage: A review

    International Nuclear Information System (INIS)

    Xue Weiling; Warshawsky, David

    2005-01-01

    Polycyclic aromatic hydrocarbons (PAHs) and heterocyclic aromatic compounds (HACs) constitute a major class of chemical carcinogens present in the environment. These compounds require activation to electrophilic metabolites to exert their mutagenic or carcinogenic effects. There are three principal pathways currently proposed for metabolic activation of PAH and HAC: the pathway via bay region dihydrodiol epoxide by cytochrome P450 enzymes (CYPs), the pathway via radical cation by one-electron oxidation, and the ortho-quinone pathway by dihydrodiol dehydrogenase (DD). In addition to these major pathways, a brief description of a minor metabolic activation pathway, sulfonation, for PAHs that contain a primary benzylic alcoholic group or secondary hydroxyl group(s) is included in this review. The DNA damages caused through the reactive metabolites of PAH/HAC are described involving the DNA covalent binding to form stable or depurinating adducts, the formation of apurinic sites, and the oxidative damage. The review emphasizes the chemical/biochemical reactions involved in the metabolic processes and the chemical structures of metabolites and DNA adducts

  19. Anomalous length dependence of conductance of aromatic nanoribbons with amine anchoring groups

    KAUST Repository

    Bilić, Ante

    2012-09-06

    Two sets of aromatic nanoribbons, based around a common hexagonal scaffolding, with single and dual terminal amine groups have been considered as potential molecular wires in a junction formed by gold leads. Charge transport through the two-terminal device has been modeled using density functional theory (with and without self-interaction correction) and the nonequilibrium Green\\'s function method. The effects of wire length, multiple terminal contacts, and pathways across the junction have been investigated. For nanoribbons with the oligopyrene motif and conventional single amine terminal groups, an increase in the wire length causes an exponential drop in the conductance. In contrast, for the nanoribbons with the oligoperylene motif and dual amine anchoring groups the predicted conductance rises with the wire length over the whole range of investigated lengths. Only when the effects of self-interaction correction are taken into account, the conductance of the oligoperylene ribbons exhibits saturation for longer members of the series. The oligoperylene nanoribbons, with dual amine groups at both terminals, show the potential to fully harness the highly conjugated system of π molecular orbitals across the junction. © 2012 American Physical Society.

  20. N-type doping effect of single-walled carbon nanotubes with aromatic amines

    Energy Technology Data Exchange (ETDEWEB)

    Koizhaiganova, Raushan B.; Hwang, Doo Hee; Lee, Cheol Jin; Dettlaff-Weglikowska, Urszula [School of Electrical Engineering, Korea University, Seoul 136-713 (Korea, Republic of); Roth, Siegmar [School of Electrical Engineering, Korea University, Seoul 136-713 (Korea, Republic of); Sineurop Nanotech GmbH, Nobelstreet15, 70569 Stuttgart (Germany)

    2010-12-15

    We investigated the chemical doping of the single-walled carbon nanotubes (SWCNTs) networks by a treatment with aromatic amines. Adsorption and intercalation of amine molecules in bundled SWCNTs leads to typical n-type doping observed already for alkali metals. The electron donation to SWCNTs is demonstrated by the X-ray-induced photoelectron spectra (XPS), where the carbon C 1s peak observed at 284.4 eV for the sp{sup 2} carbon in pristine samples is shifted by up to 0.3 eV to higher binding energy upon chemical treatment. The development of a Breit-Wigner-Fano component on the lower energy side of the G{sup -} mode in the Raman spectrum as well as a shift of the G{sup +} to lower frequency provide evidence for charge accumulation in the nanotube {pi} system, and indication for the n-type doping. The spectroscopic changes are accompanied by the modification of the electrical properties of the SWCNTs. A reduction of conductivity depends on the doping level and implies the decreasing concentration of the charge carriers in the naturally p-doped tubes. Comparing the two selected n-type dopants, the tetramethyl-p-phenylenediamine, shows more pronounced changes in the XPS and the Raman spectra than tetramethylpyrazine, indicating that the sp{sup 3} hybridization of nitrogen in the amine groups attached to phenyl ring is much more effective in interaction with the tube {pi} system than the sp{sup 2} hybridization of nitrogen in the aromatic pyrazine ring. (Copyright copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  1. Stereoselective synthesis of organosulfur compounds incorporating N-aromatic heterocyclic motifs and quaternary carbon centers via a sulfa-Michael triggered tandem reaction.

    Science.gov (United States)

    Qin, Tianyou; Cheng, Lu; Zhang, Sean Xiao-An; Liao, Weiwei

    2015-06-14

    A novel sulfa-Michael addition (SMA)-triggered tandem reaction was developed by combining a SMA reaction with a simultaneous rearomatization process utilizing a less reactive carbonyl group as an intramolecular electrophile partner, which provided a unique synthetic route to access various organosulfur compounds incorporating an N-aromatic heterocyclic motif and quaternary carbon centers.

  2. Bacterial Degradation of Aromatic Compounds

    Directory of Open Access Journals (Sweden)

    Qing X. Li

    2009-01-01

    Full Text Available 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.

  3. Nucleophilic addition of amines to the activated ethylene bond in non-aqueous media

    International Nuclear Information System (INIS)

    Perepichka, Igor F.; Popov, Anatolii F.

    1995-01-01

    The kinetics of addition of a number of primary and secondary aliphatic amines to trans-(2-furyl) nitro ethylene (1) has been studied in solvents of various polarities (from acetonitrile, ε 37.5, to heptane, ε 1.89). It has been shown that the reaction is catalysed both by the amine reagent and by tertiary amines. On the basis of analyzing the observed kinetic regularities a stepwise reaction mechanism has been proposed which involves formation of zwitterionic intermediate (3) at the first equilibrium step (k 1 , K 1 ) which is then converted into the reaction product by means of proton transfer in parallel routes, the non-catalytic one (k 2 ) and that catalysed by the initial (K 3 ) or tertiary (K 4 ) amine. The observed high values of the deuterium isotope effects in the reaction (K H /K D ∼ 2.3 - 8.9) confirm that proton transfer occurs in the rate-limiting step of the reaction (primary kinetic isotope effect). The third order by amine kinetic route is observed in low polar media which is due to participation of amine dimers (R 2 NH HNR 2 ) in the reaction. The observed kinetic regularities are compared with those for the nucleophilic aromatic substitution reactions in low-polar media, and the conclusion has been made that the reaction route of the third order by amine proceeds as reversible nucleophilic attack by amine dimer and following base-catalysed transformation of the intermediate into the product. (author)

  4. Effect of Ionic Liquid on the Determination of Aromatic Amines as Contaminants in Hair Dyes by Liquid Chromatography Coupled to Electrochemical Detection

    Directory of Open Access Journals (Sweden)

    Maria Valnice Boldrin Zanoni

    2012-07-01

    Full Text Available The room temperature ionic liquid (IL 1-butyl-3-methylimidazolium bis-(trifluorometanesulfonylimide BMIm[NTf2] was used as a novel medium for improvement of separation and quantization of 16 aromatic amines typically present as contaminants in consumer products and detected by HPLC coupled to an electrochemical detector. The aromatic amines, namely 4,4'-diaminodiphenylmethane, 4-chloroaniline, 2-methoxy-5-methyl-aniline, 3,3'-dimethylbenzidine, 2,4-diaminotoluidine, 2-chloro-4-nitroaniline, 4,4'-oxydianiline, aniline, 3,3'-dichlorobenzidine, benzidine, 4-aminobiphenyl, o-dianisidine, o-anisidine, o-toluidine, 4,4'-methylene-bis-2-chloroaniline and 2-naphthyl-amine are oxidized in methanol/BMIm[NTf2] at a potential around +0.68V to +0.93V vs. Ag/AgCl at a glassy carbon electrode, which is the base for their determination by HPLC/ED. Using the optimized conditions of methanol/BMIm[NTf2] 70:30 (v/v as mobile phase, flow-rate of 0.8 mL·min−1, column CLC-ODS, Eap = +1.0 V and T = 40 °C analytical curves were constructed for each of the tested amines. Good linearity was obtained in the concentration range of 1.09 mg·L−1 to 217 mg·L−1, with excellent correlation coefficients. The limits of detection reached 0.021 mg·L−1 to 0.246 mg·L−1 and good relative standard deviations (RSD, n = 3 were obtained from the measurements. Satisfactory recovery for each aromatic amine was achieved, ranging from 95 to 103%. The developed method was successfully applied to determine six aromatic amines present as contaminants in commercial hair dye samples.

  5. Synthesis and in vitro biological evaluation of new pyrazole chalcones and heterocyclic diamides as potential anticancer agents

    Directory of Open Access Journals (Sweden)

    Sankappa Rai U.

    2015-05-01

    Full Text Available Synthesis and characterization of new heterocyclic pyrazole chalcones (4a–e and diamide (6a–e derivatives are described. Pyrazole chalcones were synthesized by the reaction of pyrazole aldehydes and suitable aromatic ketones. Diamides were synthesized by the reaction of phthalic acid and amines. Newly synthesized compounds were characterized by spectral studies and their biological activity was assessed in vitro using MCF-7 (human breast adenocarcinoma and HeLa (human cervical tumor cells cell lines. Few of the synthesized molecules inhibited the growth of the human breast cancer cell lines and human cervical tumor cell lines at low micromolar to nanomolar concentrations.

  6. Bioreducible poly(amido amine)s for non-viral gene delivery

    NARCIS (Netherlands)

    Lin, C.

    2008-01-01

    This thesis describes the design and development of bioreducible poly(amido amine)s as non-viral vectors for gene delivery in vitro and in vivo. The structural influences of these polymers on their physico-chemical properties and gene delivery properties, transfection capability and cytotoxicity in

  7. Use of Transgenic and Mutant Animal Models in the Study of Heterocyclic Amine-induced Mutagenesis and Carcinogenesis

    Science.gov (United States)

    Dashwood, Roderick H.

    2008-01-01

    Heterocyclic amines (HCAs) are potent mutagens generated during the cooking of meat and fish, and several of these compounds produce tumors in conventional experimental animals. During the past 5 years or so, HCAs have been tested in a number of novel in vivo murine models, including the following: lacZ, lacI, cII, c-myc/lacZ, rpsL, and gptΔ transgenics, XPA−/−, XPC−/−, Msh2+/−, Msh2−/− and p53+/− knock-outs, Apc mutant mice (ApcΔ716, Apc1638N, Apcmin), and A33ΔNβ-cat knock-in mice. Several of these models have provided insights into the mutation spectra induced in vivo by HCAs in target and non-target organs for tumorigenesis, as well as demonstrating enhanced susceptibility to HCA-induced tumors and preneoplastic lesions. This review describes several of the more recent reports in which novel animal models were used to examine HCA-induced mutagenesis and carcinogenesis in vivo, including a number of studies which assessed the inhibitory activities of chemopreventive agents such as 1,2-dithiole-3-thione, conjugated linoleic acids, tea, curcumin, chlorophyllin-chitosan, and sulindac. PMID:12542973

  8. Additive scheme for calculation of solvation enthalpies of heterocyclic aromatic compounds. Sublimation/vaporization enthalpy at 298.15 K

    International Nuclear Information System (INIS)

    Solomonov, Boris N.; Nagrimanov, Ruslan N.; Mukhametzyanov, Timur A.

    2016-01-01

    Highlights: • Additivity scheme for solvation enthalpies estimation of heteroaromatic compounds was proposed. • Method for determination of vaporization/sublimation enthalpies directly at 298.15 K was developed. • Solution enthalpies of 25 heteroaromatic compounds were measured. • Vaporization/sublimation enthalpies of 44 heteroaromatic compounds were determined. • Obtained values are in good agreement with the results of conventional methods. - Abstract: Hereby we propose a method for determination of vaporization and sublimation enthalpies of heterocyclic and carbonyl-containing aromatic compounds at 298.15 K. According to this method vaporization and sublimation enthalpies at 298.15 K are determined based on enthalpies of solvation and solution. Solvation enthalpies of heteroatomatic and carbonyl-containing compounds are calculated using an additive scheme from the solvation enthalpy of closest aromatic hydrocarbon and contributions related to the exchange of CH-groups of hydrocarbon with corresponding substituent atoms or groups. Measured solution enthalpies together with calculated solvation enthalpies allowed to calculate corresponding vaporization and sublimation enthalpies at 298.15 K for a large number of heterocyclic and carbonyl-containing compounds. We have also found that in a number of cases instead of solution enthalpy in benzene at 298.15 K fusion enthalpy at the melting temperature can be used. Comparison between literature data and calculated vaporization and sublimation enthalpies demonstrates satisfactory performance of the proposed method.

  9. Additive scheme for calculation of solvation enthalpies of heterocyclic aromatic compounds. Sublimation/vaporization enthalpy at 298.15 K

    Energy Technology Data Exchange (ETDEWEB)

    Solomonov, Boris N., E-mail: boris.solomonov@kpfu.ru; Nagrimanov, Ruslan N.; Mukhametzyanov, Timur A.

    2016-06-10

    Highlights: • Additivity scheme for solvation enthalpies estimation of heteroaromatic compounds was proposed. • Method for determination of vaporization/sublimation enthalpies directly at 298.15 K was developed. • Solution enthalpies of 25 heteroaromatic compounds were measured. • Vaporization/sublimation enthalpies of 44 heteroaromatic compounds were determined. • Obtained values are in good agreement with the results of conventional methods. - Abstract: Hereby we propose a method for determination of vaporization and sublimation enthalpies of heterocyclic and carbonyl-containing aromatic compounds at 298.15 K. According to this method vaporization and sublimation enthalpies at 298.15 K are determined based on enthalpies of solvation and solution. Solvation enthalpies of heteroatomatic and carbonyl-containing compounds are calculated using an additive scheme from the solvation enthalpy of closest aromatic hydrocarbon and contributions related to the exchange of CH-groups of hydrocarbon with corresponding substituent atoms or groups. Measured solution enthalpies together with calculated solvation enthalpies allowed to calculate corresponding vaporization and sublimation enthalpies at 298.15 K for a large number of heterocyclic and carbonyl-containing compounds. We have also found that in a number of cases instead of solution enthalpy in benzene at 298.15 K fusion enthalpy at the melting temperature can be used. Comparison between literature data and calculated vaporization and sublimation enthalpies demonstrates satisfactory performance of the proposed method.

  10. Two-dimensional character of internal rotation of furfural and other five-member heterocyclic aromatic aldehydes

    Science.gov (United States)

    Bataev, Vadim A.; Pupyshev, Vladimir I.; Godunov, Igor A.

    2016-05-01

    The features of nuclear motion corresponding to the rotation of the formyl group (CHO) are studied for the molecules of furfural and some other five-member heterocyclic aromatic aldehydes by the use of MP2/6-311G** quantum chemical approximation. It is demonstrated that the traditional one-dimensional models of internal rotation for the molecules studied have only limited applicability. The reason is the strong kinematic interaction of the rotation of the CHO group and out-of-plane CHO deformation that is realized for the molecules under consideration. The computational procedure based on the two-dimensional approximation is considered for low lying vibrational states as more adequate to the problem.

  11. An etiologic prediction model incorporating biomarkers to predict the bladder cancer risk associated with occupational exposure to aromatic amines: a pilot study.

    Science.gov (United States)

    Mastrangelo, Giuseppe; Carta, Angela; Arici, Cecilia; Pavanello, Sofia; Porru, Stefano

    2017-01-01

    No etiological prediction model incorporating biomarkers is available to predict bladder cancer risk associated with occupational exposure to aromatic amines. Cases were 199 bladder cancer patients. Clinical, laboratory and genetic data were predictors in logistic regression models (full and short) in which the dependent variable was 1 for 15 patients with aromatic amines related bladder cancer and 0 otherwise. The receiver operating characteristics approach was adopted; the area under the curve was used to evaluate discriminatory ability of models. Area under the curve was 0.93 for the full model (including age, smoking and coffee habits, DNA adducts, 12 genotypes) and 0.86 for the short model (including smoking, DNA adducts, 3 genotypes). Using the "best cut-off" of predicted probability of a positive outcome, percentage of cases correctly classified was 92% (full model) against 75% (short model). Cancers classified as "positive outcome" are those to be referred for evaluation by an occupational physician for etiological diagnosis; these patients were 28 (full model) or 60 (short model). Using 3 genotypes instead of 12 can double the number of patients with suspect of aromatic amine related cancer, thus increasing costs of etiologic appraisal. Integrating clinical, laboratory and genetic factors, we developed the first etiologic prediction model for aromatic amine related bladder cancer. Discriminatory ability was excellent, particularly for the full model, allowing individualized predictions. Validation of our model in external populations is essential for practical use in the clinical setting.

  12. U.S. dietary exposures to heterocyclic amines.

    Science.gov (United States)

    Bogen, K T; Keating, G A

    2001-01-01

    Heterocyclic amines (HAs) formed in fried, broiled or grilled meats are potent mutagens that increase rates of colon, mammary, prostate and other cancers in bioassay rodents. Studies of how human dietary HA exposures may affect cancer risks have so far relied on fairly crudely defined HA-exposure categories. Recently, an integrated, quantitative approach to HA-exposure assessment (HAEA) was developed to estimate compound-specific intakes for particular individuals based on corresponding HA-concentration estimates that reflect their meat-type, intake-rate, cooking-method and meat-doneness preferences. This method was applied in the present study to U.S. national Continuing Survey of Food Intakes by Individuals (CSFII) data on meats consumed and cooking methods used by >25,000 people, after adjusting for underreported energy intake and conditional on meat-doneness preferences estimated from additional survey data. The U.S. population average lifetime time-weighted average of total HAs consumed was estimated to be approximately 9 ng/kg/day, with 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) estimated to comprise about two thirds of this intake. Pan-fried meats were the largest source of HA in the diet and chicken the largest source of HAs among different meat types. Estimated total HA intakes by male vs. female children were generally similar, with those by (0- to 15-year-old) children approximately 25% greater than those by (16+-year-old) adults. Race-, age- and sex-specific mean HA intakes were estimated to be greatest for African American males, who were estimated to consume approximately 2- and approximately 3-fold more PhIP than white males at ages <16 and 30+ years, respectively, after considering a relatively greater preference for more well-done items among African Americans based on national survey data. This difference in PhIP intakes may at least partly explain why prostate cancer (PC) kills approximately 2-fold more African American than white men

  13. Impact of Precursors Creatine, Creatinine, and Glucose on the Formation of Heterocyclic Aromatic Amines in Grilled Patties of Various Animal Species.

    Science.gov (United States)

    Gibis, Monika; Weiss, Jochen

    2015-11-01

    The impact of precursors such as creatine, creatinine, and glucose on the formation of mutagenic/carcinogenic heterocyclic amines (HAs) were studied in patties of 9 different animal species equally heat treated with a double-plate contact grill. All grilled patties of the various species (veal, beef, pork, lamb, horse, venison, turkey, chicken, ostrich) contained several HAs such as MeIQx (2-amino-3,8-dimethylimidazo[4,5-f] quinoxaline; 0.5-1.4 ng/g), 4,8-DiMeIQx (2-amino-3,4,8-trimethylimidazo[4,5-f] quinoxaline, 0 to 1.3 ng/g), PhIP (2-amino-1-methyl-6-phenylimidazo[4,5-b] pyridine, 1.2 to 10.5 ng/g), harman (1-methyl-9H-pyrido[3,4-b] indole; 0.5 to 3.2 ng/g), and/or norharman (9H-pyrido[3,4-b]indole 0.5 to 1.9 ng/g). Residual glycogen (glucose) content varied greatly from 0.07 to 1.46 wt% on a dry matter (DM) basis. Total creatin(in)e content in raw meat (1.36 to 2.0 wt% DM) hardly differed between species, except in turkey and ostrich (1.1 wt% DM). Chicken contained, compared to all other species, very low concentrations of glucose (0.07 wt% DM) and the highest levels of nonprotein nitrogen compounds. The free amino acids lysine (r = 0.77, P creatin(in)e to glucose, respectively. Harman as co-mutagens was linearly correlated to the concentration of glucose (r = 0.65, P < 0.001). By contrast, norharman was not significant correlated to glucose levels. © 2015 Institute of Food Technologists®

  14. Mineralization of polycyclic and n-heterocyclic aromatic compounds in hydrocarbon-contaminated soils

    International Nuclear Information System (INIS)

    Grosser, R.J.; Warshawsky, D.; Vestal, J.R.

    1995-01-01

    The comparative mineralization of eight polycyclic aromatic compounds in five soils collected from an abandoned coal tar refinery in eastern Ohio was determined. The soils showed differences only in total extractable hydrocarbon content of the soil chemical characteristics measured. The compounds studied included five polycyclic aromatic hydrocarbons (phenanthrene, anthracene, pyrene, and carcinogenic benz[a]anthracene and benzo[a]pyrene) and three N-heterocyclic aromatics (9H-carbazole, and carcinogenic 7H-dibenzo[c,g]carbazole and dibenz[a,j]acridine). Mineralization was measured by serum bottle radiorespirometry. Only phenanthrene, anthracene, pyrene, benz[a]anthracene, and carbazole were mineralized in the soils after 64 d. Two of the soils with eight to 15 times the hexane -extractable hydrocarbon content consistently showed more rapid initial rates and higher overall extents of mineralization compared to the other three soils. Overall extents of mineralization ranged from 38 to 55% for phenanthrene, 10 to 60% for anthracene, 25 to 70% for pyrene, background to 40% for benz[a]anthracene, and 25 to 50% for carbazole after 64 d. Extents of mineralization by indigenous soil microbiota appear to be more dependent on the chemical characteristics of the soil and not soil total biomass and activity. Cultures capable of degrading phenanthrene, anthracene, and pyrene were obtained following enrichment techniques. A Mycobacterium sp. capable of degrading these three compounds was isolated and reintroduced into two of the soils, resulting in mineralization enhanced above that of the indigenous soil microbial population. These data indicate that the future success of bioremediation methods relies on the characterization of environmental parameters affecting microbial degradation as well as the isolation of microbial populations that can reduce toxicity in the environment

  15. Design, synthesis and evaluation of aromatic heterocyclic derivatives as potent antifungal agents.

    Science.gov (United States)

    Zhao, Shizhen; Zhang, Xiangqian; Wei, Peng; Su, Xin; Zhao, Liyu; Wu, Mengya; Hao, Chenzhou; Liu, Chunchi; Zhao, Dongmei; Cheng, Maosheng

    2017-09-08

    To further enhance the anti-Aspergillus efficacy of our previously discovered antifungal lead compounds (1), a series of aromatic heterocyclic derivatives were designed, synthesized and evaluated for in vitro antifungal activity. Many of the target compounds showed good inhibitory activity against Candida albicans and Cryptococcus neoformans. In particular, the isoxazole nuclei were more suited for improving the activity against Aspergillus spp. Among these compounds, 2-F substituted analogues 23g and 23h displayed the most remarkable in vitro activity against Candida spp., C. neoformans, A. fumigatus and fluconazole-resistant C.alb. strains, which is superior or comparable to the activity of the reference drugs fluconazole and voriconazole. Notably, the compounds 23g and 23h exhibited low inhibition profiles for various isoforms of human cytochrome P450 and excellent blood plasma stability. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  16. Bladder cancer mortality of workers exposed to aromatic amines: a 58-year follow-up.

    Science.gov (United States)

    Pira, Enrico; Piolatto, Giorgio; Negri, Eva; Romano, Canzio; Boffetta, Paolo; Lipworth, Loren; McLaughlin, Joseph K; La Vecchia, Carlo

    2010-07-21

    We previously investigated bladder cancer risk in a cohort of dyestuff workers who were heavily exposed to aromatic amines from 1922 through 1972. We updated the follow-up by 14 years (through 2003) for 590 exposed workers to include more than 30 years of follow-up since last exposure to aromatic amines. Expected numbers of deaths from bladder cancer and other causes were computed by use of national mortality rates from 1951 to 1980 and regional mortality rates subsequently. There were 394 deaths, compared with 262.7 expected (standardized mortality ratio = 1.50, 95% confidence interval = 1.36 to 1.66). Overall, 56 deaths from bladder cancer were observed, compared with 3.4 expected (standardized mortality ratio = 16.5, 95% confidence interval = 12.4 to 21.4). The standardized mortality ratio for bladder cancer increased with younger age at first exposure and increasing duration of exposure. Although the standardized mortality ratio for bladder cancer steadily decreased with time since exposure stopped, the absolute risk remained approximately constant at 3.5 deaths per 1000 man-years up to 29 years after exposure stopped. Excess risk was apparent 30 years or more after last exposure.

  17. Impact of biogenic amine molecular weight and structure on surfactant adsorption at the air-water interface.

    Science.gov (United States)

    Penfold, Jeffrey; Thomas, Robert K; Li, Peixun

    2016-02-01

    The oligoamines, such as ethylenediamine to pentaethylenetetramine, and the aliphatic biogenic amines, such as putrescine, spermidine and spermine, strongly interact with anionic surfactants, such as sodium dodecylsulfate, SDS. It has been shown that this results in pronounced surfactant adsorption at the air-water interface and the transition from monolayer to multilayer adsorption which depends upon solution pH and oligoamine structure. In the neutron reflectivity, NR, and surface tension, ST, results presented here the role of the oligoamine structure on the adsorption of SDS is investigated more fully using a range of different biogenic amines. The effect of the extent of the intra-molecular spacing between amine groups on the adsorption has been extended by comparing results for cadavarine with putrescine and ethylenediamine. The impact of more complex biogenic amine structures on the adsorption has been investigated with the aromatic phenethylamine, and the heterocyclic amines histamine and melamine. The results provide an important insight into how surfactant adsorption at interfaces can be manipulated by the addition of biogenic amines, and into the role of solution pH and oligoamine structure in modifying the interaction between the surfactant and oligoamine. The results impact greatly upon potential applications and in understanding some of the important biological functions of biogenic amines. Copyright © 2015 Elsevier Inc. All rights reserved.

  18. Malaria parasite carbonic anhydrase: inhibition of aromatic/heterocyclic sulfonamides and its therapeutic potential

    Science.gov (United States)

    Krungkrai, Sudaratana R; Krungkrai, Jerapan

    2011-01-01

    Plasmodium falciparum (P. falciparum) is responsible for the majority of life-threatening cases of human malaria, causing 1.5-2.7 million annual deaths. The global emergence of drug-resistant malaria parasites necessitates identification and characterization of novel drug targets and their potential inhibitors. We identified the carbonic anhydrase (CA) genes in P. falciparum. The pfCA gene encodes anα-carbonic anhydrase, a Zn2+-metalloenzme, possessing catalytic properties distinct from that of the human host CA enzyme. The amino acid sequence of the pfCA enzyme is different from the analogous protozoan and human enzymes. A library of aromatic/heterocyclic sulfonamides possessing a large diversity of scaffolds were found to be very good inhibitors for the malarial enzyme at moderate-low micromolar and submicromolar inhibitions. The structure of the groups substituting the aromatic-ureido- or aromatic-azomethine fragment of the molecule and the length of the parent sulfonamide were critical parameters for the inhibitory properties of the sulfonamides. One derivative, that is, 4- (3, 4-dichlorophenylureido)thioureido-benzenesulfonamide (compound 10) was the most effective in vitro Plasmodium falciparum CA inhibitor, and was also the most effective antimalarial compound on the in vitro P. falciparum growth inhibition. The compound 10 was also effective in vivo antimalarial agent in mice infected with Plasmodium berghei, an animal model of drug testing for human malaria infection. It is therefore concluded that the sulphonamide inhibitors targeting the parasite CA may have potential for the development of novel therapies against human malaria. PMID:23569766

  19. The effect of green tea and olive oil on the mutagenic activity of heterocyclic amines extracted from common food consumed in Saudi Arabia.

    Science.gov (United States)

    Awney, Hala

    2011-05-01

    The effect of green tea (GT) and green tea with olive oil (GT+OL) as antioxidants on the formation and mutagenic activity of heterocyclic aromatic amines (HCAs) extracted from beef shawerma, grilled chicken and fried beef liver was examined. HCAs were extracted by blue rayon, analyzed as spiked and unspiked samples with high-performance liquid chromatography and its mutagenic response was assessed by Sallmonela typhimurium 100 in the Ames test. Surprisingly, GT and GT+OL augmented HCAs measured in beef shawerma and grilled chicken but total HCAs measured in GT+OL were less than GT treatment. Both treatments altered the HCA profile as imidazoquinoline type became the most abundant. In control and GT+OL fried beef liver no HCAs were detected, but Trp-P1 was detected in GT treatment. Generally, the mutagenic response of HCAs measured in GT+OL was less than GT in beef shawerma and grilled chicken. However, the mutagenic response of control and 2% GT+OL fried liver was negative. These data suggest that GT concentrations used in this study may induce free radical formation during the Millared reaction due to its pro-oxidative effect, which augmented the HCAs formed and its mutagenic response. In order to optimize both safety and quality of our diets, more need to be done to fully understand the risk of HCAs in food.

  20. Quaternary ammonium-functionalized silica sorbents for the solid-phase extraction of aromatic amines under normal phase conditions.

    Science.gov (United States)

    Vidal, Lorena; Robin, Orlane; Parshintsev, Jevgeni; Mikkola, Jyri-Pekka; Riekkola, Marja-Liisa

    2013-04-12

    Quaternary ammonium-functionalized silica materials were synthesized and applied for solid-phase extraction (SPE) of aromatic amines, which are classified as priority pollutants by US Environmental Protection Agency. Hexamethylenetetramine used for silica surface modification for the first time was employed as SPE sorbent under normal phase conditions. Hexaminium-functionalized silica demonstrated excellent extraction efficiencies for o-toluidine, 4-ethylaniline and quinoline (recoveries 101-107%), while for N,N-dimethylaniline and N-isopropylaniline recoveries were from low to moderate (14-46%). In addition, the suitability of 1-alkyl-3-(propyl-3-sulfonate) imidazolium-functionalized silica as SPE sorbent was tested under normal phase conditions. The recoveries achieved for the five aromatic amines ranged from 89 to 99%. The stability of the sorbent was evaluated during and after 150 extractions. Coefficients of variation between 4.5 and 10.2% proved a high stability of the synthesized sorbent. Elution was carried out using acetonitrile in the case of hexaminium-functionalized silica and water for 1-alkyl-3-(propyl-3-sulfonate) imidazolium-functionalized silica sorbent. After the extraction the analytes were separated and detected by liquid chromatography ultraviolet detection (LC-UV). The retention mechanism of the materials was primarily based on polar hydrogen bonding and π-π interactions. Comparison made with activated silica proved the quaternary ammonium-functionalized materials to offer different selectivity and better extraction efficiencies for aromatic amines. Finally, 1-alkyl-3-(propyl-3-sulfonate) imidazolium-functionalized silica sorbent was successfully tested for the extraction of wastewater and soil samples. Copyright © 2013 Elsevier B.V. All rights reserved.

  1. Primary aromatic amines (PAAs) in black nylon and other food-contact materials, 2004-2009

    DEFF Research Database (Denmark)

    Trier, Xenia Thorsager; Okholm, B.; Foverskov, Annie

    2010-01-01

    Primary aromatic amines (PAAs) were analysed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) in migrates from 234 samples of food-contact materials, including black nylon (polyamide) kitchen utensils (n = 136), coloured plastics (28), and clear/printed multilayer film/laminates (41......), from retailers, importers, and food producers. A further 29 utensils in use were obtained from colleagues. Very high PAA migration was found from black nylon kitchen utensils to the food simulant 3% acetic acid: the 'non-detectable' limit (20 mu g aniline equivalents kg-1 food) was exceeded by up...... migration test conditions influenced the final test results. Long-term release of PAAs was fitted by diffusion modelling experiments and long-term release was also seen as expected from used utensils. Toxicologists consider these migration levels of the suspected carcinogenic PAAs as a problem of major...

  2. Identification of metabolites in urine and feces from rats dosed with the heterocyclic amine, 2-amino-3-methyl-9H-pyrido[2,3-b]indole (MeA alpha C)

    DEFF Research Database (Denmark)

    Frederiksen, H.; Frandsen, Henrik Lauritz

    2004-01-01

    2-Amino-3-methyl-9H-pyrido[2,3-b]indole (MeAalphaC) is a proximate mutagenic and carcinogenic heterocyclic amine formed during ordinary cooking. In model systems, MeAalphaC can be formed by pyrolyses of either tryptophan or proteins of animal or vegetable origin. In the present study, the in vivo...

  3. Highly efficient blue OLEDs based on diphenylaminofluorenylstyrenes end-capped with heterocyclic aromatics

    Energy Technology Data Exchange (ETDEWEB)

    Oh, Suhyun [Department of Chemistry, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of); Lee, Kum Hee; Kim, Young Kwan [Department of Information Display, Hongik University, Seoul 121-791 (Korea, Republic of); Yoon, Seung Soo, E-mail: ssyoon@skku.edu [Department of Chemistry, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of)

    2012-10-15

    In this paper, we have designed four diphenylaminofluorenylstyrene derivatives end-capped with heterocyclic aromatic groups, such as 9-phenylcabazole, 4-dibenzofuran, 2-benzoxazole, 2-quinoxaline, respectively. These materials showed blue to red fluorescence with maximum emission wavelengths of 476–611 nm, respectively, which were dependent on the structural and electronic nature of end-capping groups. To explore the electroluminescent properties of these materials, multilayer OLEDs were fabricated in the following sequence: ITO/DNTPD (40 nm)/NPB (20 nm)/2% doped in MADN (20 nm)/Alq{sub 3} (40 nm)/Liq. (1 nm)/Al. Among those, a device exhibited a highly efficient blue emission with the maximum luminance of 14,480 cd/m{sup 2} at 9 V, the luminous efficiency of 5.38 cd/A at 20 mA/cm{sup 2}, power efficiency of 2.77 lm/W at 20 mA/cm{sup 2}, and CIE{sub x,y} coordinates of (0.147, 0.152) at 8 V, respectively.

  4. Accumulation of 19 environmental phenolic and xenobiotic heterocyclic aromatic compounds in human adipose tissue.

    Science.gov (United States)

    Wang, Lei; Asimakopoulos, Alexandros G; Kannan, Kurunthachalam

    2015-05-01

    The extensive use of environmental phenols (e.g., bisphenol A) and heterocyclic aromatic compounds (e.g., benzothiazole) in consumer products as well as widespread exposure of humans to these compounds have been well documented. Biomonitoring studies have used urinary measurements to assess exposures, based on the assumption that these chemicals are metabolized and eliminated in urine. Despite the fact that some of these chemicals are moderately lipophilic, the extent of their accumulation in adipose fat tissues has not been convincingly demonstrated. In this study, human adipose fat samples (N=20) collected from New York City, USA, were analyzed for the presence of environmental phenols, including bisphenol A (BPA), benzophenone-3 (BP-3), triclosan (TCS), and parabens, as well as heterocyclic aromatic compounds, including benzotriazole (BTR), benzothiazole (BTH), and their derivatives. BPA and TCS were frequently detected in adipose tissues at concentrations (geometric mean [GM]: 3.95ng/g wet wt for BPA and 7.21ng/g wet wt for TCS) similar to or below the values reported for human urine. High concentrations of BP-3 were found in human adipose tissues (GM: 43.4; maximum: 4940ng/g wet wt) and a positive correlation between BP-3 concentrations and donor's age was observed. The metabolite of parabens, p-hydroxybenzoic acid (p-HB), also was found at elevated levels (GM: 4160; max.: 17,400ng/g wet wt) and a positive correlation between donor's age and sum concentration of parabens and p-HB were found. The GM concentrations of BTR and BTH in human adipose tissues were below 1ng/g, although the methylated forms of BTR (i.e., TTR and XTR) and the hydrated form of BTH (i.e., 2-OH-BTH) were frequently detected in adipose samples, indicating widespread exposure to these compounds. Our results suggest that adipose tissue is an important repository for BP-3 and parabens, including p-HB, in the human body. Copyright © 2015 Elsevier Ltd. All rights reserved.

  5. Cancer mortality and occupational exposure to aromatic amines and inhalable aerosols in rubber tire manufacturing in Poland.

    NARCIS (Netherlands)

    de Vocht, F.; Sobala, W.; Wilczynska, U.; Kromhout, H.; Szeszenia-Dabrowska, N.; Peplonska, B.

    2009-01-01

    AIM: Most data on carcinogenic risk in the rubber industry are based on data from Western countries. This study assessed cancer risks in a retrospective cohort in a Polish tire manufacturing plant, relying on quantified exposure to inhalable aerosols and aromatic amines instead of job titles or

  6. Development of four-component synthesis of tetra- and pentasubstituted polyfunctional dihydropyrroles: free permutation and combination of aromatic and aliphatic amines.

    Science.gov (United States)

    Lv, Longyun; Zheng, Sichao; Cai, Xiaotie; Chen, Zhipeng; Zhu, Qiuhua; Liu, Shuwen

    2013-04-08

    We previously reported the novel efficient proton/heat-promoted four-component reactions (4CRs) of but-2-ynedioates, two same/different primary amines, and aldehydes for the synthesis of tetra- and pentasubstituted polyfunctional dihydropyrroles. If aromatic and aliphatic amines were used as reagents, four different series of products should be obtained via the permutation and combination of aromatic and aliphatic primary amines. However, only three/two rather four different series of tetra-/pentasubstisuted dihydropyrroles could be prepared via the proton/heat-promoted 4CRs. Herein, Cu(OAc)2·H2O, a Lewis acid being stable in air and water, was found to be an efficient catalyst for the 4CR synthesis of all the four different series of tetra-/pentasubstisuted dihydropyrroles. The copper-catalyzed 4CR could produce target products at room temperature in good to excellent yields. Interestingly, benzaldehyde, in addition to being used as a useful reactant for the synthesis of pentasubstituted dihydropyrroles, was found to be an excellent additive for preventing the oxidation of aromatic amines with copper(II) and ensuring the sooth conduct of the 4CRs for the synthesis of tetrasubstituted dihydropyrroles with aryl R(3). In addition, salicylic acid was found to be needed to increase the activities and yields of the copper-catalyzed 4CRs for the synthesis of petasubstituted diyhydropyrroles. On the basis of experimental results, the enamination/amidation/intramolecular cyclization mechanism was proposed and amidation is expected to be the rate-limited step in the copper-catalyzed 4CRs.

  7. Aerobic sludge granulation for simultaneous anaerobic decolorization and aerobic aromatic amines mineralization for azo dye wastewater treatment.

    Science.gov (United States)

    Yan, Lawrence K Q; Fung, Ka Y; Ng, Ka M

    2018-06-01

    In this study, the capability of using aerobic granules to undergo simultaneous anaerobic decolorization and aerobic aromatic amines degradation was demonstrated for azo dye wastewater treatment. An integrated acclimation-granulation process was devised, with Mordant Orange 1 as the model pollutant. Performance tests were carried out in a batch column reactor to evaluate the effect of various operating parameters. The optimal condition was to use 1.0-1.7 mm (1.51 ± 0.33 mm) granules, 5 g/L biomass, and 4000 mg/L organics as nutrient; and supplement the wastewater with 1  mg/L dissolved oxygen. This led to a dye mineralization of 61 ± 2%, an anaerobic dye removal of 88 ± 1%, and an aerobic aromatic amines removal of 70 ± 3% within 48 h. This study showed that simultaneous anaerobic/aerobic process by aerobic granules could be a possible alternative to the conventional activated sludge process.

  8. Absolute fragmentation cross sections in atom-molecule collisions: Scaling laws for non-statistical fragmentation of polycyclic aromatic hydrocarbon molecules

    Energy Technology Data Exchange (ETDEWEB)

    Chen, T.; Gatchell, M.; Stockett, M. H.; Alexander, J. D.; Schmidt, H. T.; Cederquist, H.; Zettergren, H., E-mail: henning@fysik.su.se [Department of Physics, Stockholm University, S-106 91 Stockholm (Sweden); Zhang, Y. [Department of Mathematics, Faculty of Physics, M. V. Lomonosov Moscow State University, Leninskie Gory, 119991 Moscow (Russian Federation); Rousseau, P.; Maclot, S.; Delaunay, R.; Adoui, L. [CIMAP, UMR 6252, CEA/CNRS/ENSICAEN/Université de Caen Basse-Normandie, bd Henri Becquerel, BP 5133, F-14070 Caen Cedex 05 (France); Université de Caen Basse-Normandie, Esplanade de la Paix, F-14032 Caen (France); Domaracka, A.; Huber, B. A. [CIMAP, UMR 6252, CEA/CNRS/ENSICAEN/Université de Caen Basse-Normandie, bd Henri Becquerel, BP 5133, F-14070 Caen Cedex 05 (France); Schlathölter, T. [Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747AG Groningen (Netherlands)

    2014-06-14

    We present scaling laws for absolute cross sections for non-statistical fragmentation in collisions between Polycyclic Aromatic Hydrocarbons (PAH/PAH{sup +}) and hydrogen or helium atoms with kinetic energies ranging from 50 eV to 10 keV. Further, we calculate the total fragmentation cross sections (including statistical fragmentation) for 110 eV PAH/PAH{sup +} + He collisions, and show that they compare well with experimental results. We demonstrate that non-statistical fragmentation becomes dominant for large PAHs and that it yields highly reactive fragments forming strong covalent bonds with atoms (H and N) and molecules (C{sub 6}H{sub 5}). Thus nonstatistical fragmentation may be an effective initial step in the formation of, e.g., Polycyclic Aromatic Nitrogen Heterocycles (PANHs). This relates to recent discussions on the evolution of PAHNs in space and the reactivities of defect graphene structures.

  9. Knock-Limited Power Outputs from a CFR Engine Using Internal Coolants. 3; Four Alkyl Amines, Three Alkanolamines, Six Amides, and Eight Heterocyclic Compounds

    Science.gov (United States)

    Imming, Harry S.; Bellman, Donald R.

    1947-01-01

    An investigation of the antiknock effectiveness of various additive-water solutions when used as internal coolants has been conducted at the NACA Cleveland laboratory. Nine compounds have been previously run in a CFR engine and the results are presented. In an effort to find a good anti-knock-coolant additive with more desirable physical properties than those of the nine compounds previously investigated, water solutions of four alkyl amines, three alkanolamines, six amides, and eight heterocyclic compounds were investigated and the results are presented.

  10. Laboratory Studies of Stabilities of Heterocyclic Aromatic Molecules: Suggested Gas Phase Ion-Molecule Routes to Production in Interstellar Gas Clouds

    Science.gov (United States)

    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.

  11. Analysis of primary aromatic amines (PAA) in black nylon kitchenware 2014

    DEFF Research Database (Denmark)

    Trier, Xenia; Granby, Kit

    is 0,01 mg of substance per kg of food or food simulant. The detection limit applies to the sum of primary aromatic amines released’ Since July 1st 2011, an additional EU regulation has come into place, which states that each consignment of polyamide (nylon) kitchen utensils from China and Hong Kong......% acetic acid as food simulant at an exposure temperature of 100°C and time from ½-4 hours, depending on the foreseeable use of the utensil. The samples were collected by the Norwegian Food Safety Authority at importers and retail shops. Of the 20 PAAs analysed. four PAAs were detected, being aniline (ANL...

  12. Solvent-free functionalization of carbon nanotube buckypaper with amines

    International Nuclear Information System (INIS)

    Basiuk, Elena V.; Ramírez-Calera, Itzel J.; Meza-Laguna, Victor; Abarca-Morales, Edgar; Pérez-Rey, Luis A.; Re, Marilena; Prete, Paola; Lovergine, Nico

    2015-01-01

    Graphical abstract: - Abstract: We demonstrate the possibility of fast and efficient solvent-free functionalization of buckypaper (BP) mats prefabricated from oxidized multiwalled carbon nanotubes (MWCNTs-ox), by using three representative amines of different structure: one monofunctional aliphatic amine, octadecylamine (ODA), one monofunctional aromatic amine, 1-aminopyrene (AP), and one aromatic diamine, 1,5-diaminonaphthalene (DAN). The functionalization procedure, which relies on the formation of amide bonds with carboxylic groups of MWCNTs-ox, is performed at 150–180 °C under reduced pressure and takes about 4 h including auxiliary degassing. The amine-treated BP samples (BP-ODA, BP-AP and BP-DAN, respectively) were characterized by means of a variety of analytical techniques such as Fourier-transform infrared and Raman spectroscopy, thermogravimetric and differential thermal analysis, scanning and transmission electron microscopy, scanning helium ion microscopy, and atomic force microscopy. The highest amine content was found for BP-ODA, and the lowest one was observed for BP-DAN, with a possible contribution of non-covalently bonded amine molecules in all three cases. Despite of some differences in spectral and morphological characteristics for amine-functionalized BP samples, they have in common a dramatically increased stability in water as compared to pristine BP and, on the other hand, a relatively invariable electrical conductivity.

  13. Two-dimensional character of internal rotation of furfural and other five-member heterocyclic aromatic aldehydes.

    Science.gov (United States)

    Bataev, Vadim A; Pupyshev, Vladimir I; Godunov, Igor A

    2016-05-15

    The features of nuclear motion corresponding to the rotation of the formyl group (CHO) are studied for the molecules of furfural and some other five-member heterocyclic aromatic aldehydes by the use of MP2/6-311G** quantum chemical approximation. It is demonstrated that the traditional one-dimensional models of internal rotation for the molecules studied have only limited applicability. The reason is the strong kinematic interaction of the rotation of the CHO group and out-of-plane CHO deformation that is realized for the molecules under consideration. The computational procedure based on the two-dimensional approximation is considered for low lying vibrational states as more adequate to the problem. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. N,S,O-Heterocycles in Aged Champagne Reserve Wines and Correlation with Free Amino Acid Concentrations.

    Science.gov (United States)

    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.

  15. Mechanochemical synthesis and structural characterization of three novel cocrystals of dimethylglyoxime with N-heterocyclic aromatic compounds and acetamide

    Science.gov (United States)

    Abidi, Syed Sibte Asghar; Azim, Yasser; Gupta, Abhishek Kumar; Pradeep, Chullikkattil P.

    2017-12-01

    With an aim to explore the interactions of (RR'Cdbnd Nsbnd OH) oxime moiety of dimethylglyoxime (DMG) with pyridyl ring of N-heterocyclic aromatic compounds and acetamide, three novel cocrystals of dimethylglyoxime with acridine (ACR), 1,10-phenanthroline monohydrate (PT) and acetamide (ACT) are reported. These three cocrystals were obtained with a mechanochemical synthesis approach and were characterized by single crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), fourier transform-infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Additionally, Hirshfeld surface analysis is used to investigate the intermolecular interaction and the crystal packing of cocrystals.

  16. Water purification by reverse osmosis using heterocyclic polymer membranes

    Science.gov (United States)

    Scott, H.

    1972-01-01

    Pyrrone (polyimidazopyrrolone) polymers are a new class of thermally stable, radiation and chemical resistant aromatic-heterocyclic polymers featuring a greater chemical and mechanical durability than cellulose acetate.

  17. Simultaneous determination of various aromatic amines and metabolites of aromatic nitro compounds in urine for low level exposure using gas chromatography-mass spectrometry.

    Science.gov (United States)

    Weiss, Tobias; Angerer, Jürgen

    2002-10-05

    A newly developed method permits the simultaneous quantitative determination of various aromatic amines (or metabolites of aromatic nitro compounds, respectively) in human urine in one analytical run. Applying this method it is possible to determine aniline, toluidines, 4-isopropylaniline, o-anisidine, 3- and 4-chloroaniline, 4-bromoaniline, aminonitrotoluenes, aminodinitrotoluenes, 3,5- and 3,4-dichloroaniline, alpha- and beta-naphtylamine and 4-aminodiphenyl. After separation from the urinary matrix by a simple liquid-liquid extraction at pH 6.2-6.4 the analytes are converted into their pentafluoropropionic acid amides. Separation and quantitative analysis is carried out by capillary gas chromatography and mass-selective detection in the single ion monitoring mode. The limits of detection were within the range from 0.05 microg/l (4-aminobiphenyl, o-anisidine, 3,5-dichloroaniline) to 2 microg/l urine (4-amino-2,6-dinitrotoluene). The relative standard deviation of the within-series imprecision (determined at spiked concentrations of 2.0 microg/l and 10 microg/l) was between 2.9 and 13.6% depending on analyte and concentration. The relative recovery rates were in the range of 70-121%. The analytes that do not contain a nitro function showed better performance regarding the analytical reliability criteria. In order to determine the suitability of this new method for biological monitoring we analysed 20 12-h urine samples of persons without known exposure to aromatic amines, nitroaromatics or precursors in a pilot study. In these samples various aromatic amines could be clearly identified. The general population renally excretes aniline (median: 3.5 microg/l; 95th percentile: 7.9 microg/l), o- (0.12 microg/l; 2.7 microg/l), m- (0.17 microg/l; 2.2 microg/l) and p-toluidine (0.11 microg/l; 0.43 microg/l), and o-anisidine (0.22 microg/l; 0.68 microg/l). Additionally, we found that the persons investigated also excrete 3- (<0.05 microg/l; 0.55 microg/l) and 4

  18. Specific determination of 20 primary aromatic amines in aqueous food simulants by liquid chromatography-electrospray ionization-tandem mass spectrometry

    DEFF Research Database (Denmark)

    Mortensen, Sarah Kelly; Trier, Xenia Thorsager; Foverskov, Annie

    2005-01-01

    A multi-analyte method without any pre-treatment steps using reversed-phase liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) was developed and applied for the determination of 20 primary aromatic amines (PAA) associated with polyurethane (PUR) products or azo...

  19. Thermometric titrations of amines with nitrosyl perchlorate in acetonitrile solvent.

    Science.gov (United States)

    Gündüz, T; Kiliç, E; Cakirer, O

    1996-05-01

    Thirteen aliphatic and four aromatic amines, namely diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n-butylamine, isopropylamine, di-isopropylamine, n-butylamine, di-n-butylamine, tri-n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, aniline, N,N-dimethylaniline, 2-nitroaniline and 4-nitroaniline were titrated thermometrically with nitrosyl perchlorate in acetonitrile solvent. All the aliphatic amines gave very well-shaped thermometric titration curves. The calculated recovery values of the amines were very good. In comparison, the aromatic amines, aniline and N,N-dimethylaniline gave rather well-shaped titration curves, but the recovery values were fairly low. 2-Nitro- and 4-nitro anilines gave no thermometric response at all. The heats of reaction of the amines with nitrosyl perchlorate are rather high. However, the average heat of reaction of the aromatic amines is approximately two-thirds that of the average heat of the aliphatic amines. To support this method all the amines were also titrated potentiometrically and very similar results to those obtained with the thermometric method are seen. The nitrosyl ion is a Lewis acid, strong enough to titrate quantitatively aliphatic amines in acetonitrile solvent, but not strong enough to titrate aromatic amines at the required level in the same solvent.

  20. Synthesis,spectroscopic and biological study of 2-(3,3-dimethyl-1-triazeno) benzothiazole and morpholino acetyl-2- aminobenzothiazole derivatives

    International Nuclear Information System (INIS)

    Al-Azawi, A.M.

    1985-01-01

    Generally triazenes are prepared by coupling the diazonium salts of aromatic amines or heterocyclic amines with dimethyl amine or other amines.Primary aromatic amines react with nitrous acid to give diazonium compounds.Diazotization of 2-aminothiazoles and 2-aminobenzothiazoles occurs most readily in concentrated solutions of the oxygencontaining acids,such as sulfuric,perchloric,phosphoric and nitric acid.Diazotization in perchloric acid leads to the formation of diazonium perchlorate without by products.Diazotization takes place equally readily with sulphuric acid but with nitric acid the reaction proceeds less smoothyl owing to the low solubility of 2-aminothiazole nitrate.(11 tabs., 24 figs., 54 refs.)

  1. Comparative analysis of quasi-linear spectra of organic boron compounds and their heterocyclic and aromatic analogs

    International Nuclear Information System (INIS)

    Klimova, L.A.; Volkova, V.P.; Kugemova, M.E.; Mikhajlov, B.M.

    1976-01-01

    Quasiline absorption and luminescence spectra of polycyclic compounds containing boron, nitrogen, or oxygen atoms have been obtained and studied for the first time. Electron-vibrating spectra of these compounds have been compared with the corresponding spectra of nitrogen- and oxygen-containing heterocycles as well as with spectra of their aromatic analog - phenanthrene. Vibrational analysis of the spectra of all the compounds reveals, within the accuracy limit of measurements, the relative closeness of the vibrational frequencies. However, the great difference between the positions of electron transitions points to a change in π-electron structure of the molecules when heteroatoms are introduced. High sensitivity of the frequency of electron transition to structural changes makes it possible to determine the degree of influence of separate heteroatoms

  2. Weathering trend characterization of medium-molecular weight polycyclic aromatic disulfur heterocycles by Fourier transform ion cyclotron resonance mass spectrometry.

    Science.gov (United States)

    Hegazi, Abdelrahman H; Fathalla, Eiman M; Andersson, Jan T

    2014-09-01

    Different weathering factors act to change petroleum composition once it is spilled into the environment. n-Alkanes, biomarkers, low-molecular weight polyaromatic hydrocarbons and sulfur heterocycles compositional changing in the environment have been extensively studied by different researchers and many parameters have been used for oil source identification and monitoring of weathering and biological degradation processes. In this work, we studied the fate of medium-molecular weight polycyclic aromatic disulfur heterocycles (PAS2Hs), up to ca. 900Da, of artificially weathered Flotta North Sea crude oil by ultra high-resolution Fourier transform ion cyclotron resonance mass spectrometry. It was found that PAS2Hs in studied crude oil having double bond equivalents (DBE) from 5 to 8 with a mass range from ca 316 to 582Da were less influenced even after six months artificial weathering experiment. However, compounds having DBEs 12, 11 and 10 were depleted after two, four and six months weathering, respectively. In addition, DBE 9 series was more susceptible to weathering than those of DBE 7 and 8. Copyright © 2014 Elsevier Ltd. All rights reserved.

  3. N- AND O-HETEROCYCLES PRODUCED FROM THE IRRADIATION OF BENZENE AND NAPHTHALENE IN H2O/NH3-CONTAINING ICES

    International Nuclear Information System (INIS)

    Materese, Christopher K.; Nuevo, Michel; Sandford, Scott A.

    2015-01-01

    Aromatic heterocyclic molecules are an important class of molecules of astrophysical and biological significance that include pyridine, pyrimidine, and their derivatives. Such compounds are believed to exist in interstellar and circumstellar environments, though they have never been observed in the gas phase. Regardless of their presence in the gas phase in space, numerous heterocycles have been reported in carbonaceous meteorites, which indicates that they are formed under astrophysical conditions. The experimental work described here shows that N- and O-heterocyclic molecules can form from the ultraviolet (UV) irradiation of the homocyclic aromatic molecules benzene (C 6 H 6 ) or naphthalene (C 10 H 8 ) mixed in ices containing H 2 O and NH 3 . This represents an alternative way to generate aromatic heterocycles to those considered before and may have important implications for astrochemistry and astrobiology

  4. Screening for heterocyclic amines in chicken cooked in various ways.

    Science.gov (United States)

    Solyakov, A; Skog, K

    2002-08-01

    Chicken cooked under well-controlled conditions and commercial chicken products were screened for heterocyclic amines (HAs). Chicken samples were boiled, deep-fried, pan-fried, oven-roasted, cooked in an unglazed clay pot or in a roasting bag in the oven, and oven broiled. 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx), 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline (4,8-DiMeIQx), 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), 1-methyl-9H-pyrido[3,4-b]indole (harman) and 9H-pyrido[3,4-b]indole (norharman) were identified in several samples. Chicken cooked at low temperatures contained low amounts of HAs. In pan-fried chicken breasts, MeIQx was detected in amounts below 2 ng/g, 4,8-DiMeIQx below 0.6 ng/g, and PhIP in amounts up to 38 ng/g. Harman and norharman were detected in almost all samples (below 15 ng/g). In skin from a commercially barbecued chicken, MeIQx, 4,8-DiMeIQx and PhIP were detected, while only traces of MeIQx were detected in the meat. MeIQx was detected in a commercial chicken flavour, 0.1 ng/ml. No HAs were detected in pan-fried chicken liver. The results show that the content of HAs in chicken cooked in various ways is low if prepared at low temperatures, and increases with increasing cooking temperature. PhIP formation seems to start accelerating at cooking temperatures around or above 200 degrees C. Colour development increases with cooking temperature, but no correlation with HA content was observed.

  5. Determination of aromatic amines in aqueous extracts of polyurethane foam using hydrophilic interaction liquid chromatography and mass spectrometry

    International Nuclear Information System (INIS)

    Riddar Johnson, Jakob; Karlsson, Daniel; Dalene, Marianne; Skarping, Gunnar

    2010-01-01

    A method is presented for the determination of aromatic amines in aqueous extracts of polyurethane (PUR) foam. The method is based on the extraction of PUR foam using aqueous acetic acid (0.1%, w/v) followed by determination of extracted aromatic amines using hydrophilic interaction liquid chromatography (HILIC) and tandem mass spectrometry (MS/MS) with positive electrospray ionisation. The injections of volumes up to 5 μL of aqueous solutions were made possible by on-column focusing with partially filled loop injections. The fragmentation patterns for 2,4- and 2,6-toluene diamine (TDA) and 4,4'-methylene dianiline (MDA) were clarified by performing a hydrogen-deuterium exchange study. TDA and MDA were determined using trideuterated 2,4- and 2,6-TDA and dideuterated 4,4'-MDA as internal standards. Linear calibration graphs were obtained over the range 0.025-0.5 μg mL -1 with correlation coefficients >0.996 and the instrumental detection limit for each compound was <50 fmol. The stability of the amines was influenced by the matrix, so their concentrations decreased over time. Agreement was observed between the results of analyses of PUR foam extracts by HILIC-MS/MS and results obtained by ethyl chloroformate derivatisation and reversed phase (RP) liquid chromatography-mass spectrometry (LC-MS/MS). TDA was observed to be unstable in extracts of foam but not in pure solutions.

  6. Some heterocyclic aromatic compounds are Ah receptor agonists in the DR-CALUX assay and the EROD assay with RTL-W1 cells.

    Science.gov (United States)

    Hinger, Gunnar; Brinkmann, Markus; Bluhm, Kerstin; Sagner, Anne; Takner, Helena; Eisenträger, Adolf; Braunbeck, Thomas; Engwall, Magnus; Tiehm, Andreas; Hollert, Henner

    2011-09-01

    Heterocyclic aromatic compounds containing nitrogen, sulfur, or oxygen heteroatoms (NSO-HET) have been detected in air, soil, marine, and freshwater systems. However, only few publications are available investigating NSO-HET using in vitro bioassays. To support better characterization of environmental samples, selected NSO-HET were screened for dioxin-like activity in two bioassays. The present study focuses on the identification and quantification of dioxin-like effects of 12 NSO-HET using the DR-CALUX assay, and the 7-ethoxyresorufin-O-deethylase (EROD) assay with the permanent fish liver cell line RTL-W1. Changes of the total medium compound concentrations during the test procedure due to, e.g., sorption or volatilization were quantified using GC/MS. The NSO-HET benzofuran, 2,3-dimethylbenzofuran, dibenzofuran, dibenzothiophen, acridine, xanthene, and carbazole caused a response in the DR-CALUX assay. Only benzofuran and 2,3-dimethylbenzofuran were also positive in the EROD assay. All other compounds were inactive in the EROD assay. Relative potency (REP) values ranged from (2.80 ± 1.32) · 10(-8) to (3.26 ± 2.03) · 10(-6) in the DR-CALUX and from (3.26 ± 0.91) · 10(-7) to (4.87 ± 1.97) · 10(-7) in the EROD assay. The REP values were comparable to those of larger polycyclic aromatic hydrocarbons, e.g., fluoranthene and pyrene. Thus, and because of the ubiquitous distribution of heterocyclic aromatic compounds in the environment, the provided data will further facilitate the bioanalytical and analytical characterization of environmental samples towards these toxicants.

  7. Formation of heterocyclic amines in Chinese marinated meat: effects of animal species and ingredients (rock candy, soy sauce and rice wine).

    Science.gov (United States)

    Wang, Pan; Hong, Yanting; Ke, Weixin; Hu, Xiaosong; Chen, Fang

    2017-09-01

    Heterocyclic aromatic amines (HAAs) are one type of neo-formed contaminants in protein-rich foods during heat processing. Recently, accumulative studies have focused on the formation of HAs in Western foods. However, there is little knowledge about the occurrence of HAAs in traditional Chinese foods. The objective of this study was to determinate the contents of main HAs in traditional marinated meat products by UPLC-MS/MS, and to investigate the effects of animal species and the ingredients (soy sauce, rock candy, and rice wine) on the formation of HAAs in marinated meats. Five HAs - 2-amino-3-methylimidazo[4,5-f]-quinolone (IQ), 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx), 2-amino-3,4-dimethylimidazo[4,5-f]quinoxaline (MeIQ), 9H-pyrido[3,4-b]indole (Norharman) and l-methyl-9H-pyrido[3,4-b]indole (Harman) - were detected in 12 marinated meats, but 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) was only found in three chicken marinates. The animal species and ingredients (soy sauce, rock candy and rice wine) have significant influence on the formation of HAAs in meat marinates. Beef had the highest content of total HAAs compared with pork, mutton and chicken. Meanwhile, soy sauce contributed to the formation of HAAs more greatly than rock candy, soy sauce, and rice wine. Choice of raw materials and optimisation of ingredients recipe should be become a critical point to control the HAAs formation in marinated meats. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

  8. Cu(OAc)2/TFA-promoted formal [3 + 3] cycloaddition/oxidation of enamines and enones for synthesis of multisubstituted aromatic amines.

    Science.gov (United States)

    Li, Liang; Zhao, Mi-Na; Ren, Zhi-Hui; Li, Jian-Li; Guan, Zheng-Hui

    2012-07-06

    New strategies for the oxidative cycloaddition of enones with enamines are developed. These cycloaddition reactions directly afford substituted aromatic amines, which are important in organic chemistry, in moderate to good yield. Cu(OAc)(2)/TFA is shown to be essential to achieve high reaction efficiency.

  9. Excretion of metabolites in urine and faeces from rats dosed with the heterocyclic amine, 2-amino-9H-pyrido[2,3-b]indole (A alpha C)

    DEFF Research Database (Denmark)

    Frederiksen, H.; Frandsen, Henrik Lauritz

    2004-01-01

    2-amino-9H-pyrido[2,3-b]indole (AalphaC) is a mutagenic and carcinogenic heterocyclic amine formed during ordinary cooking. In model systems AalphaC can be formed by pyrolysing either tryptophan or proteins of animal or vegetable origin. In the present study, the in vivo metabolism of Aalpha....... Any activated metabolites of AalphaC were not detected in rat urine or faeces. In future accumulation or binding of AalphaC to macromolecules such as DNA and proteins has to be studied....

  10. Degradation of phenolics, nitrogen-heterocyclics and polynuclear aromatic hydrocarbons in a rotating biological contactor.

    Science.gov (United States)

    Jeswani, Hansa; Mukherji, Suparna

    2012-05-01

    The degradation of phenolics, heterocyclics and polynuclear aromatic hydrocarbons (PAHs) in a synthetic biomass gasifier wastewater with average COD of 1388 mg/L was studied in a three stage rotating biological contactor (RBC) using the pyrene degrader, Exiguobacterium aurantiacum and activated sludge consortia (1:3 v/v). As the organic loading rate (OLR) was varied from 3.3 to 14 g/m(2)/d, the COD removal ranged from 63.3% to 92.6%. Complete removal of all the constituents was observed at the lowest OLR of 3.3g/m(2)/d. At 24h hydraulic retention time (HRT) and OLR of 6.6g/m(2)/d complete removal of pyridine, quinoline and benzene and 85-96% removal of phenol, naphthalene, phenanthrene, fluoranthene and pyrene was observed. E. aurantiacum was found to be the dominant bacteria in the biofilm. Clark's model provided good fits to data for all the three stages of the RBC. Copyright © 2012 Elsevier Ltd. All rights reserved.

  11. Predictors of dietary heterocyclic amine intake in three prospective cohorts.

    Science.gov (United States)

    Byrne, C; Sinha, R; Platz, E A; Giovannucci, E; Colditz, G A; Hunter, D J; Speizer, F E; Willett, W C

    1998-06-01

    Cooking meat creates heterocyclic amines (HCAs) through pyrolysis of amino acids and creatinine. Although recognized as mutagenic, the etiological role of HCA in human cancer is unclear, due to the lack of information on the effect of typical food cooking methods on HCA concentrations and on variation in HCA exposure in populations. We estimated overall daily dietary HCA intake and variation in intake between individuals, using recent data on HCA concentrations in various meats prepared by cooking methods, temperatures, and times common in United States in the 1990s. Random samples of 250 participants from each of three large prospective cohorts were mailed a questionnaire to assess frequency of consumption, cooking method, and typical outside appearance of pan-fried, broiled, and grilled or barbecued chicken, fish, hamburger, and steak; fried, microwaved, and broiled bacon; fried sausage; roast beef; and homemade gravy. The 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx), 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), and 2-amino-3,4,8-trimethylimidazo[4,5,f]quinoxaline (DiMeIQx) concentrations, measured in composite samples by solid-phase extraction and high-performance liquid chromatography, were assigned to each food, cooking method, and doneness level. The dietary reports showed approximately 30-fold relative variation in 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline intake, 20-fold for 2-amino- -methyl-6-phenylimidazo[4,5-b]pyridine, and over 110-fold for 2-amino-3,4,8-trimethylimidazo[4,5,f]quinoxaline, when the 10th and 90th percentiles of HCA intake were compared (90th/10th percentile value). These reported variations in HCA exposure among participants in these three large cohorts indicates that estimation of HCA intake and determination of association with disease risk are feasible, if additional information on meat cooking methods is obtained.

  12. N- AND O-HETEROCYCLES PRODUCED FROM THE IRRADIATION OF BENZENE AND NAPHTHALENE IN H{sub 2}O/NH{sub 3}-CONTAINING ICES

    Energy Technology Data Exchange (ETDEWEB)

    Materese, Christopher K.; Nuevo, Michel; Sandford, Scott A., E-mail: christopher.k.materese@nasa.gov [NASA Ames Research Center, Moffett Field, CA 94035 (United States)

    2015-02-20

    Aromatic heterocyclic molecules are an important class of molecules of astrophysical and biological significance that include pyridine, pyrimidine, and their derivatives. Such compounds are believed to exist in interstellar and circumstellar environments, though they have never been observed in the gas phase. Regardless of their presence in the gas phase in space, numerous heterocycles have been reported in carbonaceous meteorites, which indicates that they are formed under astrophysical conditions. The experimental work described here shows that N- and O-heterocyclic molecules can form from the ultraviolet (UV) irradiation of the homocyclic aromatic molecules benzene (C{sub 6}H{sub 6}) or naphthalene (C{sub 10}H{sub 8}) mixed in ices containing H{sub 2}O and NH{sub 3}. This represents an alternative way to generate aromatic heterocycles to those considered before and may have important implications for astrochemistry and astrobiology.

  13. Pulse shape discrimination in non-aromatic plastics

    Energy Technology Data Exchange (ETDEWEB)

    Paul Martinez, H.; Pawelczak, Iwona; Glenn, Andrew M.; Leslie Carman, M.; Zaitseva, Natalia; Payne, Stephen

    2015-01-21

    Recently it has been demonstrated that plastic scintillators have the ability to distinguish neutrons from gamma rays by way of pulse shape discrimination (PSD). This discovery has lead to new materials and new capabilities. Here we report our work with the effects of aromatic, non-aromatic, and mixed aromatic/non-aromatic matrices have on the performance of PSD plastic scintillators.

  14. A facile synthesis of substituted 2-alkylquinolines through [3+3] annulation between 3-ethoxycyclobutanones and aromatic amines at room temperature.

    Science.gov (United States)

    Shan, Gang; Sun, Xiuyun; Xia, Qian; Rao, Yu

    2011-11-04

    An efficient single-step approach toward the synthesis of 2-alkylquinolines is described. Through a Lewis acid mediated [3+3] annulation reaction between 3-ethoxycyclobutanones and aromatic amines, a variety of multisubstituted 2-alkylquinoline derivatives were prepared regioselectively at room temperature. © 2011 American Chemical Society

  15. High intake of heterocyclic amines from meat is associated with oxidative stress.

    Science.gov (United States)

    Carvalho, A M; Miranda, A M; Santos, F A; Loureiro, A P M; Fisberg, R M; Marchioni, D M

    2015-04-28

    High meat intake has been related to chronic diseases such as cancer and CVD. One hypothesis is that heterocyclic amines (HCA), which are formed during the cooking process of meat, can generate reactive species. These compounds can cause oxidation of lipids, proteins and DNA, resulting in oxidative stress, cell damage and loss of biological function. This association has been seen in vitro; however, it remains unclear in vivo. The aim of the present study was to investigate the association between oxidative stress and HCA intake, and oxidative stress and meat intake. Data were from the Health Survey for Sao Paulo--ISA-Capital (561 adult and elderly). Food intake was estimated by one 24-h dietary recall (24HR) complemented by a detailed FFQ with preferences of cooking methods and level of doneness for meat. HCA intake was estimated linking the meat from the 24HR to a database of HCA. Oxidative stress was estimated by malondialdehyde (MDA) concentration in the plasma, after derivatisation with thiobarbituric acid and quantification by HPLC/diode array. Analyses were performed using multivariate logistic regressions adjusted for smoking, sex, age, BMI, skin colour, energy intake, fruit and vegetable intake, and physical activity. A positive association between HCA intake and MDA concentration (OR 1·17; 95% CI 1·01, 1·38) was observed, showing that HCA from meat may contribute to increase oxidative stress, and may consequently increase the risk of chronic diseases.

  16. Synthesis and properties of heterocyclic type I photoinitiators

    International Nuclear Information System (INIS)

    Liska, R.; Knaus, S.; Wendrinsky, J.

    1999-01-01

    The synthesis and properties of a series of new heterocyclic hydroxyalkylphenone-analogous photoinitiators (PIs) is described. The PIs are obtained by reaction of aromatic organolithium compounds with nitriles or by Friedel-Craft's-acylation. Preliminary photocalorimetric tests and UV absorption data are included

  17. Synthesis of propargylic and allenic carbamates via the C-H amination of alkynes.

    Science.gov (United States)

    Grigg, R David; Rigoli, Jared W; Pearce, Simon D; Schomaker, Jennifer M

    2012-01-06

    Propargylic amines are important intermediates for the synthesis of nitrogen-containing heterocycles. The insertion of a nitrene into a propargylic C-H bond has not been explored, despite the attention directed toward the Rh-catalyzed amination of other types of C-H bonds. In this communication, the conversion of a series of homopropargylic carbamates to propargylic carbamates and aminated allenes is described. © 2011 American Chemical Society

  18. Effects of different types of soy sauce on the formation of heterocyclic amines in roasted chicken.

    Science.gov (United States)

    Alam Shah, Syifaa; Selamat, Jinap; Haque Akanda, Md Jahurul; Sanny, Maimunah; Khatib, Alfi

    2018-05-01

    The objective of the study was to determine the effect of different types of soy sauce and marinating time on the formation of heterocyclic amines (HCAs) in roasted chicken. Chicken breast samples were marinated with sweet, salty, light and dark soy sauce at 0, 3, 6 and 12 h (control treatment was the chicken without marinade). The concentrations of free amino acids, sugars and creatinine were determined before roasting while HCA concentrations were determined after roasting. All types of soy sauce significantly increased (p ≤ 0.05) the concentration of HCAs in roasted chicken with increasing marinating time. The highest increment of total concentration of HCAs was found in samples marinated with light soy sauce (887%) followed by dark (375%), salty (193%) and sweet (169%) at 12 h. PhIP (2-amino-1-methyl-6-phenylimidazo(4,5-b)pyridine) showed a substantial reduction in samples only momentarily marinated with sweet, salty and dark soy sauce (0 h). Free amino acids were found to be more strongly correlated with the formation of HCAs than reducing sugars or creatinine.

  19. Methods for estimating heterocyclic amine concentrations in cooked meats in the US diet.

    Science.gov (United States)

    Keating, G A; Bogen, K T

    2001-01-01

    Heterocyclic amines (HAs) are formed in numerous cooked foods commonly consumed in the diet. A method was developed to estimate dietary HA levels using HA concentrations in experimentally cooked meats reported in the literature and meat consumption data obtained from a national dietary survey. Cooking variables (meat internal temperature and weight loss, surface temperature and time) were used to develop relationships for estimating total HA concentrations in six meat types. Concentrations of five individual HAs were estimated for specific meat type/cooking method combinations based on linear regression of total and individual HA values obtained from the literature. Using these relationships, total and individual HA concentrations were estimated for 21 meat type/cooking method combinations at four meat doneness levels. Reported consumption of the 21 meat type/cooking method combinations was obtained from a national dietary survey and the age-specific daily HA intake calculated using the estimated HA concentrations (ng/g) and reported meat intakes. Estimated mean daily total HA intakes for children (to age 15 years) and adults (30+ years) were 11 and 7.0 ng/kg/day, respectively, with 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) estimated to comprise approximately 65% of each intake. Pan-fried meats were the largest source of HA in the diet and chicken the largest source of HAs among the different meat types.

  20. Evaluation of a new model system for studying the formation of heterocyclic amines.

    Science.gov (United States)

    Messner, C; Murkovic, M

    2004-03-25

    Heterocyclic amines (HAs) are an important class of food mutagens and carcinogens, which can be found in cooked meat and fish. Increasing heating temperatures and times usually increase mutagenic activity in meat and meat extracts during cooking. We developed a model system, which allows to examine the effects of precursor composition and heating conditions (time and temperature) on the formation of HAs in meat. Homogenized and freeze dried meat samples (beef, pork chops, chicken breast and turkey breast) are heated with diethylene glycol in closed vials under stirring in a thermostated heating block. After an appropriate sample preparation (extraction and clean-up) ten different HAs were measured by HPLC analyses with gradient elution and mass selective detection. The time courses of HA-formation in the different kinds of meat at varying heating temperatures were determined up to heating times of 30 min. 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) was the most abundant HA in these experiments and reached the highest concentrations in the beef meat samples, as did the other HAs (MeIQ, AalphaC) at 220 degrees C in the heating block under stirred conditions. Additionally the influence of the antioxidant TBHQ (t-butylhydroquinone) on the formation of HAs in the model system was tested. However TBHQ effected only slight reductions of HA formation in all kinds of meat.

  1. 2-Amino-1-methyl-6-(5-hydroxy-)phenylimidazo[4,5-b]pyridine (5-OH-PhIP), a biomarker for the genotoxic dose of the heterocyclic amine, 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP)

    DEFF Research Database (Denmark)

    Frandsen, H; Frederiksen, H; Alexander, J

    2002-01-01

    2-Amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) is a mutagenic and carcinogenic heterocyclic amine formed during ordinary cooking. PhIP is metabolically activated by CYP P450 mediated N-hydroxylation followed by phase II esterification. The ultimate mutagenic metabolite reacts with DNA...

  2. Concentration, size distribution and dry deposition of amines in atmospheric particles of urban Guangzhou, China

    Science.gov (United States)

    Liu, Fengxian; Bi, Xinhui; Zhang, Guohua; Peng, Long; Lian, Xiufeng; Lu, Huiying; Fu, Yuzhen; Wang, Xinming; Peng, Ping'an; Sheng, Guoying

    2017-12-01

    Size-segregated PM10 samples were collected in Guangzhou, China during autumn of 2014. Nine amines, including seven aliphatic amines and two heterocyclic amines, were detected using a gas chromatography-mass spectrometer after derivatization by benzenesulfonyl chloride. The total concentration of the nine aminesamines) was 79.6-140.9 ng m-3 in PM10. The most abundant species was methylamine (MA), which had a concentration of 29.2-70.1 ng m-3. MA, dimethylamine (DMA), diethylamine (DEA) and dibutylamine (DBA) were the predominant amines in the samples and accounted for approximately 80% of Ʃamines in each size segment. Two heterocyclic amines, pyrrolidine (PYR) and morpholine (MOR), were detected in all samples and had average concentrations of 1.14 ± 0.37 and 1.89 ± 0.64 ng m-3, respectively, in particles with aerodynamic diameters ammonium ranged from 0.0068 to 0.0107 in particles with diameters <1.5 μm, and the maximum ratio occurred in the smallest particles (diameter< 0.49 μm). The average dry deposition flux and velocity of Ʃamines in PM10 were 7.9 ± 1.6 μg m-2 d-1 and 0.084 ± 0.0021 cm s-1, respectively. The results of this study provide essential information on the contribution of amines to secondary organic aerosols and dry removal mechanisms in urban areas.

  3. Biodegradation of Various Aromatic Compounds by Enriched Bacterial Cultures: Part B--Nitrogen-, Sulfur-, and Oxygen-Containing Heterocyclic Aromatic Compounds.

    Science.gov (United States)

    Oberoi, Akashdeep Singh; Philip, Ligy; Bhallamudi, S Murty

    2015-07-01

    Present study focused on the biodegradation of various heterocyclic nitrogen, sulfur, and oxygen (NSO) compounds using naphthalene-enriched culture. Target compounds in the study were pyridine, quinoline, benzothiophene, and benzofuran. Screening studies were carried out using different microbial consortia enriched with specific polycyclic aromatic hydrocarbon (PAH) and NSO compounds. Among different microbial consortia, naphthalene-enriched culture was the most efficient consortium based on high substrate degradation rate. Substrate degradation rate with naphthalene-enriched culture followed the order pyridine > quinoline > benzofuran > benzothiophene. Benzothiophene and benzofuran were found to be highly recalcitrant pollutants. Benzothiophene could not be biodegraded when concentration was above 50 mg/l. It was observed that 2-(1H)-quinolinone, benzothiophene-2-one, and benzofuran-2,3-dione were formed as metabolic intermediates during biodegradation of quinoline, benzothiophene, and benzofuran, respectively. Quinoline-N and pyridine-N were transformed into free ammonium ions during the biodegradation process. Biodegradation pathways for various NSO compounds are proposed. Monod inhibition model was able to simulate single substrate biodegradation kinetics satisfactorily. Benzothiophene and benzofuran biodegradation kinetics, in presence of acetone, was simulated using a generalized multi-substrate model.

  4. Variations in the 6.2 μm emission profile in starburst-dominated galaxies: a signature of polycyclic aromatic nitrogen heterocycles (PANHs)?

    Science.gov (United States)

    Canelo, Carla M.; Friaça, Amâncio C. S.; Sales, Dinalva A.; Pastoriza, Miriani G.; Ruschel-Dutra, Daniel

    2018-04-01

    Analyses of the polycyclic aromatic hydrocarbon (PAH) feature profiles, especially the 6.2 μm feature, could indicate the presence of nitrogen incorporated in their aromatic rings. In this work, 155 predominantly starburst-dominated galaxies (including H II regions and Seyferts, for example), extracted from the Spitzer/Infrared Spectrograph ATLAS project, have their 6.2 μm profiles fitted allowing their separation into the Peeters' A, B, and C classes. 67 per cent of these galaxies were classified as class A, 31 per cent were as class B, and 2 per cent as class C. Currently, class A sources, corresponding to a central wavelength near 6.22 μm, seem only to be explained by polycyclic aromatic nitrogen heterocycles (PANHs), whereas class B may represent a mix between PAHs and PANHs emissions or different PANH structures or ionization states. Therefore, these spectra suggest a significant presence of PANHs in the interstellar medium (ISM) of these galaxies that could be related to their starburst-dominated emission. These results also suggest that PANHs constitute another reservoir of nitrogen in the Universe, in addition to the nitrogen in the gas phase and ices of the ISM.

  5. Electrochemical methods for monitoring of environmental carcinogens.

    Science.gov (United States)

    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.

  6. Discovery of the aryl heterocyclic amine insecticides: synthesis, insecticidal activity, field results, mode of action and bioavailability of a leading field candidate.

    Science.gov (United States)

    Dent, William H; Pobanz, Mark A; Geng, Chaoxian; Sparks, Thomas C; Watson, Gerald B; Letherer, Theodore J; Beavers, Kenneth W; Young, Cathy D; Adelfinskaya, Yelena A; Ross, Ronald R; Whiteker, Greg; Renga, James

    2017-04-01

    γ-Amino butyric acid (GABA) antagonists are proven targets for control of lepidopteran and other pests. New heterocyclic compounds with high insecticidal activity were discovered using a competitive-intelligence-inspired scaffold-hopping approach to generate analogs of fipronil, a known GABA antagonist. These novel aryl heterocyclic amines (AHAs) displayed broad-spectrum activity on a number of chewing insect pests. Through >370 modifications of the core AHA structure, a 7-pyrazolopyridine lead molecule was found to exhibit much improved activity on a number of insect pests. In field trial studies, its performance was 2-4 times lower than commercial standards and also appeared to be species dependent, with good activity seen for larvae of Spodoptera exigua, but inactivity on larvae of Trichoplusia ni. An extensive investigational biology effort demonstrated that these AHA analogs appear to have multiple modes of action, including GABA receptor antagonism and mitopotential or uncoupler activity. The limited capability in larvae of T. ni to convert the lead molecule to its associated open form correlates with the low toxicity of the lead molecule in this species. This work has provided information that could aid investigations of novel GABA antagonists. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

  7. Synthesis of heterocycles via transition-metal-catalyzed hydroarylation of alkynes.

    Science.gov (United States)

    Yamamoto, Yoshihiko

    2014-03-07

    Transition-metal (TM)-catalyzed hydroarylation reactions of alkynes have received much attention, because they enable the net insertion of alkyne C-C triple bonds into C-H bonds of aromatic precursors, resulting in regio- and stereo-selective formation of synthetically useful arylalkenes. Taking advantage of this feature, TM-catalyzed alkyne hydroarylations have been successfully used for the synthesis of heterocycles. TM-catalyzed alkyne hydroarylations can be classified into three major categories depending on the type of reaction and precursors involved: (1) palladium-catalyzed reductive Heck reactions of alkynes with aryl halides, (2) TM-catalyzed conjugate arylation reactions of activated alkynes with arylboronic acids, and (3) TM-catalyzed aromatic C-H alkenylations with alkynes. This review surveys heterocycle synthesis via TM-catalyzed hydroarylation of alkynes according to the above classification, with an emphasis on the scope and limitations, as well as the underlying mechanisms.

  8. A versatile family of degradable non-viral gene carriers based on hyperbranched poly(ester amine)s

    NARCIS (Netherlands)

    Zhong, Zhiyuan; Song, Y.; Engbersen, Johannes F.J.; Lok, Martin C.; Hennink, Wim E.; Feijen, Jan

    2005-01-01

    A variety of degradable hyperbranched poly(ester amine)s containing primary, secondary and tertiary amino groups, were synthesized and evaluated as non-viral gene carriers. The polymers were obtained in high yields through a Michael-type conjugate addition of diacrylate monomers with trifunctional

  9. 2-(2′-Pyridyl)-4,6-diphenylphosphinine versus 2-(2′-Pyridyl)-4,6-diphenylpyridine: Synthesis, Characterization, and Reactivity of Cationic RhIII and IrIII Complexes Based on Aromatic Phosphorus Heterocycles

    NARCIS (Netherlands)

    de Krom, I.; Broeckx, L.E.E.; Lutz, M.; Müller, Christian

    2013-01-01

    The bidentate P,N hybrid ligand 1 allows access for the first time to novel cationic phosphinine-based RhIII and IrIII complexes, broadening significantly the scope of low-coordinate aromatic phosphorus heterocycles for potential applications. The coordination chemistry of 1 towards RhIII and IrIII

  10. CYP-450 isoenzymes catalyze the generation of hazardous aromatic amines after reaction with the azo dye Sudan III.

    Science.gov (United States)

    Zanoni, Thalita Boldrin; Lizier, Thiago M; Assis, Marilda das Dores; Zanoni, Maria Valnice B; de Oliveira, Danielle Palma

    2013-07-01

    This work describes the mutagenic response of Sudan III, an adulterant food dye, using Salmonella typhimurium assay and the generation of hazardous aromatic amines after different oxidation methods of this azo dye. For that, we used metabolic activation by S9, catalytic oxidation by ironporphyrin and electrochemistry oxidation in order to simulate endogenous oxidation conditions. The oxidation reactions promoted discoloration from 65% to 95% of Sudan III at 1 × 10(-4)molL(-1) and generation of 7.6 × 10(-7)molL(-1) to 0.31 × 10(-4)molL(-1) of aniline, o-anisidine, 2-methoxi-5-methylaniline, 4-aminobiphenyl, 4,4'-oxydianiline; 4,4'-diaminodiphenylmethane and 2,6-dimethylaniline. The results were confirmed by LC-MS-MS experiments. We also correlate the mutagenic effects of Sudan III using S. typhimurium with the strain TA1535 in the presence of exogenous metabolic activation (S9) with the metabolization products of this compound. Our findings clearly indicate that aromatic amines are formed due to oxidative reactions that can be promoted by hepatic cells, after the ingestion of Sudan III. Considering that, the use of azo compounds as food dyestuffs should be carefully controlled. Copyright © 2013 Elsevier Ltd. All rights reserved.

  11. Photocatalytic organic transformation by layered double hydroxides: highly efficient and selective oxidation of primary aromatic amines to their imines under ambient aerobic conditions.

    Science.gov (United States)

    Yang, Xiu-Jie; Chen, Bin; Li, Xu-Bing; Zheng, Li-Qiang; Wu, Li-Zhu; Tung, Chen-Ho

    2014-06-25

    We report the first application of layered double hydroxide as a photocatalyst in the transformation of primary aromatic amines to their corresponding imines with high efficiency and selectivity by using oxygen in an air atmosphere as a terminal oxidant under light irradiation.

  12. Effect of donor orientation on ultrafast intermolecular electron transfer in coumarin-amine systems

    International Nuclear Information System (INIS)

    Singh, P. K.; Nath, S.; Bhasikuttan, A. C.; Kumbhakar, M.; Mohanty, J.; Sarkar, S. K.; Mukherjee, T.; Pal, H.

    2008-01-01

    Effect of donor amine orientation on nondiffusive ultrafast intermolecular electron transfer (ET) reactions in coumarin-amine systems has been investigated using femtosecond fluorescence upconversion measurements. Intermolecular ET from different aromatic and aliphatic amines used as donor solvents to the excited coumarin-151 (C151) acceptor occurs with ultrafast rates such that the shortest fluorescence lifetime component (τ 1 ) is the measure of the fastest ET rate (τ 1 =τ ET fast =(k ET fast ) -1 ), assigned to the C151-amine contact pairs in which amine donors are properly oriented with respect to C151 to maximize the acceptor-donor electronic coupling (V el ). It is interestingly observed that as the amine solvents are diluted by suitable diluents (either keeping solvent dielectric constant similar or with increasing dielectric constant), the τ 1 remains almost in the similar range as long as the amine dilution does not cross a certain critical limit, which in terms of the amine mole fraction (x A ) is found to be ∼0.4 for aromatic amines and ∼0.8 for aliphatic amines. Beyond these dilutions in the two respective cases of the amine systems, the τ 1 values are seen to increase very sharply. The large difference in the critical x A values involving aromatic and aliphatic amine donors has been rationalized in terms of the largely different orientational restrictions for the ET reactions as imposed by the aliphatic (n-type) and aromatic (π-type) nature of the amine donors [A. K. Satpati et al., J. Mol. Struct. 878, 84 (2008)]. Since the highest occupied molecular orbital (HOMO) of the n-type aliphatic amines is mostly centralized at the amino nitrogen, only some specific orientations of these amines with respect to the close-contact acceptor dye [also of π-character; A. K. Satpati et al., J. Mol. Struct. 878, 84 (2008) and E. W. Castner et al., J. Phys. Chem. A 104, 2869 (2000)] can give suitable V el and thus ultrafast ET reaction. In contrary, the

  13. [Simultaneous determination of 33 primary aromatic amines of free state in fine pigments by ultra-performance liquid chromatography coupled with triple quadrupole mass spectrometry].

    Science.gov (United States)

    Man, Zhengyin; Wang, Quanlin; Li, Hesheng; Zhang, Aizhi

    2014-12-01

    A comprehensive analytical method based on ultra-performance liquid chromatography coupled with triple quadrupole mass spectrometry (UPLC-MS/MS) has been developed for the simultaneous determination of 33 primary aromatic amines (PAAs) in fine pigments such as gouache paint, oil painting pigment and acrylic paint. The primary aromatic amines in samples were extracted with acetonitrile. Then the extract was concentrated by centrifugation and nitrogen blow, finally diluted to 2 mL with methanol-water (1:9, v/v) and filtered through 0. 22 im membrane before UPLC-MS/MS analysis. The analytes were separated on a BEH Phenyl column (100 mm x 2. 1 mm, 1. 7 1µm) with 0. 07% (v/v) formic acid in methanol-water as mobile phases in gradient elution. The PAAs were detected by UPLC-MS/MS under multiple reaction monitoring (MRM) mode and quantified by the internal standard method. The separation conditions, fragment voltages and collision energies were optimized. The impacts of extraction times, extraction solvents and concentration methods on recoveries were studied. The limits of detection and limits of quantitation for the 33 primary aromatic amines were 5-50 µg/kg and 15-150 µg/kg respectively. The mean recoveries of three different dye products at three spiked levels were 70. 1% - 115. 8%. The relative standard deviations were 2. 1% - 15%. The expenmental results indicated that the method is simple, rapid, sensitive, accurate and can meet the requirements for the determination.

  14. Effect of different types of sugars in a marinating formulation on the formation of heterocyclic amines in grilled chicken.

    Science.gov (United States)

    Hasnol, N D S; Jinap, S; Sanny, M

    2014-02-15

    The aim of the study was to determine the effect of different types of sugar on the formation of heterocyclic amines (HCA) in marinated grilled chicken. Chicken breast samples were marinated with table sugar, brown sugar, and honey for 24h at 4 °C. The internal temperature, weight loss, free amino acids, sugars, and HCA were determined. The concentrations of all types of HCA (except IQx) in samples that were marinated with table sugar were significantly higher (pbrown sugar; whereas those were marinated with honey had the lowest HCA concentrations. A substantial reduction in the concentration of MeIQ, PhIP, DiMeIQx, IQ, IQx, and norharman was achieved in chicken marinated with honey. A correlation study indicated that adding honey into the recipe retarded the formation of most HCA (MeIQ, DiMeIQx, IQ, IQx, norharman, and harman), whereas table sugars enhanced the formation of all HCA except norharman, harman, and AαC. Copyright © 2013 Elsevier Ltd. All rights reserved.

  15. Microwave-Accelerated Iodination of Some Aromatic Amines, Using Urea-Hydrogen Peroxide Addition Compound (UHP as the Oxidant

    Directory of Open Access Journals (Sweden)

    Lech Skulski

    2002-12-01

    Full Text Available A fast and simple method for the oxidative iodination of some aromatic amines, under microwave irradiation, is reported, using diiodine and the the strongly Hbonded urea-hydrogen peroxide addition compound (H2NCONH2···H2O2, UHP as the oxidant. The reactions were carried out in boiling CHCl3 under a reflux condenser to afford, within 10 minutes, the purified monoiodinated products in 40-80% yields.

  16. Quantum mechanical design of efficient second-order nonlinear optical materials based on heteroaromatic imido-substituted hexamolybdates: first theoretical framework of POM-based heterocyclic aromatic rings.

    Science.gov (United States)

    Janjua, Muhammad Ramzan Saeed Ashraf

    2012-11-05

    This work was inspired by a previous report (Janjua et al. J. Phys. Chem. A 2009, 113, 3576-3587) in which the nonlinear-optical (NLO) response strikingly improved with an increase in the conjugation path of the ligand and the nature of hexamolybdates (polyoxometalates, POMs) was changed into a donor by altering the direction of charge transfer with a second aromatic ring. Herein, the first theoretical framework of POM-based heteroaromatic rings is found to be another class of excellent NLO materials having double heteroaromatic rings. First hyperpolarizabilities of a large number of push-pull-substituted conjugated systems with heteroaromatic rings have been calculated. The β components were computed at the density functional theory (DFT) level (BP86 geometry optimizations and LB94 time-dependent DFT). The largest β values are obtained with a donor (hexamolybdates) on the benzene ring and an acceptor (-NO(2)) on pyrrole, thiophene, and furan rings. The pyrrole imido-substituted hexamolybdate (system 1c) has a considerably large first hyperpolarizability, 339.00 × 10(-30) esu, and it is larger than that of (arylimido)hexamolybdate, calculated as 0.302 × 10(-30) esu (reference system 1), because of the double aromatic rings in the heteroaromatic imido-substituted hexamolybdates. The heteroaromatic rings act as a conjugation bridge between the electron acceptor (-NO(2)) and donor (polyanion). The introduction of an electron donor into heteroaromatic rings significantly enhances the first hyperpolarizabilities because the electron-donating ability is substantially enhanced when the electron donor is attached to the heterocyclic aromatic rings. Interposing five-membered auxiliary fragments between strong donor (polyanion) or acceptor (-NO(2)) groups results in a large computed second-order NLO response. The present investigation provides important insight into the NLO properties of (heteroaromatic) imido-substituted hexamolybdate derivatives because these compounds

  17. Oxidations of N-(3-indoleethyl) cyclic aliphatic amines by horseradish peroxidase: the indole ring binds to the enzyme and mediates electron-transfer amine oxidation.

    Science.gov (United States)

    Ling, Ke-Qing; Li, Wen-Shan; Sayre, Lawrence M

    2008-01-23

    Although oxidations of aromatic amines by horseradish peroxidase (HRP) are well-known, typical aliphatic amines are not substrates of HRP. In this study, the reactions of N-benzyl and N-methyl cyclic amines with HRP were found to be slow, but reactions of N-(3-indoleethyl) cyclic amines were 2-3 orders of magnitude faster. Analyses of pH-rate profiles revealed a dominant contribution to reaction by the amine-free base forms, the only species found to bind to the enzyme. A metabolic study on a family of congeneric N-(3-indoleethyl) cyclic amines indicated competition between amine and indole oxidation pathways. Amine oxidation dominated for the seven- and eight-membered azacycles, where ring size supports the change in hybridization from sp3 to sp2 that occurs upon one-electron amine nitrogen oxidation, whereas only indole oxidation was observed for the six-membered ring congener. Optical difference spectroscopic binding data and computational docking simulations suggest that all the arylalkylamine substrates bind to the enzyme through their aromatic termini with similar binding modes and binding affinities. Kinetic saturation was observed for a particularly soluble substrate, consistent with an obligatory role of an enzyme-substrate complexation preceding electron transfer. The significant rate enhancements seen for the indoleethylamine substrates suggest the ability of the bound indole ring to mediate what amounts to medium long-range electron-transfer oxidation of the tertiary amine center by the HRP oxidants. This is the first systematic investigation to document aliphatic amine oxidation by HRP at rates consistent with normal metabolic turnover, and the demonstration that this is facilitated by an auxiliary electron-rich aromatic ring.

  18. Combining molecular docking and QSAR studies for modeling the anti-tyrosinase activity of aromatic heterocycle thiosemicarbazone analogues

    Science.gov (United States)

    Dong, Huanhuan; Liu, Jing; Liu, Xiaoru; Yu, Yanying; Cao, Shuwen

    2018-01-01

    A collection of thirty-six aromatic heterocycle thiosemicarbazone analogues presented a broad span of anti-tyrosinase activities were designed and obtained. A robust and reliable two-dimensional quantitative structure-activity relationship model, as evidenced by the high q2 and r2 values (0.848 and 0.893, respectively), was gained based on the analogues to predict the quantitative chemical-biological relationship and the new modifier direction. Inhibitory activities of the compounds were found to greatly depend on molecular shape and orbital energy. Substituents brought out large ovality and high highest-occupied molecular orbital energy values helped to improve the activity of these analogues. The molecular docking results provided visual evidence for QSAR analysis and inhibition mechanism. Based on these, two novel tyrosinase inhibitors O04 and O05 with predicted IC50 of 0.5384 and 0.8752 nM were designed and suggested for further research.

  19. Direct α-C-H bond functionalization of unprotected cyclic amines

    Science.gov (United States)

    Chen, Weijie; Ma, Longle; Paul, Anirudra; Seidel, Daniel

    2018-02-01

    Cyclic amines are ubiquitous core structures of bioactive natural products and pharmaceutical drugs. Although the site-selective abstraction of C-H bonds is an attractive strategy for preparing valuable functionalized amines from their readily available parent heterocycles, this approach has largely been limited to substrates that require protection of the amine nitrogen atom. In addition, most methods rely on transition metals and are incompatible with the presence of amine N-H bonds. Here we introduce a protecting-group-free approach for the α-functionalization of cyclic secondary amines. An operationally simple one-pot procedure generates products via a process that involves intermolecular hydride transfer to generate an imine intermediate that is subsequently captured by a nucleophile, such as an alkyl or aryl lithium compound. Reactions are regioselective and stereospecific and enable the rapid preparation of bioactive amines, as exemplified by the facile synthesis of anabasine and (-)-solenopsin A.

  20. Iridium‐Catalyzed Condensation of Amines and Vicinal Diols to Substituted Piperazines

    DEFF Research Database (Denmark)

    Lorentz-Petersen, Linda Luise Reeh; Nordstrøm, Lars Ulrik Rubæk; Madsen, Robert

    2012-01-01

    is believed to involve dehydrogenation of the 1,2‐diol to the α‐hydroxy aldehyde, which condenses with the amine to form the α‐hydroxy imine. The latter rearranges to the corresponding α‐amino carbonyl compound, which then reacts with another amine followed by reduction of the resulting imine.......A straightforward procedure is described for the synthesis of piperazines from amines and 1,2‐diols. The heterocyclization is catalyzed by [Cp*IrCl2]2 and sodium hydrogen carbonate and can be achieved with either toluene or water as solvent. The transformation does not require any stoichiometric...

  1. Cancer mortality and occupational exposure to aromatic amines and inhalable aerosols in rubber tire manufacturing in Poland.

    Science.gov (United States)

    de Vocht, Frank; Sobala, Wojciech; Wilczynska, Urszula; Kromhout, Hans; Szeszenia-Dabrowska, Neonila; Peplonska, Beata

    2009-08-01

    Most data on carcinogenic risk in the rubber industry are based on data from Western countries. This study assessed cancer risks in a retrospective cohort in a Polish tire manufacturing plant, relying on quantified exposure to inhalable aerosols and aromatic amines instead of job titles or external comparisons. Cumulative exposure for all exposures was assigned to cohort members based on estimates from a company-specific JEM. Cancer risks associated with cumulative exposure adjusted for co-exposures, gender and year of birth were calculated. Exposure levels were higher for women than for men. Aromatic amine exposure was significantly associated with increased urinary bladder cancer risk (RR=7.32-8.27), depending on exposure level, and prostate cancer at low levels only (RR=5.86). In women, increased risks were found for all cancers (RR=2.50) and of the digestive organs and peritoneum (RR=4.54) at low level only, while an exposure-response association with breast cancer risk was found. Inhalable aerosol exposure was associated with cancers of the liver and intrahepatic bile ducts in a dose-dependent manner, while dose-dependent reduced risks were found for respiratory cancers (most notably the larynx) and cancer of the colon. Increased risks for specific cancer sites in this rubber plant were similar to Western Europe and the US. However, several cancer risks were gender-specific which could relate to higher exposure levels in women or to differences in exposures to chemicals not assessed in this study.

  2. Elution behavior of N-heterocyclic derivatives of mixed ruthenium(II)-sulfoxide complexes in reversed-phase high-performance liquid chromatography

    International Nuclear Information System (INIS)

    Toma, H.E.; Silva, D.O.

    1991-01-01

    The elution behaviour of a series of dichlorobis-(dimethylsulfoxide)bis(N-heterocyclic) ruthenium(II) complexes has been investigated using reversed-phase HPLC. Similar trends as those displayed by the free N-heterocyclic bases have been observed for the complexes, essentially reflecting the hydrophobic properties of the aromatic ligands. (orig.)

  3. Protonation sites of aromatic compounds in (+) atmospheric pressure photoionization

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Sung Hwan; Ahmed, Arif [Dept. of Chemistry, Kyungpoo k National University, Daegu (Korea, Republic of)

    2017-02-15

    Reaction enthalpy of hydrogen transfer reactions of aromatic compounds has been observed to be greatly affected by the exact location of the protonation site. Therefore, to clearly identify the protonation location, each candidate protonation site for 43 aromatic compounds were theoretically determined and their location was compared with that determined based on experimental MS data. Only the basic nitrogen atom is favorable as a protonation site for pyridine-type aromatic compounds, whereas carbon atoms are preferable for the protonation of pyrrole-type compounds. The most favorable protonation sites for aniline or methylated aniline-type aromatic compounds are either the nitrogen atom in the amine group or the carbon atom at the para-position to the amine group. Like pyrrole-type compounds, aromatic compounds with amine groups also favor protonation at the carbon atom instead of at the nitrogen atom. In addition, hydrocarbons having an anthracene structural motif without heteroatoms produced higher or equal percentages of protonated ions compared to that achieved with molecular ions. The results of this study can be used to improve the analyses of aromatic compounds.

  4. Metal-Mediated Couplings of Primary Alcohols with Amines and Carbohydrates

    DEFF Research Database (Denmark)

    Maggi, Agnese; Madsen, Robert

    . The reaction is proposed to proceed by initial dehydrogenation of the alcohol to the aldehyde, which stays coordinated to the ruthenium centre. Then, nucleophilic attack of the amine affords the hemiaminal, which is released from ruthenium and converted into the imine. Project 2: Tin-mediated regioselective 6...... from alcohols and amines catalyzed by a ruthenium N-heterocyclic carbene complex. The successful method development and application of a convenient and direct (one step) synthesis of imines from alcohols and amines is described. The developed method provides quick andextended access to structurally...... and amines have been coupled in the presence of the catalyst to afford the corresponding imines in moderate to good yields. Optically pure amines gave the corresponding imines without any sign of racemization. Moreover, the one-pot diastereoselective addition of different organometallic reagents to the imine...

  5. Risk of colorectal adenomas in relation to meat consumption, meat preparation, and genetic susceptibility in a Dutch population

    NARCIS (Netherlands)

    Tiemersma, E.W.; Voskuil, D.W.; Bunschoten, A.; Kok, F.J.; Kampman, E.

    2004-01-01

    Objective: We studied the association between meat consumption and colorectal adenomas, and potential influence of genetic susceptibility to heterocyclic aromatic amines (HCAs) formed during meat cooking at high temperatures. Methods: We studied HCA concentration in relation to preparation habits

  6. The effect of heterocyclic S,S’-ligands on the electrochemical properties of some cobalt(III complexes in acid

    Directory of Open Access Journals (Sweden)

    V. M. JOVANOVIC

    2005-02-01

    Full Text Available Eight mixed-ligand cobalt(III complexes with the macrocyclic amine 1,4,8,11-tetraazacyclotetradecane (cyclam and a heterocyclic dithiocarbamate (Rdtc- i.e., morpholine- (Morphdtc, thiomorpholine- (Timdtc, piperazine- (Pzdtc, N-methylpiperazine-(Mepzdtc, piperidine- (Pipdtc, 2-, 3- or 4-methylpiperidine- (2-, 3- and 4-Mepipdtc carbodithionato-S,S ions, of the general formula [Co(cyclamRdtc](ClO42, were investigated in deoxygenated 0.1MHClO4 solutions. Cyclic voltammetry data at a glassy carbon (GC electrode demonstrate a redox reaction of cobalt(III from the complexes at potentials strongly influenced by the presence of different heterocyclic Rdtc- ligands. In this respect, the complexes were separated into two groups: the first, with a heteroatom O, S or N in the heterocyclic ring, and the second, with a methyl group on the piperidine ring of the Rdtc- ligand. Anodic polarization of an Fe electrode in the presence of the complexes shows their influence not only on the dissolution of iron but also on the hydrogen evolution reactions and on this basis complexes the complexes could be divided into the same two groups. It was found that the weaker the inhibiting effect of the free heterocyclic amines is, the significantly higher is the efficiency of the corresponding complexes.

  7. Meat consumption, heterocyclic amines and colorectal cancer risk: the Multiethnic Cohort Study.

    Science.gov (United States)

    Ollberding, Nicholas J; Wilkens, Lynne R; Henderson, Brian E; Kolonel, Laurence N; Le Marchand, Loïc

    2012-10-01

    Greater consumption of red and processed meat has been associated with an increased risk of colorectal cancer in several recent meta-analyses. Heterocyclic amines (HCAs) have been hypothesized to underlie this association. In this prospective analysis conducted within the Multiethnic Cohort Study, we examined whether greater consumption of total, red or processed meat was associated with the risk of colorectal cancer among 165,717 participants who completed a detailed food frequency questionnaire at baseline. In addition, we examined whether greater estimated intake of HCAs was associated with the risk of colorectal cancer among 131,763 participants who completed a follow-up questionnaire that included a meat-cooking module. A total of 3,404 and 1,757 invasive colorectal cancers were identified from baseline to the end of follow-up and from the date of administration of the meat-cooking module to the end of follow-up, respectively. Proportional hazard models were used to estimate basic and multivariable-adjusted relative risks (RRs) and 95% confidence intervals for colorectal cancer associated with dietary exposures. In multivariable models, no association with the risk of colorectal cancer was detected for density-adjusted total meat (RR(Q5 vs. Q1) = 0.93 [0.83-1.05]), red meat (RR = 1.02 [0.91-1.16]) or processed meat intake (RR = 1.06 [0.94-1.19]) or for total (RR = 0.90 [0.76-1.05]) or specific HCA intake whether comparing quintiles of dietary exposure or using continuous variables. Although our results do not support a role for meat or for HCAs from meat in the etiology of colorectal cancer, we cannot rule out the possibility of a modest effect. Copyright © 2012 UICC.

  8. Meat and fat intake and pancreatic cancer risk in the Netherlands Cohort Study

    NARCIS (Netherlands)

    Heinen, M.M.; Verhage, B.A.J.; Goldbohm, R.A.; Brandt, P.A. van den

    2009-01-01

    Meat contains numerous carcinogens, such as heterocyclic amines, polycyclic aromatic hydrocarbons, and N-nitroso compounds, which can be derived either from natural food or during the process of food preparation. These carcinogens may increase pancreatic cancer risk. Furthermore, studies in animals

  9. Heterocyclic amines: Mutagens/carcinogens produced during cooking of meat and fish.

    Science.gov (United States)

    Sugimura, Takashi; Wakabayashi, Keiji; Nakagama, Hitoshi; Nagao, Minako

    2004-04-01

    Research leading to the discovery of a series of mutagenic and carcinogenic heterocyclic amines (HCAs) was inspired by the idea that smoke produced during cooking of food, especially meat or fish, might be carcinogenic. More than ten kinds of HCAs, actually produced by cooking or heating of meat or fish, have now been isolated and their structures determined, most being previously unregistered compounds. They are highly mutagenic towards Salmonella typhimurium in the presence of S9 mix and are also mutagenic in vitro and in vivo toward mammalian cells. HCAs have now been chemically synthesized in quantity and subjected to long-term animal testing. When HCAs were fed in the diet, rodents developed cancers in many organs, including the colon, breast and prostate, and one HCA produced hepatomas in monkeys. The lesions exhibited alteration in genes including Apc, beta-catenin and Ha-ras, and these changes provide clues to the induction mechanisms. The HCAs are oxidized to hydroxyamino derivatives by cytochrome P450s, and further converted to ester forms by acetyltransferase and sulfotransferase. Eventually, they produce DNA adducts through the formation of N-C bonds at guanine bases. There are HCA-sensitive and resistant strains of rodents and a search for the responsible genes is now under way. While the content of HCAs in dishes consumed in ordinary life is low and not sufficient in itself to explain human cancer, the coexistence of many other mutagens/carcinogens of either autobiotic or xenobiotic type and the possibility that HCAs induce genomic instability and heightened sensitivity to tumor promoters suggest that avoidance of exposure to HCAs or reduction of HCAs' biological effects as far as possible are to be highly recommended. Usage of microwave ovens for cooking and supplementation of the diet, for example with soy-isoflavones, which have been found to suppress the occurrence of HCA-induced breast cancers, should be encouraged. Advice to the general public

  10. Formation of Haloacetonitriles, Haloacetamides, and Nitrogenous Heterocyclic Byproducts by Chloramination of Phenolic Compounds.

    Science.gov (United States)

    Nihemaiti, Maolida; Le Roux, Julien; Hoppe-Jones, Christiane; Reckhow, David A; Croué, Jean-Philippe

    2017-01-03

    The potential formation of nitrogenous disinfection byproducts (N-DBPs) was investigated from the chloramination of nitrogenous and non-nitrogenous aromatic compounds. All molecules led to the formation of known N-DBPs (e.g., dichloroacetonitrile, dichloroacetamide) with various production yields. Resorcinol, a major precursor of chloroform, also formed di/trichloroacetonitrile, di/trichloroacetamide, and haloacetic acids, indicating that it is a precursor of both N-DBPs and carbonaceous DBPs (C-DBPs) upon chloramination. More detailed experiments were conducted on resorcinol to understand N-DBPs formation mechanisms and to identify reaction intermediates. Based on the accurate mass from high resolution Quadrupole Time-of-Flight GC-MS (GC-QTOF) and fragmentation patterns from electronic impact and positive chemical ionization modes, several products were tentatively identified as nitrogenous heterocyclic compounds (e.g., 3-chloro-5-hydroxy-1H-pyrrole-2-one with dichloromethyl group, 3-chloro-2,5-pyrroledione). These products were structurally similar to the heterocyclic compounds formed during chlorination, such as the highly mutagenic MX (3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone) or halogenated pyrroles. To our knowledge, this is the first time that the formation of halogenated nitrogenous heterocyclic compounds is reported from chloramination process. The formation of these nitrogenous byproducts during chloramination might be of concern considering their potential toxicity.

  11. Computational Methods to Predict the Regioselectivity of Electrophilic Aromatic Substitution Reactions of Heteroaromatic Systems

    DEFF Research Database (Denmark)

    Kruszyk, Monika; Jessing, Mikkel; Kristensen, Jesper L

    2016-01-01

    The validity of calculated NMR shifts to predict the outcome of electrophilic aromatic substitution reactions on different heterocyclic compounds has been examined. Based on an analysis of >130 literature examples it was found that the lowest calculated 13C and/or 1H chemical shift of a heterocycle...... correlates qualitatively with the regiochemical outcome of halogenation reactions in >80% of the investigated cases. In the remaining cases, the site of electrophilic aromatic substitution can be explained by the calculated HOMO orbitals obtained using density functional theory. Using a combination...

  12. Application of heterocyclic aldehydes as components in Ugi–Smiles couplings

    Directory of Open Access Journals (Sweden)

    Katelynn M. Mason

    2016-09-01

    Full Text Available Efficient one-pot Ugi–Smiles couplings are reported for the use of furyl-substituted aldehyde components. In the presence of these heterocyclic aldehydes, reactions tolerated variations in amine components and led to either isolated N-arylamide Ugi–Smiles adducts or N-arylepoxyisoindolines, products of tandem Ugi–Smiles Diels–Alder cyclizations, in moderate yields. A thienyl-substituted aldehyde was also a competent component for Ugi–Smiles adduct formation.

  13. Partitioning-separation of metal ions using heterocyclic ligands

    International Nuclear Information System (INIS)

    Hudson, M.J.; Drew, M.G.B.; Iveson, P.B.; Russell, M.L.

    2001-01-01

    Some guidelines are proposed for the effective design of heterocyclic ligands for partitioning because there is no doubt that the correct design of a molecular extractant is required for the effective separation of metal ions such as actinides(III) from lanthanides(III). Heterocyclic ligands with aromatic ring systems have a rich chemistry, which is only now becoming sufficiently well understood in relation to the partitioning process. The synthesis, characterisation and structures of some chosen molecules will be introduced in order to illustrate some important features. For example, the molecule N-carboxy-butyl-2-amino-4,6-di (2-pyridyl)-1,3,5-triazine (BADPTZ), which is an effective solvent extraction reagent for actinides and lanthanides, has been synthesised, characterised and its interaction with lanthanide ions studied. The interesting and important features of this molecule will be compared with those of other heterocyclic molecules such as 2,6-bis(5-butyl-1,2,4-triazole-3-yl) pyridine (DBTZP), which is a candidate molecule for the commercial separation of actinides and lanthanide elements. (author)

  14. Redox self-sufficient whole cell biotransformation for amination of alcohols.

    Science.gov (United States)

    Klatte, Stephanie; Wendisch, Volker F

    2014-10-15

    Whole cell biotransformation is an upcoming tool to replace common chemical routes for functionalization and modification of desired molecules. In the approach presented here the production of various non-natural (di)amines was realized using the designed whole cell biocatalyst Escherichia coli W3110/pTrc99A-ald-adh-ta with plasmid-borne overexpression of genes for an l-alanine dehydrogenase, an alcohol dehydrogenase and a transaminase. Cascading alcohol oxidation with l-alanine dependent transamination and l-alanine dehydrogenase allowed for redox self-sufficient conversion of alcohols to the corresponding amines. The supplementation of the corresponding (di)alcohol precursors as well as amino group donor l-alanine and ammonium chloride were sufficient for amination and redox cofactor recycling in a resting buffer system. The addition of the transaminase cofactor pyridoxal-phosphate and the alcohol dehydrogenase cofactor NAD(+) was not necessary to obtain complete conversion. Secondary and cyclic alcohols, for example, 2-hexanol and cyclohexanol were not aminated. However, efficient redox self-sufficient amination of aliphatic and aromatic (di)alcohols in vivo was achieved with 1-hexanol, 1,10-decanediol and benzylalcohol being aminated best. Copyright © 2014 Elsevier Ltd. All rights reserved.

  15. Heterocycles by Transition Metals Catalyzed Intramolecular Cyclization of Acetylene Compounds

    International Nuclear Information System (INIS)

    Vizer, S.A.; Yerzhanov, K.B.; Dedeshko, E.C.

    2003-01-01

    Review shows the new strategies in the synthesis of heterocycles, having nitrogen, oxygen and sulfur atoms, via transition metals catalyzed intramolecular cyclization of acetylenic compounds on the data published at the last 30 years, Unsaturated heterocyclic compounds (pyrroles and pyrroline, furans, dihydro furans and benzofurans, indoles and iso-indoles, isoquinolines and isoquinolinones, aurones, iso coumarins and oxazolinone, lactams and lactones with various substitutes in heterocycles) are formed by transition metals, those salts [PdCl 2 , Pd(OAc) 2 , HgCl 2 , Hg(OAc) 2 , Hg(OCOCF 3 ) 2 , AuCl 3 ·2H 2 O, NaAuCl 4 ·2H 2 O, CuI, CuCl], oxides (HgO) and complexes [Pd(OAc) 2 (PPh 3 )2, Pd(PPh 3 ) 4 , PdCl 2 (MeCN) 2 , Pd(OAc ) 2 /TPPTS] catalyzed intramolecular cyclization of acetylenic amines, amides, ethers, alcohols, acids, ketones and βdiketones. More complex hetero polycyclic systems typical for natural alkaloids can to obtain similar. Proposed mechanisms of pyrroles, isoquinolines, iso indoles and indoles, benzofurans and iso coumarins, thiazolopyrimidinones formation are considered. (author)

  16. Chronic toxicity of polycyclic aromatic compounds to the springtail Folsomia candida and the enchytraeid Enchytraeus crypticus.

    NARCIS (Netherlands)

    Droge, S.T.J.; Leon Paumen, M; Bleeker, E.A.J.; Kraak, M.H.S.; van Gestel, C.A.M.

    2006-01-01

    An urgent need exists for incorporating heterocyclic compounds and (bio)transformation products in ecotoxicological test schemes and risk assessment of polycyclic aromatic compounds (PACs). The aim of the present study therefore was to determine the chronic effects of (heterocyclic) PACs on two

  17. Synthesis of New N-Arylpyrimidin-2-amine Derivatives Using a Palladium Catalyst

    Directory of Open Access Journals (Sweden)

    So Ha Lee

    2008-04-01

    Full Text Available New N-aryl-4-(pyridin-3-ylpyrimidin-2-amine derivatives were synthesizedfrom the corresponding amines, applying optimized Buchwald-Hartwig aminationconditions using dichlorobis(triphenylphosphinePd(II, xantphos and sodium tertbutoxidein refluxing toluene under a nitrogen atmosphere. The target N-aryl derivativeswere obtained in moderate to good yields ranging from 27% to 82%. The proceduredescribed could be widely employed for the preparation of new heterocyclic compounds.The structures of the new compounds were confirmed by FT-NMR, FT-IR and elementalanalysis.

  18. Simple and Efficient Procedure for Synthesis of N'-Arylamidines Using Trimethylaluminum

    International Nuclear Information System (INIS)

    Korbad, Balaji L.; Lee, Sanghyeup

    2013-01-01

    In conclusion, we have developed simple and efficient procedure for the synthesis of N'-arylamidines using tri-methylaluminum, nitriles and aryl amines under mild condition. Aliphatic, aromatic nitriles were reacted well with a variety of aromatic amine to afford corresponding amidines in good to high yields. Amidines are an important class of compounds that have wide range of application in the fields of catalyst design, material science, medicinal chemistry and also shown the promising anti-inflammatory and analgesic activity. They are valuable synthons for synthesis of various heterocyclic compounds. In addition, recent studies have demonstrated their capacity to fix carbon dioxide

  19. Direct Amination of Nitro(pentafluorosulfanyl)benzenes through Vicarious Nucleophilic Substitution of Hydrogen

    Czech Academy of Sciences Publication Activity Database

    Pastýříková, Tereza; Iakobson, George; Vida, Norbert; Pohl, Radek; Beier, Petr

    -, č. 11 (2012), s. 2123-2126 ISSN 1434-193X R&D Projects: GA ČR GAP207/12/0072 Institutional research plan: CEZ:AV0Z40550506 Keywords : sulfur * amination * nucleophilic substitution * nitrogen heterocycles Subject RIV: CC - Organic Chemistry Impact factor: 3.344, year: 2012

  20. Inhibitory activity of Asian spices on heterocyclic amines formation in cooked beef patties.

    Science.gov (United States)

    Puangsombat, Kanithaporn; Jirapakkul, Wannee; Smith, J Scott

    2011-10-01

    Heterocyclic amines (HCAs) are mutagenic compounds formed when foods are cooked at high temperatures. Numerous reports have shown that natural antioxidants from spices, fruits, chocolate, and tea can inhibit formation. In this study, we evaluated HCA formation in the presence of 5 of Asian spices: galangal (Alpinia galangal), fingerroot (Boesenbergia pandurata), turmeric (Curcuma longa), cumin (Cuminum cyminum), and coriander seeds (Coriandrum sativum). HCA levels were compared to patties containing rosemary (Rosmarinus officinalis), of which the inhibitory effect is well documented. Inhibition of HCA formation by the spices was evaluated in beef patties cooked at 204 °C (400 °F) for 10 min. All spices were mixed into patties at 0.2% before cooking, and HCAs levels were measured in the final product. All patties, including the control, contained 2-amino-3,8-dimethylimidazo [4,5-f]quinoxaline (MeIQx) and 2-amino-1-methyl -6-phenylimidazo [4,5-b]pyridine (PhIP). The average HCA content of the control patties was 7 ng/g MeIQx and 6.53 ng/g PhIP. Turmeric (39.2% inhibition), fingerroot (33.5% inhibition), and galangal (18.4% inhibition) significantly decreased HCAs compared with the control. But, only turmeric and fingerroot were as effective as rosemary in preventing HCA formation. The HCA inhibition in patties containing spices was significantly correlated to the total phenolic content (R(2) = 0.80) and the scavenging activity (R(2) = 0.84) of the spices as measured by the 2,2-diphenyl-β-picrylhydrazyl assay. Results of this study suggest that addition of Asian spices can be an important factor in decreasing the levels of HCAs in fried beef patties. © 2011 Institute of Food Technologists®

  1. Influence of aromatic amine hardeners in the cure kinetics of an epoxy resin used in advanced composites

    Directory of Open Access Journals (Sweden)

    Michelle Leali Costa

    2005-03-01

    Full Text Available Composite structures for aerospace applications are mainly made by the well-known prepreg technology. In order to achieve adequate prepreg processing schedules, and consequently maximum fiber strength utilization, one has to know in deep the cure kinetics of matrix, which held the fibers together. This work describes a procedure to study the cure kinetic and has as example how aromatic amine hardeners influence the cure kinetics of an epoxy resin used in advanced composites. The investigation was carried out by using the DSC technique and it was found that depending on the system used the cure kinetics of the formulation obeys order n or autocatalytic order.

  2. Adsorbed States of phosphonate derivatives of N-heterocyclic aromatic compounds, imidazole, thiazole, and pyridine on colloidal silver: comparison with a silver electrode.

    Science.gov (United States)

    Podstawka, Edyta; Olszewski, Tomasz K; Boduszek, Bogdan; Proniewicz, Leonard M

    2009-09-03

    Here, we report a systematic surface-enhanced Raman spectroscopy (SERS) study of the structures of phosphonate derivatives of the N-heterocyclic aromatic compounds imidazole (ImMeP ([hydroxy(1H-imidazol-5-yl)methyl]phosphonic acid) and (ImMe)(2)P (bis[hydroxy-(1H-imidazol-4-yl)-methyl]phosphinic acid)), thiazole (BAThMeP (butylaminothiazol-2-yl-methyl)phosphonic acid) and BzAThMeP (benzylaminothiazol-2-yl-methyl)phosphonic acid)), and pyridine ((PyMe)(2)P (bis[(hydroxypyridin-3-yl-methyl)]phosphinic acid)) adsorbed on nanometer-sized colloidal particles. We compared these structures to those on a roughened silver electrode surface to determine the relationship between the adsorption strength and the geometry. For example, we showed that all of these biomolecules interact with the colloidal surface through aromatic rings. However, for BzAThMeP, a preferential interaction between the benzene ring and the colloidal silver surface is observed more so than that between the thiazole ring and this substrate. The PC(OH)C fragment does not take part in the adsorption process, and the phosphonate moiety of ImMeP and (ImMe)(2)P, being removed from the surface, only assists in this process.

  3. Palladium-catalyzed aryl amination-heck cyclization cascade: A one-flask approach to 3-substituted Indoles

    DEFF Research Database (Denmark)

    Jensen, Thomas; Pedersen, Henrik; Bang-Andersen, B.

    2008-01-01

    Two for the price of one: A Pd/dppf-based catalyst provides access to the title compounds from 1,2-dihalogenated aromatic compounds and allylic amines in a single reaction flask. The initial aryl amination step occurs with excellent selectivity for the aryl iodide to ensure the formation of a sin......Two for the price of one: A Pd/dppf-based catalyst provides access to the title compounds from 1,2-dihalogenated aromatic compounds and allylic amines in a single reaction flask. The initial aryl amination step occurs with excellent selectivity for the aryl iodide to ensure the formation...

  4. Identification of sulfur heterocycles in coal liquids and shale oils. Technical progress report, August 1, 1980-May 1, 1981

    Energy Technology Data Exchange (ETDEWEB)

    Lee, M. L.; Castle, R. N.

    1981-01-01

    The sulfur heterocycle separation scheme which was described in the last progress report was evaluated for quantitative recovery of individual components. The results indicate that recoveries can range from 10% to approx. 30% depending on the structure of the compound. During this period, 23 unsubstituted sulfur-containing heterocyclic ring systems were synthesized in oder to confirm GC/MS identifications and for biological testing. The four possible 3-ring heterocycles and the thirteen possible 4-ring heterocycles were tested for mutagenic activity in the histidine reversion (Ames assay) system. One of the 3-ring isomers, naphtho(1,2-b)-thiophene, and six of the 4-ring isomers induced mutations in Salmonella test strains. One of these compounds, phenanthro(3,4-b)thiophene, displayed approximately the same mutagenic activity as benzo(a)pyrene. A two-step adsorption chromatographic procedure was developed in order to fractionate synthetic fuels into various chemical-type classes for studying the relative concentrations and mutagenic activities of the various types. An SRC-II Heavy Distillate was fractionated into aliphatic hydrocarbons, polycyclic aromatic hydrocarbons, sulfur heterocycles, indoles and carbazoles, azaarenes, and amino polycyclic aromatic hydrocarbons. It was found that the amino-PAH fraction contained most of the mutagenic activity. A survey was made for compounds containing both nitrogen and sulfur heteroatoms in their structures. A number of these compounds were detected by GC using nitrogen- and sulfur-selective detection.

  5. Aryl hydrocarbon receptor activation and CYP1A induction by cooked food-derived carcinogenic heterocyclic amines in human HepG2 cell lines.

    Science.gov (United States)

    Sekimoto, Masashi; Sumi, Haruna; Hosaka, Takuomi; Umemura, Takashi; Nishikawa, Akiyoshi; Degawa, Masakuni

    2016-11-01

    The ability of nine cooked food-derived heterocyclic aromatic amines (HCAs), such as 3-amino-1,4-dimethyl-5H-pyrido[4,3-b]indole (Trp-P-1), 3-amino-1-methyl-5H-pyrido[4,3-b]indole (Trp-P-2), 2-amino-6-methylpyrido[12-a:3',2'-d]imidazole (Glu-P-1), 2-amino-pyrido[12-a:3',2'-d]imidazole hydrochloride (Glu-P-2), 2-amino-9H-pyrido[2,3-b]indole (AαC), 2-amino-3-methyl-9H-pyrido[2,3-b]indole (MeAαC), 2-amino-3-methylimidazo[4,5-f]quinolone (IQ), 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx) and 2-amino-1-methyl-6-phenyl-1H-imidazo[4,5-b]pyridine (PhIP), to activate human aryl hydrocarbon receptor (hAhR) was examined using a HepG2-A10 cell line, which has previously established from human hepatocarcinoma-derived HepG2 cells for use in hAhR-based luciferase reporter gene assays. Trp-P-1, Trp-P-2, AαC, MeAαC, IQ and MeIQx showed a definite ability to induce not only luciferase (hAhR activation) in HepG2-A10 cells but also cytochrome P450 (CYP)1A1/1A2 mRNAs in HepG2 cells, while such the ability of Glu-P-1, Glu-P-2, and PhIP was very low. In addition, all the HCAs examined, especially MeAαC and MeIQx, had a definite capacity for inhibiting the activity of ethoxyresorfin O-deethylase (CYP1As, especially CYP1A1). The present findings demonstrate that all the HCAs examined have the ability to activate hAhR and its target genes, and further confirm that these HCAs become good substrates for human CYP1A subfamily enzyme(s). Copyright © 2016 Elsevier Ltd. All rights reserved.

  6. 15N NMR investigation of the covalent binding of reduced TNT amines to soil humic acid, model compounds, and lignocellulose

    Science.gov (United States)

    Thorn, K.A.; Kennedy, K.R.

    2002-01-01

    The five major reductive degradation products of TNT-4ADNT (4-amino-2,6-dinitrotoluene), 2ADNT (2-amino-4,6-dinitrotoluene), 2,4DANT (2,4-diamino-6-nitrotoluene), 2,6DANT (2,6-diamino-4-nitrotoluene), and TAT (2,4,6-triaminotoluene)-labeled with 15N in the amine positions, were reacted with the IHSS soil humic acid and analyzed by 15N NMR spectrometry. In the absence of catalysts, all five amines underwent nucleophilic addition reactions with quinone and other carbonyl groups in the soil humic acid to form both heterocyclic and nonheterocyclic condensation products. Imine formation via 1,2-addition of the amines to quinone groups in the soil humic acid was significant with the diamines and TAT but not the monoamines. Horseradish peroxidase (HRP) catalyzed an increase in the incorporation of all five amines into the humic acid. In the case of the diamines and TAT, HRP also shifted the binding away from heterocyclic condensation product toward imine formation. A comparison of quantitative liquid phase with solid-state CP/MAS 15N NMR indicated that the CP experiment underestimated imine and heterocyclic nitrogens in humic acid, even with contact times optimal for observation of these nitrogens. Covalent binding of the mono- and diamines to 4-methylcatechol, the HRP catalyzed condensation of 4ADNT and 2,4DANT to coniferyl alcohol, and the binding of 2,4DANT to lignocellulose with and without birnessite were also examined.

  7. Vertical distribution and environmental significance of sulfur and oxygen heterocyclic aromatic hydrocarbons in soil samples collected from Beijing, China

    International Nuclear Information System (INIS)

    Zhang Zhihuan; He Fengpeng; Bu Qingwei; Lu Song

    2008-01-01

    Vertical distribution of the concentration and composition of some sulfur and oxygen heterocyclic aromatic hydrocarbons (SOHAHs), such as, fluorene, dibenzofuran, dibenzothiophene and their alkyl homologues in 10 soil profiles in Beijing have been investigated. The results showed that the concentrations and composition of SOHAHs in topsoil (0-30 cm) from different profiles are different. The concentrations of SOHAHs in topsoils are much higher than that in bottom soils where the concentrations are relatively constant. The fingerprints of SOHAHs from same profile are similar in topsoil samples, which are obviously different at the deep part, which suggested that the sources of these compounds are consistent in topsoil and are discriminating between surface and bottom soils. The main sources of SOHAHs in surface soil were fossil fuel combustion, petroleum and wastewater irrigation, while those at deep part were likely derived from the degradation products of soil organic matters. - The vertical distribution of SOHAHs was provided and possible sources were different between topsoils and deep part

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

    Science.gov (United States)

    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.

  9. Interactions between 9,10-anthraquinone and aromatic amines in homogeneous and micellar media: A laser flash photolysis and magnetic field effect study

    International Nuclear Information System (INIS)

    Chowdhury, Adity; Basu, Samita

    2006-01-01

    The interactions between 9,10-anthraquinone (AQ) and different aromatic amines, N,N-dimethylaniline and 4,4'-bis (dimethylamino) diphenylmethane (DMDPM), have been studied using absorption, steady-state fluorescence, and laser flash photolysis techniques in organic homogeneous and heterogeneous micellar media. In polar organic homogeneous medium, electron transfer (ET) occurs from amines to excited AQ. In micellar medium, similar intermolecular ET is observed. However, in latter medium, ET predominates over hydrogen abstraction from micelles by excited AQ itself. The occurrence of ET has been further supported by the application of an external magnetic field during laser flash photolysis experiments, which modulates the yield of radical ion pairs formed through ET. Another novel feature, which has also been discussed here, is the abnormal behavior of DMDPM in micellar medium pertaining to energy transfer

  10. Fluoroalkyl Amino Reagents (FARs): A General Approach towards the Synthesis of Heterocyclic Compounds Bearing Emergent Fluorinated Substituents.

    Science.gov (United States)

    Commare, Bruno; Schmitt, Etienne; Aribi, Fallia; Panossian, Armen; Vors, Jean-Pierre; Pazenok, Sergiy; Leroux, Frédéric R

    2017-06-12

    Fluorinated heterocycles are important building blocks in pharmaceutical, agrochemical and material sciences. Therefore, organofluorine chemistry has witnessed high interest in the development of efficient methods for the introduction of emergent fluorinated substituents (EFS) onto heterocycles. In this context, fluoroalkyl amino reagents (FARs)-a class of chemicals that was slightly forgotten over the last decades-has emerged again recently and proved to be a powerful tool for the introduction of various fluorinated groups onto (hetero)aromatic derivatives.

  11. Inhibitory action of an heterocyclic organic compound containing amine group for copper corrosion in 5,0 M nitric acid solution

    Energy Technology Data Exchange (ETDEWEB)

    El-Naggar, M.M.; Abdallah, M. [Benha Univ., Benha (Egypt). Chemistry Dept., Faculty of Science

    2000-10-01

    An heterocyclic organic compound containing amine group namely: 3-mercaptomethyl-4amino-5-hydroxy-1, 2, 4-triazole compound 1{sub a} was tested as a new inhibitor for copper corrosion in 5.0 M HNO{sub 3} solution. It proved to have a high value of inhibition efficiency (> 99.9%) at an inhibitor concentration of {>=} 2.5 x 10{sup -}3 M. A parallelism is established between the results obtained from weight loss, thermometric and galvanostatic polarization techniques. The high protective effect of compound I{sub a} is related to the decomposition of HNO{sub 2} formed through the autocatalytic cycle. The decomposition of HNO{sub 2} could be attributed to its reaction with the adsorbed inhibitor amine group. Furthermore, the results indicated that compound I{sub a} provides long-term protection and behaves as a mixed inhibitor type with a predominant cathodic effectiveness. [Italian] E' stato valutato, quale nuovo inibitore della corrosione del rame in soluzione 5.0 M di HNO{sub 3}, un composto organico eterociclico contenente un amino gruppo, chiamato: 3-mercaptometil-4amino-5-idrossi-1, 2, 4-triazolo composto I{sub a}. Questi, ad una concentrazione {>=} 2.5 x 10{sup -}3 M, ha dimostrato di possedere un elevato valore di efficienza di inibizione (> 99.9%). E' stato stabilito un parallelismo tra i risultati ottenuti dalla perdita di peso, da misure termometriche e di polarizzazione galvanostatica. L'elevato effetto protettivo del composto I{sub a} e' correlato alla decomposizione dell'HNO{sub 2} formatosi attraverso il ciclo autocatalitico. La decomposizione di HNO{sub 2} puo' essere attribuita alla sua reazione con il gruppo inibitore aminico adsorbito. Inoltre, i risultati indicano che il composto I{sub a} fornisce una protezione a lungo termine e si comporta come un inibitore di tipo misto con una predominante efficienza catodica.

  12. Rapid estimation of organic nitrogen in oil shale wastewaters

    Energy Technology Data Exchange (ETDEWEB)

    Jones, B.M.; Harris, G.J.; Daughton, C.G.

    1984-03-01

    Many of the characteristics of oil shale process wastewaters (e.g., malodors, color, and resistance to biotreatment) are imparted by numerous nitrogen heterocycles and aromatic amines. For the frequent performance assessment of waste treatment procsses designed to remove these nitrogenous organic compounds, a rapid and colligative measurement of organic nitrogen is essential.

  13. Oxidation of tertiary amines by cytochrome p450-kinetic isotope effect as a spin-state reactivity probe.

    Science.gov (United States)

    Li, Chunsen; Wu, Wei; Cho, Kyung-Bin; Shaik, Sason

    2009-08-24

    Two types of tertiary amine oxidation processes, namely, N-dealkylation and N-oxygenation, by compound I (Cpd I) of cytochrome P450 are studied theoretically using hybrid DFT calculations. All the calculations show that both N-dealkylation and N-oxygenation of trimethylamine (TMA) proceed preferentially from the low-spin (LS) state of Cpd I. Indeed, the computed kinetic isotope effects (KIEs) for the rate-controlling hydrogen abstraction step of dealkylation show that only the KIE(LS) fits the experimental datum, whereas the corresponding value for the high-spin (HS) process is much higher. These results second those published before for N,N-dimethylaniline (DMA), and as such, they further confirm the conclusion drawn then that KIEs can be a sensitive probe of spin state reactivity. The ferric-carbinolamine of TMA decomposes most likely in a non-enzymatic reaction since the Fe-O bond dissociation energy (BDE) is negative. The computational results reveal that in the reverse reaction of N-oxygenation, the N-oxide of aromatic amine can serve as a better oxygen donor than that of aliphatic amine to generate Cpd I. This capability of the N-oxo derivatives of aromatic amines to transfer oxygen to the heme, and thereby generate Cpd I, is in good accord with experimental data previously reported.

  14. Influence of fused aromatic ring on the stability of charge transfer complex between iodine and some five membered heterocyclic molecules through ultrasonic and spectral studies

    Science.gov (United States)

    Ulagendran, V.; Balu, P.; Kannappan, V.; Kumar, R.; Jayakumar, S.

    2017-08-01

    The charge transfer (CT) interaction between two fused heterocyclic compounds with basic pyrrole group as donors, viz., indole (IND) and carbazole (CAR), and iodine (acceptor) in DMSO medium is investigated by ultrasonic and UV-visible spectral methods at 303 K. The formation of CT complex in these systems is established from the trend in acoustical and excess thermo acoustical properties with molar concentration. The frequency acoustic spectra (FAS) is also carried out on these two systems for two fixed concentrations 0.002 M and 0.02 M, and in the frequency range 1 MHz-10 MHz to justify the frequency chosen for ultrasonic study. The absorption coefficient values in solution are computed and discussed. The formation constants of these complexes are determined using Kannappan equation in ultrasonic method. The formation of 1:1 complexes between iodine and IND, CAR was established by the theory of Benesi - Hildebrand in the UV-visible spectroscopic method. The stability constants of the CT complexes determined by spectroscopic and ultrasonic methods show a similar trend. These values also indicate that the presence of fused aromatic ring influences significantly when compared with K values of similar CT complexes of parent five membered heterocyclic compound (pyrrole) reported by us earlier.

  15. Extrapolation of systemic bioavailability assessing skin absorption and epidermal and hepatic metabolism of aromatic amine hair dyes in vitro.

    Science.gov (United States)

    Manwaring, John; Rothe, Helga; Obringer, Cindy; Foltz, David J; Baker, Timothy R; Troutman, John A; Hewitt, Nicola J; Goebel, Carsten

    2015-09-01

    Approaches to assess the role of absorption, metabolism and excretion of cosmetic ingredients that are based on the integration of different in vitro data are important for their safety assessment, specifically as it offers an opportunity to refine that safety assessment. In order to estimate systemic exposure (AUC) to aromatic amine hair dyes following typical product application conditions, skin penetration and epidermal and systemic metabolic conversion of the parent compound was assessed in human skin explants and human keratinocyte (HaCaT) and hepatocyte cultures. To estimate the amount of the aromatic amine that can reach the general circulation unchanged after passage through the skin the following toxicokinetically relevant parameters were applied: a) Michaelis-Menten kinetics to quantify the epidermal metabolism; b) the estimated keratinocyte cell abundance in the viable epidermis; c) the skin penetration rate; d) the calculated Mean Residence Time in the viable epidermis; e) the viable epidermis thickness and f) the skin permeability coefficient. In a next step, in vitro hepatocyte Km and Vmax values and whole liver mass and cell abundance were used to calculate the scaled intrinsic clearance, which was combined with liver blood flow and fraction of compound unbound in the blood to give hepatic clearance. The systemic exposure in the general circulation (AUC) was extrapolated using internal dose and hepatic clearance, and Cmax was extrapolated (conservative overestimation) using internal dose and volume of distribution, indicating that appropriate toxicokinetic information can be generated based solely on in vitro data. For the hair dye, p-phenylenediamine, these data were found to be in the same order of magnitude as those published for human volunteers. Copyright © 2015. Published by Elsevier Inc.

  16. π-face donation from the aromatic N-substituent of N-heterocyclic carbene ligands to metal and its role in catalysis

    KAUST Repository

    Credendino, Raffaele

    2012-05-16

    In this work, we calculate the redox potential in a series of Ir and Ru complexes bearing a N-heterocyclic carbene (NHC) ligand presenting different Y groups in the para position of the aromatic N-substituent. The calculated redox potentials excellently correlate with the experimental ΔE 1/2 potentials, offering a handle to rationalize the experimental findings. Analysis of the HOMO of the complexes before oxidation suggests that electron-donating Y groups destabilize the metal centered HOMO. Energy decomposition of the metal-NHC interaction indicates that electron-donating Y groups reinforce this interaction in the oxidized complexes. Analysis of the electron density in the reduced and oxidized states of representative complexes indicates a clear donation from the C ipso of the N-substituents to an empty d orbital on the metal. In case of the Ru complexes, this mechanism involves the Ru-alkylidene moiety. All of these results suggest that electron-donating Y groups render the aromatic N-substituent able to donate more density to electron-deficient metals through the C ipso atom. This conclusion suggests that electron-donating Y groups could stabilize higher oxidation states during catalysis. To test this hypothesis, we investigated the effect of differently donating Y groups in model reactions of Ru-catalyzed olefin metathesis and Pd-catalyzed C-C cross-coupling. Consistent with the experimental results, calculations indicate an easier reaction pathway if the N-substituent of the NHC ligand presents an electron-donating Y group. © 2012 American Chemical Society.

  17. An Acetyltransferase Conferring Tolerance to Toxic Aromatic Amine Chemicals

    Science.gov (United States)

    Martins, Marta; Rodrigues-Lima, Fernando; Dairou, Julien; Lamouri, Aazdine; Malagnac, Fabienne; Silar, Philippe; Dupret, Jean-Marie

    2009-01-01

    Aromatic amines (AA) are a major class of environmental pollutants that have been shown to have genotoxic and cytotoxic potentials toward most living organisms. Fungi are able to tolerate a diverse range of chemical compounds including certain AA and have long been used as models to understand general biological processes. Deciphering the mechanisms underlying this tolerance may improve our understanding of the adaptation of organisms to stressful environments and pave the way for novel pharmaceutical and/or biotechnological applications. We have identified and characterized two arylamine N-acetyltransferase (NAT) enzymes (PaNAT1 and PaNAT2) from the model fungus Podospora anserina that acetylate a wide range of AA. Targeted gene disruption experiments revealed that PaNAT2 was required for the growth and survival of the fungus in the presence of toxic AA. Functional studies using the knock-out strains and chemically acetylated AA indicated that tolerance of P. anserina to toxic AA was due to the N-acetylation of these chemicals by PaNAT2. Moreover, we provide proof-of-concept remediation experiments where P. anserina, through its PaNAT2 enzyme, is able to detoxify the highly toxic pesticide residue 3,4-dichloroaniline in experimentally contaminated soil samples. Overall, our data show that a single xenobiotic-metabolizing enzyme can mediate tolerance to a major class of pollutants in a eukaryotic species. These findings expand the understanding of the role of xenobiotic-metabolizing enzyme and in particular of NATs in the adaptation of organisms to their chemical environment and provide a basis for new systems for the bioremediation of contaminated soils. PMID:19416981

  18. Asymmetrical/symmetrical D-π-A/D-π-D thiazole-containing aromatic heterocyclic fluorescent compounds having the same triphenylamino chromophores.

    Science.gov (United States)

    Tao, Tao; Ma, Bin-Bin; Peng, Yu-Xin; Wang, Xiao-Xu; Huang, Wei; You, Xiao-Zeng

    2013-09-06

    A family of linear asymmetrical D-π-A and symmetrical D-π-D types of thiazole-based aromatic heterocyclic fluorescent compounds bearing various electron-donating and electron-withdrawing tails (bromo, triphenylamino, pyridyl, thienyl and benzoic acid) have been designed and prepared successfully. Synthetic, structural, thermal, spectral and computational comparisons have been carried out for related compounds because of their adjustable electronic properties. It is interesting to mention that compound 2 can be prepared from 5-bromothiazole by one-pot Suzuki-Miyaura coupling and subsequent C-H activation reactions via a 5-TPA-substituted thiazole intermediate 1. X-ray single-crystal structures of six compounds indicate that they all crystallize in the triclinic P1 space group and the thiazole core exhibits different dihedral angles with its adjacent benzene ring of the triphenylamino group (3.6(3)-40.8(3)°). The photophysical and electrochemical results demonstrate that compound 7 exhibits high electrochemical activity with a green fluorescence emission. Meanwhile, compounds 1, 2, and 6 show high luminescence quantum yields, and compound 8 exhibits excellent thermal stability (T(d(10)) = 503 °C).

  19. Backflush HPLC for the isolation of polycyclic aromatic compounds - a comparative study

    Energy Technology Data Exchange (ETDEWEB)

    Oestman, C.E.; Colmsjoe, A.L.

    1987-12-01

    Semipreparative HPLC utilizing a polar bonded phase was applied to the isolation of polycyclic aromatic compounds (PAC) from complex samples using a backflush technique. Aminopropyl- and cyanopropyl-modified silica was tested. Aminopropyl-modified silica was found to be superior in achieving rapid, selective and non discriminating isolation of PAC. This was compared with the most commonly used isolation methods, dimethylsulfoxide (DMSO), dimethylformamide (DMF) and nitromethane liquid-liquid extractions, and silica and SephadexLH-20 open column chromatography. Strong discrimination of alkylated PAC and polycyclic aromatic nitrogen heterocyclics (PANH) was found for the liquid-liquid extractions and the LH-20 column chromatography. These comparisons were made using both standard compounds and a sample of used crank-case oil, indicating the necessity of using a real sample for evaluation of extraction methods. Recoveries of 42 PACs are reported.

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

    Science.gov (United States)

    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.

  1. Nutrition Frontiers - Summer 2016 | Division of Cancer Prevention

    Science.gov (United States)

    Volume 7, Issue 3 The summer issue of Nutrition Frontiers showcases the combined effects of ursolic acid and resveratrol for skin cancer, the potential chemopreventive effects of the dietary supplement 4-MU, and a method to monitor a heterocyclic aromatic amine in dyed hair. Learn about our spotlight investigators, Drs. Michael Caligiuri and Jianhua Yu, and their research on

  2. Consumption of Brussels sprouts protects peripheral human lymphocytes against 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhlP) and oxidative DNA-damage: results of a controlled human intervention trial

    Czech Academy of Sciences Publication Activity Database

    Hoelzl, C.; Glatt, H.; Meinl, W.; Sontag, G.; Haidinger, G.; Kundi, M.; Simic, T.; Chakraborty, A.; Bichler, J.; Ferk, F.; Angelis, Karel; Nersesyan, A.; Knasmüller, S.

    2008-01-01

    Roč. 52, č. 3 (2008), s. 330-341 ISSN 1613-4125 R&D Projects: GA MŠk 1M0505; GA MŠk(CZ) LC06004 Institutional research plan: CEZ:AV0Z50380511 Keywords : antioxidant * comet assay * cruciferous vegetables * heterocyclic aromatic amines Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 3.308, year: 2008

  3. Efficient and selective N-alkylation of amines with alcohols catalysed by manganese pincer complexes

    Science.gov (United States)

    Elangovan, Saravanakumar; Neumann, Jacob; Sortais, Jean-Baptiste; Junge, Kathrin; Darcel, Christophe; Beller, Matthias

    2016-01-01

    Borrowing hydrogen (or hydrogen autotransfer) reactions represent straightforward and sustainable C–N bond-forming processes. In general, precious metal-based catalysts are employed for this effective transformation. In recent years, the use of earth abundant and cheap non-noble metal catalysts for this process attracted considerable attention in the scientific community. Here we show that the selective N-alkylation of amines with alcohols can be catalysed by defined PNP manganese pincer complexes. A variety of substituted anilines are monoalkylated with different (hetero)aromatic and aliphatic alcohols even in the presence of other sensitive reducible functional groups. As a special highlight, we report the chemoselective monomethylation of primary amines using methanol under mild conditions. PMID:27708259

  4. Convergent Synthesis of Piperidines by the Union of Conjugated Alkynes with Imines: A Unique Regioselective Bond Construction for Heterocycle Synthesis

    Science.gov (United States)

    Chen, Ming Z.; Micalizio, Glenn C.

    2009-01-01

    A two-step process is described for the union of aromatic imines, conjugated alkynes and aldehydes that results in a stereoselective synthesis of highly substituted piperidines. This synthetic process has been made possible by defining a unique regioselective functionalization of conjugated alkynes that establishes a suitably functionalized substrate for subsequent heterocycle-forming cationic annulation. Given the flexibility of the coupling process, heterocycles can be accessed through a process that establishes up to four stereogenic centers and four fused rings. PMID:19817447

  5. How non-conventional feedstocks will affect aromatics technologies

    Energy Technology Data Exchange (ETDEWEB)

    Koehler, E. [Clariant Produkte (Deutschland) GmbH, Muenchen (Germany)

    2013-11-01

    The abundance of non-conventional feedstocks such as coal and shale gas has begun to affect the availability of traditional base chemicals such as propylene and BTX aromatics. Although this trend is primarily fueled by the fast growing shale gas economy in the US and the abundance of coal in China, it will cause the global supply and demand situation to equilibrate across the regions. Lower demand for gasoline and consequently less aromatics rich reformate from refineries will further tighten the aromatics markets that are expected to grow at healthy rates, however. Refiners can benefit from this trend by abandoning their traditional fuel-oriented business model and becoming producers of petrochemical intermediates, with special focus on paraxylene (PX). Cheap gas from coal (via gasification) or shale reserves is an advantaged feedstock that offers a great platform to make aromatics in a cost-competitive manner, especially in regions where naphtha is in short supply. Gas condensates (LPG and naphtha) are good feedstocks for paraffin aromatization, and methanol from coal or (shale) gas can be directly converted to BTX aromatics (MTA) or alkylated with benzene or toluene to make paraxylene. Most of today's technologies for the production and upgrading of BTX aromatics and their derivatives make use of the unique properties of zeolites. (orig.)

  6. The Synthesis of Methyl Salicylate: Amine Diazotization.

    Science.gov (United States)

    Zanger, Murray; McKee, James R.

    1988-01-01

    Notes that this experiment takes safety and noncarcinogenic reactants into account. Demonstrates the use of diazonium salts for the replacement of an aromatic amine group by a phenolic hydroxyl. Involves two pleasant-smelling organic compounds, methyl anthranilate (grape) and methyl salicylate (oil of wintergreen). (MVL)

  7. Proximate Composition, Mineral Content and Fatty Acids Analyses of Aromatic and Non-Aromatic Indian Rice

    Directory of Open Access Journals (Sweden)

    Deepak Kumar Verma

    2017-01-01

    Full Text Available Awareness on nutritive value and health benefits of rice is of vital importance in order to increase the consumption of rice in daily diet of the human beings. In this study, a total of six aromatic and two non-aromatic rice accessions grown in India were analysed for their nutritional quality attributes including proximate composition, mineral contents and fatty acids. Data with three replications were used to measure Pearson's simple correlation co-efficient in order to establish the relationship among various nutritional quality attributes. The result on proximate composition showed that Govind Bhog had the highest moisture (13.57% and fat (0.92% content, which signifies its tasty attribute. Badshah Bhog exhibited the highest fibre content (0.85%, carbohydrate content (82.70% and food energy (365.23 kCal per 100 g. Among the minerals, the higher Ca (98.75 mg/kg, Zn (17.00 mg/kg and Fe (31.50 mg/kg were in Gopal Bhog, whereas the highest Na (68.85 mg/kg was in Badshah Bhog, the highest K (500.00 mg/kg was in Swetganga, Khushboo and Sarbati. The highest contents of unsaturated fatty acids viz. oleic acid (49.14%, linoleic acid (46.99% and linolenic acid (1.27% were found in Sarbati, whereas the highest content of saturated fatty acids viz. myristic acid (4.60% and palmitic acid (31.91% were found in Govind Bhog and stearic acid (6.47% in Todal. The identified aromatic rice accessions Gopal Bhog, Govind Bhog and Badshah Bhog and non-aromatic rice accession Sarbati were found nutritionally superior among all eight tested accessions. The nutritional quality oriented attributes in this study were competent with recognized prominent aromatic and non-aromatic rice accessions as an index of their nutritional worth and recommend to farmers and consumers which may be graded as export quality rice with good unique nutritional values in international market.

  8. Yb(OTf){sub 3}-catalyzed one-pot three component synthesis for tertiary amines

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Bum Seok; Kim, Ji Hye; Nam, Tae Kyu; Jang, Doo Ok [Dept. of Chemistry, Yonsei University, Wonju (Korea, Republic of)

    2015-07-15

    Tertiary amine functionality is found in many natural bioactive products such as alkaloids, amino acids, nucleic acids, pharmaceuticals, and agrochemicals. Tertiary amines have also been used as building blocks for nitrogen-containing organic compounds and synthetic polymers. A one-pot method for direct reductive amination of aldehydes has been developed to synthesize tertiary amines using HMDS as a nitrogen source in the presence of Yb(OTf ){sub 3}. With a stoichiometric amount of HMDS, the reaction afforded the desired tertiary amines without competitive reduction of the parent carbonyl compounds. This reaction offers a convenient and efficient protocol for synthesizing aromatic and aliphatic tertiary amines under mild reaction conditions.

  9. Handbook of heterocyclic chemistry

    National Research Council Canada - National Science Library

    Katritzky, Alan R

    2010-01-01

    ... Heterocyclic Chemistry I (1984) Comprehensive Heterocyclic Chemistry II (1996) Comprehensive Heterocyclic Chemistry III (2008) Comprehensive Organic Functional Group Transformations I (1995) Compreh...

  10. Chemistry of polyhalogenated nitrobutadienes, 10: Synthesis of highly functionalized heterocycles with a rigid 6-amino-3-azabicyclo[3.1.0]hexane moiety

    Directory of Open Access Journals (Sweden)

    Viktor A. Zapol’skii

    2012-04-01

    Full Text Available The nitropolychlorobutadienes 3, 4 are valuable building blocks for various amination and successive heterocyclization products. Nucleophilic substitution reactions of the partially protected, bioactive amines 1, 2 with either vinyl, imidoyl or carbonyl chlorides result in the formation of the enamines 11, 12, 13, 16, 25, the amidine 6, and the amides 20, 21, respectively. In the following, cyclization to the highly functionalized pyrazoles 27, 28, pyrimidine 26 and pyridopyrimidine 24 succeeded. Deprotection of 21, 12 and 28 proved to be only partially feasible.

  11. Evaluation of maillard reaction variables and their effect on heterocyclic amine formation in chemical model systems.

    Science.gov (United States)

    Dennis, Cara; Karim, Faris; Smith, J Scott

    2015-02-01

    Heterocyclic amines (HCAs), highly mutagenic and potentially carcinogenic by-products, form during Maillard browning reactions, specifically in muscle-rich foods. Chemical model systems allow examination of in vitro formation of HCAs while eliminating complex matrices of meat. Limited research has evaluated the effects of Maillard reaction parameters on HCA formation. Therefore, 4 essential Maillard variables (precursors molar concentrations, water amount, sugar type, and sugar amounts) were evaluated to optimize a model system for the study of 4 HCAs: 2-amino-3-methylimidazo-[4,5-f]quinoline, 2-amino-3-methylimidazo[4,5-f]quinoxaline, 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline, and 2-amino-3,4,8-trimethyl-imidazo[4,5-f]quinoxaline. Model systems were dissolved in diethylene glycol, heated at 175 °C for 40 min, and separated using reversed-phase liquid chromatography. To define the model system, precursor amounts (threonine and creatinine) were adjusted in molar increments (0.2/0.2, 0.4/0.4, 0.6/0.6, and 0.8/0.8 mmol) and water amounts by percentage (0%, 5%, 10%, and 15%). Sugars (lactose, glucose, galactose, and fructose) were evaluated in several molar amounts proportional to threonine and creatinine (quarter, half, equi, and double). The precursor levels and amounts of sugar were significantly different (P < 0.05) in regards to total HCA formation, with 0.6/0.6/1.2 mmol producing higher levels. Water concentration and sugar type also had a significant effect (P < 0.05), with 5% water and lactose producing higher total HCA amounts. A model system containing threonine (0.6 mmol), creatinine (0.6 mmol), and glucose (1.2 mmol), with 15% water was determined to be the optimal model system with glucose and 15% water being a better representation of meat systems. © 2015 Institute of Food Technologists®

  12. Studies in Aromatic and Amine Nitration.

    Science.gov (United States)

    1980-05-20

    of Commerce, May 1978. 4. J. Hoggett , R. Moodie, F. Penton, and K. Schofield, Nitration and Aromatic Reactivity (Cambridge University Press, 1971). 5...Moodie, K. Schofield, and G. Tobin, J. Chem. Soc., Chem. Comm., 180 (1978); (b) J. Hoggett , R. Moodie, and K. Schofield, Chem. Comm. 605 (1969). 10. (a) S...Lawrence Livermore Laboratories (Received, 5th Februaty 1980; Com. 124.) 42 ’(a) J. Hoggett , R. B. Moodie, J. R. Penton, and K. Schofield, in ’Nitration

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

    DEFF Research Database (Denmark)

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

    2004-01-01

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

  14. Comparison between Different Extraction Methods for Determination of Primary Aromatic Amines in Food Simulant

    Directory of Open Access Journals (Sweden)

    Morteza Shahrestani

    2018-01-01

    Full Text Available The primary aromatic amines (PAAs are food contaminants which may exist in packaged food. Polyurethane (PU adhesives which are used in flexible packaging are the main source of PAAs. It is the unreacted diisocyanates which in fact migrate to foodstuff and then hydrolyze to PAAs. These PAAs include toluenediamines (TDAs and methylenedianilines (MDAs, and the selected PAAs were 2,4-TDA, 2,6-TDA, 4,4′-MDA, 2,4′-MDA, and 2,2′-MDA. PAAs have genotoxic, carcinogenic, and allergenic effects. In this study, extraction methods were applied on a 3% acetic acid as food simulant which was spiked with the PAAs under study. Extraction methods were liquid-liquid extraction (LLE, dispersive liquid-liquid microextraction (DLLME, and solid-phase extraction (SPE with C18 ec (octadecyl, HR-P (styrene/divinylbenzene, and SCX (strong cationic exchange cartridges. Extracted samples were detected and analyzed by HPLC-UV. In comparison between methods, recovery rate of SCX cartridge showed the best adsorption, up to 91% for polar PAAs (TDAs and MDAs. The interested PAAs are polar and relatively soluble in water, so a cartridge with cationic exchange properties has the best absorption and consequently the best recoveries.

  15. Synthesis of 3-Bromotetronamides via Amination of 3,4-Dibromofuran-2(5H)-one

    Energy Technology Data Exchange (ETDEWEB)

    Cunha, Silvio; Oliveira, Caio C., E-mail: silviodc@ufba.b [Universidade Federal da Bahia (IQ/UFBA), Salvador, BA (Brazil). Inst. de Quimica; Instituto Nacional de Ciencia e Tecnologia (INCT) em Energia, Salvador, BA (Brazil); Sabino, Jose R. [Universidade Federal de Goias (IF/UFG), Goiania (Brazil). Inst. de Fisica

    2011-07-01

    This work describes the direct synthesis of 3-bromotetronamides in good yields through the reaction of 3,4-dibromofuran-2(5H)-one, obtained from furfural, with primary and secondary amines. Aromatic amines were more tolerated than aliphatic and heteroaromatic ones. The X-ray structures of five derivatives are described. (author)

  16. Formation of heterocyclic amines in salami and ham pizza toppings during baking of frozen pizza.

    Science.gov (United States)

    Gibis, Monika; Weiss, Jochen

    2013-06-01

    Heterocyclic amines (HAs) are formed as Maillard reaction products in the crust of meat products during heating processes. Two typical pizza toppings--salami and cooked ham--were analyzed for the presence of HAs after baking frozen pizzas at top and bottom temperatures of 250 and 230 °C, respectively. After baking pizza slices for 12 min, MeIQx (2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline; 0.2 ng/g), 4,8-DiMeIQx (2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline; 0.5 ng/g), PhIP (2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine; 0.2 ng/g), norharman (4.5 ng/g), and harman (2.5 ng/g) were found in the ham toppings, whereas only the comutagenic norharman (107.4 ng/g) and harman (11.4 ng/g) were found in the salami toppings. The content of MeIQx and 4,8-DiMeIQx in ham increased from 0.3 to 1.8 ng/g and 0.8 to 1.6 ng/g, respectively, when the recommended baking time was increased from 15 min (manufacturer's specification) to 18 min at 230 °C. MeIQx was formed in salami when the heating time was extended to 18 min. Moreover, higher concentrations of PhIP in salami or ham slices were found when baking temperatures were 250 °C rather than 230 °C (baking time of 12 min). However, sensory tests showed that panelists preferred longer-baked pizzas due to an increased crispiness. Thus, results show that a substantial formation of HAs may occur in pizza toppings such as ham and salami, with ham being particularly susceptible when compared to salami. Formation of HAs increases with increasing baking time and temperature. The occurrence of the cupping of ham or salami slices during baking may also increase the formation of HAs. © 2013 Institute of Food Technologists®

  17. Ruthenium-complex catalyzed N-(cyclo)alkylation of aromatic amines with diols. Selective synthesis of N-(n-hydroixyalkyl)anilines of type PhNH(CH2)nOH and of some bioactive arylpiperazines,

    NARCIS (Netherlands)

    Koten, G. van; Abbenhuis, R.A.T.M.; Boersma, J.

    1998-01-01

    A new class of well-defined neutral mono-, and dicationic ruthenium(II) complexes containing a neutral terdentate donor system [C5H3N(CH2E)(2)-2,6] (E = PPh2 (PNP) or NMe2 (NN'N)) has been found effective as catalyst precursor in N-(cyclo)alkylation reactions of aromatic amines with diols

  18. Conversion of alcohols to enantiopure amines through dual-enzyme hydrogen-borrowing cascades.

    Science.gov (United States)

    Mutti, Francesco G; Knaus, Tanja; Scrutton, Nigel S; Breuer, Michael; Turner, Nicholas J

    2015-09-25

    α-Chiral amines are key intermediates for the synthesis of a plethora of chemical compounds at industrial scale. We present a biocatalytic hydrogen-borrowing amination of primary and secondary alcohols that allows for the efficient and environmentally benign production of enantiopure amines. The method relies on a combination of two enzymes: an alcohol dehydrogenase (from Aromatoleum sp., Lactobacillus sp., or Bacillus sp.) operating in tandem with an amine dehydrogenase (engineered from Bacillus sp.) to aminate a structurally diverse range of aromatic and aliphatic alcohols, yielding up to 96% conversion and 99% enantiomeric excess. Primary alcohols were aminated with high conversion (up to 99%). This redox self-sufficient cascade possesses high atom efficiency, sourcing nitrogen from ammonium and generating water as the sole by-product. Copyright © 2015, American Association for the Advancement of Science.

  19. Degradation of biogenetic amines by gamma radiation process and identification by GC/MS

    Energy Technology Data Exchange (ETDEWEB)

    Cardozo, Monique; Souza, Stefania P. de; Lima, Keila dos S.C.; Lima, Antonio L. dos S., E-mail: santoslima@ime.eb.br [Departamento de Quimica - IME, Instituto Militar de Engenharia, RJ (Brazil)

    2011-07-01

    Biogenic amines are low molecular weight organic bases with aliphatic (putrescine, cadaverine, spermine, spermidine), aromatic (tyramine, phenylethylamine) or heterocyclic (histamine, tryptamine) structures that can be found in several foods, in which they are mainly produced by microbial decarboxylation of amino acids. The reasons to control amines in food are their potential toxicity and their use like food quality markers. The consumption of food containing large amounts of biogenic amines can result in allergic reactions, characterized by difficulty in breathing, rash, vomiting, and hypertension. Biogenic amines are also known as possible precursors of carcinogens, such as N-nitrosamines. Traditionally, biogenic amine formation in food has been prevented, primarily by limiting microbial growth. However, control measures to reduce their levels once formed need to be also considered. The biogenic amines are frequently found in high concentrations and not reduced by high-temperature treatment, which makes difficult to use conventional methods of food preservation for this purpose. Food irradiation has been used in many countries for inhibition of sprouting, destruction of food borne insects, extension of shelf life or improvement of the technological of food. Irradiation is also known as a good method for inactivating pathogens and reducing microorganisms in food materials. Furthermore, besides the sanitary purpose, irradiation technology in new trials can be applied to induce radiolysis of toxic contaminants in food products reducing their content. This study has the objective to evaluate the effect of different gamma irradiation doses (1, 3 and 5kGy) in methanol solutions of three different biogenic amines: tryptamine, tyramine and b-phenylethylamine. The solutions were prepared using standard biogenic amines purchased from Sigma-Aldrich Brazil and methanol HPLC grade with a concentration of 100 {mu}g/mL. They were irradiated in Centro Tecnologico do Exercito

  20. Degradation of biogenetic amines by gamma radiation process and identification by GC/MS

    International Nuclear Information System (INIS)

    Cardozo, Monique; Souza, Stefania P. de; Lima, Keila dos S.C.; Lima, Antonio L. dos S.

    2011-01-01

    Biogenic amines are low molecular weight organic bases with aliphatic (putrescine, cadaverine, spermine, spermidine), aromatic (tyramine, phenylethylamine) or heterocyclic (histamine, tryptamine) structures that can be found in several foods, in which they are mainly produced by microbial decarboxylation of amino acids. The reasons to control amines in food are their potential toxicity and their use like food quality markers. The consumption of food containing large amounts of biogenic amines can result in allergic reactions, characterized by difficulty in breathing, rash, vomiting, and hypertension. Biogenic amines are also known as possible precursors of carcinogens, such as N-nitrosamines. Traditionally, biogenic amine formation in food has been prevented, primarily by limiting microbial growth. However, control measures to reduce their levels once formed need to be also considered. The biogenic amines are frequently found in high concentrations and not reduced by high-temperature treatment, which makes difficult to use conventional methods of food preservation for this purpose. Food irradiation has been used in many countries for inhibition of sprouting, destruction of food borne insects, extension of shelf life or improvement of the technological of food. Irradiation is also known as a good method for inactivating pathogens and reducing microorganisms in food materials. Furthermore, besides the sanitary purpose, irradiation technology in new trials can be applied to induce radiolysis of toxic contaminants in food products reducing their content. This study has the objective to evaluate the effect of different gamma irradiation doses (1, 3 and 5kGy) in methanol solutions of three different biogenic amines: tryptamine, tyramine and b-phenylethylamine. The solutions were prepared using standard biogenic amines purchased from Sigma-Aldrich Brazil and methanol HPLC grade with a concentration of 100 μg/mL. They were irradiated in Centro Tecnologico do Exercito

  1. Extrapolation of systemic bioavailability assessing skin absorption and epidermal and hepatic metabolism of aromatic amine hair dyes in vitro

    Energy Technology Data Exchange (ETDEWEB)

    Manwaring, John, E-mail: manwaring.jd@pg.com [Procter & Gamble Inc., Mason Business Center, Mason, OH 45040 (United States); Rothe, Helga [Procter & Gamble Service GmbH, Sulzbacher Str. 40, 65823 Schwalbach am Taunus (Germany); Obringer, Cindy; Foltz, David J.; Baker, Timothy R.; Troutman, John A. [Procter & Gamble Inc., Mason Business Center, Mason, OH 45040 (United States); Hewitt, Nicola J. [SWS, Erzhausen (Germany); Goebel, Carsten [Procter & Gamble Service GmbH, Sulzbacher Str. 40, 65823 Schwalbach am Taunus (Germany)

    2015-09-01

    Approaches to assess the role of absorption, metabolism and excretion of cosmetic ingredients that are based on the integration of different in vitro data are important for their safety assessment, specifically as it offers an opportunity to refine that safety assessment. In order to estimate systemic exposure (AUC) to aromatic amine hair dyes following typical product application conditions, skin penetration and epidermal and systemic metabolic conversion of the parent compound was assessed in human skin explants and human keratinocyte (HaCaT) and hepatocyte cultures. To estimate the amount of the aromatic amine that can reach the general circulation unchanged after passage through the skin the following toxicokinetically relevant parameters were applied: a) Michaelis–Menten kinetics to quantify the epidermal metabolism; b) the estimated keratinocyte cell abundance in the viable epidermis; c) the skin penetration rate; d) the calculated Mean Residence Time in the viable epidermis; e) the viable epidermis thickness and f) the skin permeability coefficient. In a next step, in vitro hepatocyte K{sub m} and V{sub max} values and whole liver mass and cell abundance were used to calculate the scaled intrinsic clearance, which was combined with liver blood flow and fraction of compound unbound in the blood to give hepatic clearance. The systemic exposure in the general circulation (AUC) was extrapolated using internal dose and hepatic clearance, and C{sub max} was extrapolated (conservative overestimation) using internal dose and volume of distribution, indicating that appropriate toxicokinetic information can be generated based solely on in vitro data. For the hair dye, p-phenylenediamine, these data were found to be in the same order of magnitude as those published for human volunteers. - Highlights: • An entirely in silico/in vitro approach to predict in vivo exposure to dermally applied hair dyes • Skin penetration and epidermal conversion assessed in human

  2. Extrapolation of systemic bioavailability assessing skin absorption and epidermal and hepatic metabolism of aromatic amine hair dyes in vitro

    International Nuclear Information System (INIS)

    Manwaring, John; Rothe, Helga; Obringer, Cindy; Foltz, David J.; Baker, Timothy R.; Troutman, John A.; Hewitt, Nicola J.; Goebel, Carsten

    2015-01-01

    Approaches to assess the role of absorption, metabolism and excretion of cosmetic ingredients that are based on the integration of different in vitro data are important for their safety assessment, specifically as it offers an opportunity to refine that safety assessment. In order to estimate systemic exposure (AUC) to aromatic amine hair dyes following typical product application conditions, skin penetration and epidermal and systemic metabolic conversion of the parent compound was assessed in human skin explants and human keratinocyte (HaCaT) and hepatocyte cultures. To estimate the amount of the aromatic amine that can reach the general circulation unchanged after passage through the skin the following toxicokinetically relevant parameters were applied: a) Michaelis–Menten kinetics to quantify the epidermal metabolism; b) the estimated keratinocyte cell abundance in the viable epidermis; c) the skin penetration rate; d) the calculated Mean Residence Time in the viable epidermis; e) the viable epidermis thickness and f) the skin permeability coefficient. In a next step, in vitro hepatocyte K m and V max values and whole liver mass and cell abundance were used to calculate the scaled intrinsic clearance, which was combined with liver blood flow and fraction of compound unbound in the blood to give hepatic clearance. The systemic exposure in the general circulation (AUC) was extrapolated using internal dose and hepatic clearance, and C max was extrapolated (conservative overestimation) using internal dose and volume of distribution, indicating that appropriate toxicokinetic information can be generated based solely on in vitro data. For the hair dye, p-phenylenediamine, these data were found to be in the same order of magnitude as those published for human volunteers. - Highlights: • An entirely in silico/in vitro approach to predict in vivo exposure to dermally applied hair dyes • Skin penetration and epidermal conversion assessed in human skin explants and

  3. Meat and components of meat and the risk of bladder cancer in the NIH-AARP Diet and Health Study

    OpenAIRE

    Ferrucci, Leah M.; Sinha, Rashmi; Ward, Mary H.; Graubard, Barry I.; Hollenbeck, Albert R.; Kilfoy, Briseis A.; Schatzkin, Arthur; Michaud, Dominique S.; Cross, Amanda J.

    2010-01-01

    BACKGROUND: Meat could be involved in bladder carcinogenesis via multiple potentially carcinogenic meat-related compounds related to cooking and processing, including nitrate, nitrite, heterocyclic amines (HCAs), and polycyclic aromatic hydrocarbons (PAHs). The authors comprehensively investigated the association between meat and meat components and bladder cancer. METHODS: During 7 years of follow-up, 854 transitional cell bladder-cancer cases were identified among 300,933 men and...

  4. In situ Generated Ruthenium Catalyst Systems Bearing Diverse N-Heterocyclic Carbene Precursors for Atom-Economic Amide Synthesis from Alcohols and Amines.

    Science.gov (United States)

    Cheng, Hua; Xiong, Mao-Qian; Cheng, Chuan-Xiang; Wang, Hua-Jing; Lu, Qiang; Liu, Hong-Fu; Yao, Fu-Bin; Chen, Cheng; Verpoort, Francis

    2018-02-16

    The transition-metal-catalyzed direct synthesis of amides from alcohols and amines is herein demonstrated as a highly environmentally benign and atom-economic process. Among various catalyst systems, in situ generated N-heterocyclic carbene (NHC)-based ruthenium (Ru) halide catalyst systems have been proven to be active for this transformation. However, these existing catalyst systems usually require an additional ligand to achieve satisfactory results. In this work, through extensive screening of a diverse variety of NHC precursors, we discovered an active in situ catalyst system for efficient amide synthesis without any additional ligand. Notably, this catalyst system was found to be insensitive to the electronic effects of the substrates, and various electron-deficient substrates, which were not highly reactive with our previous catalyst systems, could be employed to afford the corresponding amides efficiently. Furthermore, mechanistic investigations were performed to provide a rationale for the high activity of the optimized catalyst system. NMR-scale reactions indicated that the rapid formation of a Ru hydride intermediate (signal at δ=-7.8 ppm in the 1 H NMR spectrum) after the addition of the alcohol substrate should be pivotal in establishing the high catalyst activity. Besides, HRMS analysis provided possible structures of the in situ generated catalyst system. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Nickel-Catalyzed Synthesis of Primary Aryl and Heteroaryl Amines via C–O Bond Cleavage

    KAUST Repository

    Yue, Huifeng

    2017-03-13

    A nickel-catalyzed protocol for the conversion of aryl and heteroaryl alcohol derivatives to primary and secondary aromatic amines via C(sp2)-O bond cleavage is described. The new amination protocol can be applied to a range of substrates bearing diverse functional groups and uses readily available benzophenone imines as an effective nitrogen source.

  6. Nickel-Catalyzed Synthesis of Primary Aryl and Heteroaryl Amines via C–O Bond Cleavage

    KAUST Repository

    Yue, Huifeng; Guo, Lin; Liu, Xiangqian; Rueping, Magnus

    2017-01-01

    A nickel-catalyzed protocol for the conversion of aryl and heteroaryl alcohol derivatives to primary and secondary aromatic amines via C(sp2)-O bond cleavage is described. The new amination protocol can be applied to a range of substrates bearing diverse functional groups and uses readily available benzophenone imines as an effective nitrogen source.

  7. Development of second generation gold-supported palladium material with low-leaching and recyclable characteristics in aromatic amination.

    Science.gov (United States)

    Al-Amin, Mohammad; Arai, Satoshi; Hoshiya, Naoyoki; Honma, Tetsuo; Tamenori, Yusuke; Sato, Takatoshi; Yokoyama, Mami; Ishii, Akira; Takeuchi, Masashi; Maruko, Tomohiro; Shuto, Satoshi; Arisawa, Mitsuhiro

    2013-08-02

    An improved process for the preparation of sulfur-modified gold-supported palladium material [SAPd, second generation] is presented. The developed preparation method is safer and generates less heat (aqueous Na2S2O8 and H2SO4) for sulfur fixation on a gold surface, and it is superior to the previous method of preparing SAPd (first generation), which requires the use of the more heat-generating and dangerous piranha solution (concentrated H2SO4 and 35% H2O2) in the sulfur fixation step. This safer and improved preparation method is particularly important for the mass production of SAPd (second generation) for which the catalytic activity was examined in ligand-free Buchwald-Hartwig cross-coupling reactions. The catalytic activities were the same between the first and second generation SAPds in aromatic aminations, but the lower palladium leaching properties and safer preparative method of second generation SAPd are a significant improvement over the first generation SAPd.

  8. Determination of aromatic and PAH (polycyclic aromatic hydrocarbons) content of oily wastewaters

    Energy Technology Data Exchange (ETDEWEB)

    Lysyj, I.; Russell, E.C.

    1978-08-01

    An analytical scheme was developed for determining the total organic content and hydrocarbon concentration from a one-liter portion of a wastewater sample, and determining the volatile, suspended, and water-soluble fractions from a second, two-liter portion. Analyses of untreated and treated bilge wastewater from the U.S. Army Fort Eustis, Va., facility showed 10-300 ppm suspended organics and 10-300 ppm dissolved organics in the untreated bilge, and no suspended matter, but 700-2000 ppm dissolved organics, in the treated bilge wastewaters. Of the dissolved organics in untreated and treated wastewater, 70 and 10%, respectively, were extracted with chloroform; the organics in the treated water were probably biologically derived from petroleum degradation. Gas chromatographic/mass spectroscopic and high-pressure liquid chromatographic analyses of the chloroform extracts showed about equal parts of phenolic compounds and aromatic hydrocarbons, small amounts of heterocyclics, and traces of polycyclic aromatics in the untreated wastewater, and mainly phenolics in the treated water.

  9. Biotransformation and bioactivation reactions of alicyclic amines in drug molecules.

    Science.gov (United States)

    Bolleddula, Jayaprakasam; DeMent, Kevin; Driscoll, James P; Worboys, Philip; Brassil, Patrick J; Bourdet, David L

    2014-08-01

    Aliphatic nitrogen heterocycles such as piperazine, piperidine, pyrrolidine, morpholine, aziridine, azetidine, and azepane are well known building blocks in drug design and important core structures in approved drug therapies. These core units have been targets for metabolic attack by P450s and other drug metabolizing enzymes such as aldehyde oxidase and monoamine oxidase (MAOs). The electron rich nitrogen and/or α-carbons are often major sites of metabolism of alicyclic amines. The most common biotransformations include N-oxidation, N-conjugation, oxidative N-dealkylation, ring oxidation, and ring opening. In some instances, the metabolic pathways generate electrophilic reactive intermediates and cause bioactivation. However, potential bioactivation related adverse events can be attenuated by structural modifications. Hence it is important to understand the biotransformation pathways to design stable drug candidates that are devoid of metabolic liabilities early in the discovery stage. The current review provides a comprehensive summary of biotransformation and bioactivation pathways of aliphatic nitrogen containing heterocycles and strategies to mitigate metabolic liabilities.

  10. Influence of food condiments on the formation of carcinogenic heterocyclic amines in cooked chicken and determination by LC-MS/MS.

    Science.gov (United States)

    Khan, Mohammad Rizwan

    2015-01-01

    Heterocyclic amines (HCAs) are known to be suspected human carcinogens produced by high-temperature cooking of protein-rich foods such as meat and fish. In the present study, the influence of numerous food condiments on the formation of HCAs in cooked chicken was investigated. Chicken samples were subjected to pan-frying under controlled temperature. The levels of HCAs DMIP, MeIQx, 4,8-DiMeIQx, PhIP, harman and norharman were found to be between 0.93 and 27.52 ng g(-1), whereas IQ, MeIQ, AαC, MeAαC, Trp-P-1 and Trp-P-2 were found either below the limit of quantification or not detected in the control sample. Nevertheless, for samples cooked using food condiments, the amounts of HCAs (DMIP, MeIQx, 4,8-DiMeIQx and PhIP) were between 0.14 and 19.57 ng g(-1); harman and norharman were detected at higher concentrations up to 17.77 ng g(-1) while IQ and MeIQ were at levels below the limit of quantification; and AαC, MeAαC, Trp-P-1 and Trp-P-2 were not detected in any of the samples. The outcomes revealed that the formation of HCAs (except harman and norharman) diminished after the addition of food condiments. Edible oil contributed to the highest levels of HCA formation, followed by garlic, paprika, pepper and tomato.

  11. Presence of heterocyclic amine carcinogens in home-cooked and fast-food camel meat burgers commonly consumed in Saudi Arabia.

    Science.gov (United States)

    Rizwan Khan, Mohammad; Naushad, Mu; Abdullah Alothman, Zeid

    2017-05-10

    Heterocyclic amines (HCAs) are formed by cooking protein-rich foods, for instance, meat and fish, and are listed as possible human carcinogens. In the present study, the presence of five potential HCAs (IQ, MeIQ, MeIQx, 4,8-DiMeIQx, and PhIP) in cooked camel meat burgers was analyzed for the first time. The analysis was performed in home-cooked and fast-food burger samples containing food additives. The applied cooking technique for the home-cooked samples was pan frying for a controlled cooking time and temperature. In the control cooked meat samples (samples that contained no food additives), the concentrations of MeIQx, 4,8-DiMeIQx, and PhIP ranged from 2.47 ng/g to 4.89 ng/g, whereas IQ and MeIQ were found to be below the limit of quantification. The concentrations contents of MeIQx, 4,8-DiMeIQx, and PhIP in the home-cooked and fast-food samples ranged from 1.52 ng/g to 2.13 ng/g and 1.85 ng/g to 3.46 ng/g, respectively. IQ and MeIQ were not detected in either type of sample. In comparison to the control samples, the home-cooked and fast-food samples produced lower levels of HCAs. Such observations could result from the existence of antioxidants in incorporated food additives, which induce pro-oxidative effects with the successive formation and/or scavenging of free radicals.

  12. Catalytic chemical amide synthesis at room temperature: one more step toward peptide synthesis.

    Science.gov (United States)

    Mohy El Dine, Tharwat; Erb, William; Berhault, Yohann; Rouden, Jacques; Blanchet, Jérôme

    2015-05-01

    An efficient method has been developed for direct amide bond synthesis between carboxylic acids and amines via (2-(thiophen-2-ylmethyl)phenyl)boronic acid as a highly active bench-stable catalyst. This catalyst was found to be very effective at room temperature for a large range of substrates with slightly higher temperatures required for challenging ones. This methodology can be applied to aliphatic, α-hydroxyl, aromatic, and heteroaromatic acids as well as primary, secondary, heterocyclic, and even functionalized amines. Notably, N-Boc-protected amino acids were successfully coupled in good yields with very little racemization. An example of catalytic dipeptide synthesis is reported.

  13. Antioxidant capacity and inhibitory effect of grape seed and rosemary extract in marinades on the formation of heterocyclic amines in fried beef patties.

    Science.gov (United States)

    Gibis, Monika; Weiss, Jochen

    2012-09-15

    The effect of oil-based marinades containing grape seed extract (Vitis vinifera L.; 0.2, 0.4, 0.6 and 0.8 g/100g) formulated in a water/oil emulsion or rosemary extract (Rosmarinus officinalis; 0.12, 0.2, 0.6, 1.0 and 1.5 g/100g) in oil on the formation of heterocyclic amines (HAs) in fried beef patties was examined. After application of marinades and frying, four HAs MeIQx (2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline), PhIP (2-amino-1-methyl-6-phenylimidazo[4,5b]pyridine), Norharman, and Harman were found at low levels in all fried patties, MeIQx (0.3-1.0 ng/g), and PhIP (0.02-0.3 ng/g). The content of MeIQx and PhIP were significantly reduced by approx. 57% and 90% (pextract concentration. The antioxidant capacity of grape seed was about two-times greater than that of rosemary extract. A correlation between inhibition of HAs and Trolox-equivalents (MeIQx, R(2)=0.85, p<0.001; PhIP, R(2)=0.83, p<0.001) was found. Sensory tests showed a high acceptance of flavour and colour for controls and samples. Copyright © 2012 Elsevier Ltd. All rights reserved.

  14. In vitro disposition profiling of heterocyclic compounds.

    Science.gov (United States)

    Keemink, Janneke; Wuyts, Benjamin; Nicolaï, Johan; Jonghe, Steven De; Stella, Alessandro; Herdewijn, Piet; Augustijns, Patrick; Annaert, Pieter

    2015-08-01

    Compound libraries that are screened for biological activity commonly contain heterocycles. Besides potency, drug-like properties need to be evaluated to ensure in vivo efficacy of test compounds. In this context, we determined hepatic and intestinal disposition profiles for 17 heterocyclic compounds. All studied compounds showed rapid uptake in suspended rat hepatocytes, whereas metabolism was poor and the rate-limiting step in hepatic elimination. In vitro assays demonstrated a relatively low solubility and high intestinal permeability. Based on these in vitro data, heterocycles were categorized in the biopharmaceutics classification system (BCS) and the biopharmaceutics drug disposition classification system (BDDCS) to predict disposition characteristics before clinical data are available. Our findings emphasized the importance to use hepatocytes in addition to microsomes to study metabolism, since the latter lack non-microsomal enzymes and cellular context. Moreover, intracellular exposure should be considered to gain insight in the relevant fraction of the compound available at the enzymatic site. Finally, the study reveals discrepancies associated with the classification of heterocycles in BCS versus BDDCS. These probably originate from the binary character of both systems. Copyright © 2015 Elsevier B.V. All rights reserved.

  15. Solid-supported synthesis: From pharmacologically relevant heterocycles to biologically active surfaces

    DEFF Research Database (Denmark)

    Komnatnyy, Vitaly V.

    for solid-phase synthesis, methods for on - and off-bead screening of combinatorial libraries and their applic ation to various biological targets. The first part of the thesis is dedicated to the development of methodology for the synthesis of structurally diverse heterocyclic scaffolds via N...... methods for the controlled organo-functionalization of titanium, one of the most prominent materials in medicinal device industry, have been suggested . Initial acidic and oxidative treatment s of the metal surface genera te reactive hydroxyl moieties , which are subsequently modified with synthetically...... versatile amine -containing reagents. Subsequent applications in antimicrobial peptide synthesis, metal -catalysis, release from the surface, and polymer grafti ng, are also presented....

  16. Assembly of Four Diverse Heterocyclic Libraries Enabled by Prins Cyclization, Au-Catalyzed Enyne Cycloisomerization, and Automated Amide Synthesis

    Science.gov (United States)

    Cui, Jiayue; Chai, David I.; Miller, Christopher; Hao, Jason; Thomas, Christopher; Wang, JingQi; Scheidt, Karl A.; Kozmin, Sergey A.

    2013-01-01

    We describe a unified synthetic strategy for efficient assembly of four new heterocyclic libraries. The synthesis began by creating a range of structurally diverse pyrrolidinones or piperidinones. Such compounds were obtained in a simple one-flask operation starting with readily available amines, ketoesters, and unsaturated anhydrides. The use of tetrahydropyran-containing ketoesters, which were rapidly assembled by our Prins cyclization protocol, enabled efficient fusion of pyran and piperidinone cores. A newly developed Au(I)-catalyzed cycloisomerization of alkyne-containing enamides further expanded heterocyclic diversity by providing rapid entry into a wide range of bicyclic and tricyclic dienamides. The final stage of the process entailed diversification of each of the initially produced carboxylic acids using a fully automated platform for amide synthesis, which delivered 1872 compounds in high diastereomeric and chemical purity. PMID:22860634

  17. [Simultaneous determination of 33 primary aromatic amines in polystyrene and polyethylene masterbatches for foods by ultra-performance liquid chromatography-tandem mass spectrometry

    Science.gov (United States)

    Man, Zhengyin; Wang, Quanlin; Li, Hesheng; Zhang, Aizhi; Shen, Jian

    2015-03-01

    A comprehensive analytical method based on ultra-performance liquid chromatography coupled with triple quadrupole mass spectrometry (UPLC-MS/MS) has been developed for the simultaneous determination of 33 primary aromatic amines (PAAs) in polystyrene (PS) and polyethylene (PE) masterbatches for foods. The PS masterbatches were dissolved with dichloromethane, and methanol was added to precipitate after extraction by ultrasound extraction. Then the extract was purified by passing through a carbon graphite solid phase extraction column. The PE masterbatches were swelled and extracted with dichloromethane by ultrasound. The purified PS solution and PE extract were concentrated, and diluted to 2 mL with methanol-water (1:9, v/v), and filtered through the membranes of 0.22 µm before UPLC-MS/MS analysis. The analytes were separated on a BEH Phenyl column (100 mm x 2.1 mm, 1.7 µm), eluted by gradient with 0.07% (v/v) formic acid in methanol-water (1:9, v/v). The PAAs were detected by UPLC-MS/MS under multiple reaction monitoring (MRM) mode and quantified by the internal standard method. The separation conditions, fragment voltages and collision energies were optimized. The impacts of extraction times, extraction solvents and concentration methods on recoveries were studied. The limits of detection for the 33 primary aromatic amines were 6-10 µg/kg, and the limits of quantitation were 20-30 µg/kg. The mean recoveries of the two different masterbatch products at three spiked levels of 20, 100, 200 µg/kg were 61.3%-119.8%, and the relative standard deviations were 1.4%-14.8%. The experimental results indicated that the method is simple, rapid, sensitive, accurate, and can meet the related requirements for determination.

  18. 2-Phenyl-tetrahydropyrimidine-4(1H-ones – cyclic benzaldehyde aminals as precursors for functionalised β2-amino acids

    Directory of Open Access Journals (Sweden)

    Markus Nahrwold

    2009-09-01

    Full Text Available Novel procedures have been developed to condense benzaldehyde effectively with β-amino acid amides to cyclic benzyl aminals. Double carbamate protection of the heterocycle resulted in fully protected chiral β-alanine derivatives. These serve as universal precursors for the asymmetric synthesis of functionalised β2-amino acids containing acid-labile protected side chains. Diastereoselective alkylation of the tetrahydropyrimidinone is followed by a chemoselective two step degradation of the heterocycle to release the free β2-amino acid. In the course of this study, an L-asparagine derivative was condensed with benzaldehyde and subsequently converted to orthogonally protected (R-β2-homoaspartate.

  19. The Effect of n vs. iso Isomerization on the Thermophysical Properties of Aromatic and Non-aromatic Ionic Liquids.

    Science.gov (United States)

    Rodrigues, Ana S M C; Almeida, Hugo F D; Freire, Mara G; Lopes-da-Silva, José A; Coutinho, João A P; Santos, Luís M N B F

    2016-09-15

    This work explores the n vs. iso isomerization effects on the physicochemical properties of different families of ionic liquids (ILs) with variable aromaticity and ring size. This study comprises the experimental measurements, in a wide temperature range, of the ILs' thermal behavior, heat capacities, densities, refractive indices, surface tensions, and viscosities. The results here reported show that the presence of the iso -alkyl group leads to an increase of the temperature of the glass transition, T g . The iso- pyrrolidinium (5 atoms ring cation core) and iso -piperidinium (6 atoms ring cation core) ILs present a strong differentiation in the enthalpy and entropy of melting. Non-aromatic ILs have higher molar heat capacities due to the increase of the atomic contribution, whereas it was not found any significant differentiation between the n and iso -alkyl isomers. A small increase of the surface tension was observed for the non-aromatic ILs, which could be related to their higher cohesive energy of the bulk, while the lower surface entropy observed for the iso isomers indicates a structural resemblance between the IL bulk and surface. The significant differentiation between ILs with a 5 and 6 atoms ring cation in the n -alkyl series (where 5 atoms ring cations have higher surface entropy) is an indication of a more efficient arrangement of the non-polar region at the surface in ILs with smaller cation cores. The ILs constituted by non-aromatic piperidinium cation, and iso -alkyl isomers were found to be the most viscous among the studied ILs due to their higher energy barriers for shear stress.

  20. Studium interakce cytochromů P450 s potravními karcinogeny

    OpenAIRE

    Brabencová, Eliška

    2011-01-01

    Humans are exposed to various carcinogens during their life. One of the main sources of carcinogens is a human diet which plays an important role in the cancer development. This bachelor thesis deals with carcinogens that are formed during a technological food processing or cooking of food - polycyclic aromatic hydrocarbons, heterocyclic amines and nitrosamines, then carcinogens produced by fungi - mycotoxins, and carcinogens that are produced by plants - safrole, estragole and pyrrolizidine ...

  1. Synthesis and Antimicrobial Activity of New Schiff Base Compounds Containing 2-Hydroxy-4-pentadecylbenzaldehyde Moiety

    Directory of Open Access Journals (Sweden)

    Gadada Naganagowda

    2014-01-01

    Full Text Available Various novel Schiff base compounds have been synthesized by reaction of 2-hydroxy-4-pentadecylbenzaldehyde with substituted benzothiophene-2-carboxylic acid hydrazide and different substituted aromatic or heterocyclic amines in the presence of acetic acid in ethanol. The structures of all these compounds were confirmed by elemental analysis, IR, 1H-NMR, 13C-NMR, and mass spectral data and have been screened for antibacterial and antifungal activity.

  2. Extraction and spectrophotometric determination of molybdenum with omicron-hydroxythiophenols and aromatic amines

    International Nuclear Information System (INIS)

    Zalov, A.Z.; Verdizade, N.A.

    2015-01-01

    The interaction of molybdenum (VI) with o-hydroxythiophenol derivatives (HTPDs) and aromatic amines (AAs) was studied. The following three HTPDs, which contain different halogen atoms at position 5, were used: 2-hydroxy-5-chlorothiophenol(HCTP), 2-hydroxy-5-bromothiophenol (HBTP), 2-hydroxy-5-iodothiophenol (HITP)). The examined AAs were aniline (An), Nmethylaniline (mAn) and N,N-dimethylaniline (dAn). The obtained ternary complexes have a composition of 1:2:2 (Mo(V):HBTP:AA). Optimal conditions for their liquid-liquid extraction (LLE) were found: organic solvent (chloroform), pH (4-6), concentration of the reagents 10-3moldm-3 (AA)) and 10-3moldm-3 (HTPD) and (1.2-1.5) ((1.3-1.5) extraction time(colour develops almost immediately after the reagents addition). The absorbance of the extracts is stable for at least 48 hours. The optimum shaking time is 10 min.). Under the optimal max) at 515-538 conditions, the complexes have absorption maxima ( 104dm3mol-1 cm-1. The max) between 3.1 nm and molar absorptivities ( 98.4%. The results suggested that linear degrees of extraction were max or relationships exist between the spectral characteristics ( max) and some fundamental properties of the halogen substituent in the HTPD (atomic mass and electronegativity). The effect of foreign ions on the LLE-spectrophotometric determination of molybdenum was examined and two sensitive, selective and precise procedures for molybdenum determination were proposed. The relative standard deviations for Mo 10-4 % were 4% (HCTP-An procedure) and 3% (HBTP-An content of (3-5) procedure). (author)

  3. Ultrasound accelerated sulfonylation of amines by p-acetamidobenzenesulfonyl chloride using Mg–Al hydrotalcite as an efficient green base catalyst

    DEFF Research Database (Denmark)

    Truong, Binh Nhat; Le, Luong Huu; Chau, Duy-Khiem Nguyen

    2016-01-01

    The sulfonylation reaction of various aliphatic, alicyclic, aromatic, and hetero-aromatic amines with p-acetamidobenzenesulfonyl chloride has been investigated using different types of base catalysis under varied reaction conditions. Mg–Al hydrotalcite, characterizable as an inexpensive, reusable...

  4. Amide Synthesis from Alcohols and Amines by the Extrusion of Dihydrogen

    DEFF Research Database (Denmark)

    Nordstrøm, Lars Ulrik Rubæk; Vogt, Henning; Madsen, R.

    2008-01-01

    An environmentally friendly method for synthesis of amides is presented where a simple ruthenium catalyst mediates the direct coupling between an alcohol and an amine with the liberation of two molecules of dihydrogen. The active catalyst is generated in situ from an easily available ruthenium...... complex, an N-heterocyclic carbene and a phosphine. The reaction allows primary alcohols to be coupled with primary alkyamines to afford the corresponding secondary amides in good yields. The amide formation presumably proceeds through a catalytic cycle where the intermediate aldehyde and hemiaminal...

  5. Efficient one-pot, four-component synthesis of N,N-dibenzyl-N-{1-[5-(3-aryl-1,3,4-oxadiazol-2-yl]cyclobutyl}amine derivatives from the reaction of (isocyanoiminotriphenylphosphorane, dibenzylamine, an aromatic carboxylic acid and cyclobutanone

    Directory of Open Access Journals (Sweden)

    Shajari Nahid

    2012-01-01

    Full Text Available Four-component reaction of cyclobutanone, dibenzylamine and (Nisocyanimino triphenylphosphorane in the presence of aromatic carboxylic acids proceed smoothly at room temperature and under neutral conditions to afford N,N-dibenzyl-N-{1-[5-(3-aryl-1,3,4-oxadiazol-2-yl]cyclobutyl}amine derivatives in high yields.

  6. Rapid trifluoromethylation and perfluoroalkylation of five-membered heterocycles by photoredox catalysis in continuous flow.

    Science.gov (United States)

    Straathof, Natan J W; Gemoets, Hannes P L; Wang, Xiao; Schouten, Jaap C; Hessel, Volker; Noël, Timothy

    2014-06-01

    Trifluoromethylated and perfluoroalkylated heterocycles are important building blocks for the synthesis of numerous pharmaceutical products, agrochemicals and are widely applied in material sciences. To date, trifluoromethylated and perfluoroalkylated hetero-aromatic systems can be prepared utilizing visible light photoredox catalysis methodologies in batch. While several limitations are associated with these batch protocols, the application of microflow technology could greatly enhance and intensify these reactions. A simple and straightforward photocatalytic trifluoromethylation and perfluoroalkylation method has been developed in continuous microflow, using commercially available photocatalysts and microflow components. A selection of five-membered hetero-aromatics were successfully trifluoromethylated (12 examples) and perfluoroalkylated (5 examples) within several minutes (8-20 min). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Generation of N-Heterocycles via Tandem Reactions of N '-(2-Alkynylbenzylidene)hydrazides.

    Science.gov (United States)

    Qiu, Guanyinsheng; Wu, Jie

    2016-02-01

    As a powerful synthon, N '-(2-alkynylbenzylidene)hydrazides have been utilized efficiently for the construction of N-heterocycles. Since N '-(2-alkynylbenzylidene)hydrazides can easily undergo intramolecular 6-endo cyclization promoted by silver triflate or electrophiles, the resulting isoquinolinium-2-yl amides can proceed through subsequent transformations including [3 + 2] cycloaddition, nucleophilic addition, and [3 + 3] cycloaddition. Several unexpected rearrangements via radical processes were observed in some cases, which afforded nitrogen-containing heterocycles with molecular complexity. Reactive partners including internal alkynes, arynes, ketenimines, ketenes, allenoates, and activated alkenes reacted through [3 + 2] cycloaddition and subsequent aromatization, leading to diverse H-pyrazolo[5,1-a]isoquinolines with high efficiency. Nucleophilic addition to the in situ generated isoquinolinium-2-yl amide followed by aromatization also produced H-pyrazolo[5,1-a]isoquinoline derivatives when terminal alkynes, carbonyls, enamines, and activated methylene compounds were used as nucleophiles. Isoquinoline derivatives were obtained when indoles or phosphites were employed as nucleophiles in the reactions of N '-(2-alkynylbenzylidene)hydrazides. A tandem 6-endo cyclization and [3 + 3] cycloaddition of cyclopropane-1,1-dicarboxylates with N '-(2-alkynylbenzylidene)hydrazides was observed as well. Small libraries of these compounds were constructed. Biological evaluation suggested that some compounds showed promising activities for inhibition of CDC25B, TC-PTP, HCT-116, and PTP1B. © 2015 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. [2++2+2] Cycloisomerisation of Aromatic Cyanodiynes in the Synthesis of Pyridohelicenes and Their Analogues

    Czech Academy of Sciences Publication Activity Database

    Klívar, Jiří; Jančařík, Andrej; Šaman, David; Pohl, Radek; Fiedler, Pavel; Bednárová, Lucie; Starý, Ivo; Stará, Irena G.

    2016-01-01

    Roč. 22, č. 40 (2016), s. 14401-14405 ISSN 0947-6539 R&D Projects: GA ČR(CZ) GA14-29667S Institutional support: RVO:61388963 Keywords : aromatic compounds * chiral ity * helical structures * helicenes * heterocycles Subject RIV: CC - Organic Chemistry Impact factor: 5.317, year: 2016

  9. A study of structure–activity relationships of commercial tertiary amines for post-combustion CO_2 capture

    International Nuclear Information System (INIS)

    Xiao, Min; Liu, Helei; Idem, Raphael; Tontiwachwuthikul, Paitoon; Liang, Zhiwu

    2016-01-01

    Highlights: • Ethyl group is beneficial for tertiary amines of CO_2 absorption. • The existence of side carbon chain may promote the activity of tertiary amine. • Hydroxyl group reduces the equilibrium CO_2 solubility, k_2 and pKa. • Heterocyclic structure decrease the equilibrium CO_2 solubility, k_2 and pKa. • Hydroxyl group results in higher CO_2 absorption heat. - Abstract: This work examined the relationship between the structure of various commercial tertiary amines and their activity in CO_2 absorption/desorption in terms of rate of CO_2 absorption, equilibrium CO_2 loading, pKa and heat of CO_2 absorption in order to establish possible guidelines for selection of tertiary amine components for amine blends. Results show that any electron donating group linked directly to the nitrogen atom increases their reactivity with CO_2. In addition, the presence of steric hindrance effect and good water solubility also show enhancements in activity. In contrast, the existence of a hydroxyl group leads to a decrease in all the activity of the tertiary amine. The heat of CO_2 absorption of tertiary amines, which is closely related to the regeneration energy, can be reduced by decreasing the number of hydroxyethyl groups or by positing the hydroxyl group at the proper carbon relative to the nitrogen atom.

  10. Polycyclic aromatic hydrocarbons (PAHs) in a coal tar standard reference material - SRM 1597a updated

    Energy Technology Data Exchange (ETDEWEB)

    Wise, Stephen A.; Poster, Dianne L.; Rimmer, Catherine A.; Schubert, Patricia; Sander, Lane C.; Schantz, Michele M. [National Institute of Standards and Technology (NIST), Analytical Chemistry Division, Gaithersburg, MD (United States); Leigh, Stefan D. [National Institute of Standards and Technology (NIST), Statistical Engineering Division, Gaithersburg, MD (United States); Moessner, Stephanie [National Institute of Standards and Technology (NIST), Analytical Chemistry Division, Gaithersburg, MD (United States); GMP/Comparator Labs, Werthenstein Chemie AG, Industrie Nord, Schachen (Switzerland)

    2010-09-15

    SRM 1597 Complex Mixture of Polycyclic Aromatic Hydrocarbons from Coal Tar, originally issued in 1987, was recently reanalyzed and reissued as SRM 1597a with 34 certified, 46 reference, and 12 information concentrations (as mass fractions) for polycyclic aromatic hydrocarbons (PAHs) and polycyclic aromatic sulfur heterocycles (PASHs) including methyl-substituted PAHs and PASHs. The certified and reference concentrations (as mass fractions) were based on results of analyses of the coal tar material using multiple analytical techniques including gas chromatography/mass spectrometry on four different stationary phases and reversed-phase liquid chromatography. SRM 1597a is currently the most extensively characterized SRM for PAHs and PASHs. (orig.)

  11. Enhancing trichloroethylene degradation using non-aromatic compounds as growth substrates.

    Science.gov (United States)

    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.

  12. Quantitative LC–MS for water-soluble heterocyclic amines in fine aerosols (PM2.5) at Duke Forest, USA

    Science.gov (United States)

    In this study, a quantitative liquid chromatography-mass spectrometry (LC-MS) technique capable of measuring the concentrations of heterocyclic nitrogen compounds in ambient fine aerosols (PM2.5) has been developed. Quadrupole time-of-flight (Q-TOF) MS technology is used to provi...

  13. Multipotent MAO and cholinesterase inhibitors for the treatment of Alzheimer's disease: synthesis, pharmacological analysis and molecular modeling of heterocyclic substituted alkyl and cycloalkyl propargyl amine.

    Science.gov (United States)

    Samadi, Abdelouahid; de los Ríos, Cristóbal; Bolea, Irene; Chioua, Mourad; Iriepa, Isabel; Moraleda, Ignacio; Bartolini, Manuela; Andrisano, Vincenza; Gálvez, Enrique; Valderas, Carolina; Unzeta, Mercedes; Marco-Contelles, José

    2012-06-01

    The synthesis, pharmacological evaluation and molecular modeling of heterocyclic substituted alkyl and cycloalkyl propargyl amines 1-7 of type I, and 9-12 of type II, designed as multipotent inhibitors able to simultaneously inhibit monoamine oxidases (MAO-A/B) as well as cholinesterase (AChE/BuChE) enzymes, as potential drugs for the treatment of Alzheimer's disease, are described. Indole derivatives 1-7 of type I are well known MAO inhibitors whose capacity to inhibit AChE and BuChE was here investigated for the first time. As a result, compound 7 was identified as a MAO-B inhibitor (IC(50) = 31 ± 2 nM) and a moderately selective eqBuChE inhibitor (IC(50) = 4.7 ± 0.2 μM). Conversely, the new and readily available 5-amino-7-(prop-2-yn-1-yl)-6,7,8,9-tetrahydropyrido[2,3-b][1,6]naphthyridine derivatives 9-13 of type II are poor MAO inhibitors, but showed AChE selective inhibition, compound 12 being the most attractive as it acts as a non-competitive inhibitor on EeAChE (IC(50) = 25 ± 3 nM, K(i) = 65 nM). The ability of this compound to interact with the AChE peripheral binding site was confirmed by kinetic studies and by molecular modeling investigation. Studies on human ChEs confirmed that 12 is a selective AChE inhibitor with inhibitory potency in the submicromolar range. Moreover, in agreement with its mode of action, 12 was shown to be able to inhibit Aβ aggregation induced by hAChE by 30.6%. Copyright © 2012 Elsevier Masson SAS. All rights reserved.

  14. Microwave Assisted Condensation Reactions of 2-Aryl Hydrazonopropanals with Nucleophilic Reagents and Dimethyl Acetylenedicarboxylate

    Directory of Open Access Journals (Sweden)

    Rita M. Borik

    2007-08-01

    Full Text Available The reaction of methyl ketones 1a-g with dimethylformamide dimethylacetal (DMFDMA afforded the enaminones 2a-g, which were coupled with diazotized aromatic amines 3a,b to give the corresponding aryl hydrazones 6a-h. Condensation of compounds 6a-h with some aromatic heterocyclic amines afforded iminoarylhydrazones 9a-m. Enaminoazo compounds 12a,b could be obtained from condensation of 6c with secondary amines. The reaction of 6e,h with benzotriazolylacetone yielded 14a,b. Also, the reaction of 6a,b,d-f,h with glycine and hippuric acid in acetic anhydride afforded pyridazinone derivatives 17a-f. Synthesis of pyridazine carboxylic acid derivatives 22a,b from the reaction of 6b,e with dimethyl acetylenedicarboxylate (DMAD in the presence of triphenylphosphine at room temperature is also reported. Most of these reactions were conducted under irradiation in a microwave oven in the absence of solvent in an attempt to improve the product yields and to reduce the reaction times.

  15. Simultaneous analysis of nine aromatic amines in mainstream cigarette smoke using online solid-phase extraction combined with liquid chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Zhang, Jie; Bai, Ruoshi; Zhou, Zhaojuan; Liu, Xingyu; Zhou, Jun

    2017-04-01

    A fully automated analytical method was developed and validated by this present study. The method was based on two-dimensional (2D) online solid-phase extraction liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) to determine nine aromatic amines (AAs) in mainstream smoke (MSS) simultaneously. As a part of validation process, AAs yields for 16 top-selling commercial cigarettes from China market were evaluated by the developed method under both Health Canada Intensive (HCI) and ISO machine smoking regimes. The gas phase of MSS was trapped by 25 mL 0.6 M hydrochloric acid solution, while the particulate phase was collected on a glass fiber filter. Then, the glass fiber pad was extracted with hydrochloric acid solution in an ultrasonic bath. The extract was analyzed with 2D online SPE-LC-MS/MS. In order to minimize the matrix effects of sample on each analyte, two cartridges with different extraction mechanisms were utilized to cleanup disturbances of different polarity, which were performed by the 2D SPE. A phenyl-hexyl analytical column was used to achieve a chromatographic separation. Under the optimized conditions, the isomers of p-toluidine, m-toluidine and o-toluidine, 3-aminobiphenyl and 4-aminobiphenyl, and 1-naphthylamine and 2-naphthylamine were baseline separated with good peak shapes for the first time. The limits of detection for nine AAs ranged from 0.03 to 0.24 ng cig -1 . The recovery of the measurement of nine AAs was from 84.82 to 118.47%. The intra-day and inter-day precisions of nine AAs were less than 10 and 16%, respectively. Compared with ISO machine smoking regime, the AAs yields in MSS were 1.17 to 3.41 times higher under HCI machine smoking regime. Graphical abstract New method using online SPE-LC/MS/MS for analysis of aromatic amines in mainstream cigarette smoke.

  16. Inorganic heterocycles with two manganes or rhenium carbonyl units

    International Nuclear Information System (INIS)

    Kuellmer, V.; Vahrenkamp, H.

    1977-01-01

    From the reactive complexes [(CO) 4 M-E-Sn(CH 3 ) 3 ] 2 (M = Mn,Re; E = S,Se) with (CH 3 ) 2 PCl via the non-isolable four-membered ring intermediates [(CO) 4 M-E-P(CH 3 ) 2 ] 2 the six-membered heterocycles[-(CO) 4 M-P(CH 3 ) 2 -E-] 2 are formed. By use of (CH 3 ) 2 AsCl both the four-membered ring intermediates and the six-membered ring products can be isolated. The six-membered heterocycles can be opened by trimethylphosphine. (orig./HK) [de

  17. Biochemical interpretation of quantitative structure-activity relationships (QSAR) for biodegradation of N-heterocycles: a complementary approach to predict biodegradability.

    Science.gov (United States)

    Philipp, Bodo; Hoff, Malte; Germa, Florence; Schink, Bernhard; Beimborn, Dieter; Mersch-Sundermann, Volker

    2007-02-15

    Prediction of the biodegradability of organic compounds is an ecologically desirable and economically feasible tool for estimating the environmental fate of chemicals. We combined quantitative structure-activity relationships (QSAR) with the systematic collection of biochemical knowledge to establish rules for the prediction of aerobic biodegradation of N-heterocycles. Validated biodegradation data of 194 N-heterocyclic compounds were analyzed using the MULTICASE-method which delivered two QSAR models based on 17 activating (OSAR 1) and on 16 inactivating molecular fragments (GSAR 2), which were statistically significantly linked to efficient or poor biodegradability, respectively. The percentages of correct classifications were over 99% for both models, and cross-validation resulted in 67.9% (GSAR 1) and 70.4% (OSAR 2) correct predictions. Biochemical interpretation of the activating and inactivating characteristics of the molecular fragments delivered plausible mechanistic interpretations and enabled us to establish the following biodegradation rules: (1) Target sites for amidohydrolases and for cytochrome P450 monooxygenases enhance biodegradation of nonaromatic N-heterocycles. (2) Target sites for molybdenum hydroxylases enhance biodegradation of aromatic N-heterocycles. (3) Target sites for hydratation by an urocanase-like mechanism enhance biodegradation of imidazoles. Our complementary approach represents a feasible strategy for generating concrete rules for the prediction of biodegradability of organic compounds.

  18. Rational synthesis of AB-type N-substituted core-functionalized naphthalene diimides (cNDIs).

    Science.gov (United States)

    Berezin, Andrey A; Sciutto, Andrea; Demitri, Nicola; Bonifazi, Davide

    2015-04-17

    Acid-mediated transformation of tetraethyl 2,6-diethoxynaphthalene-1,4,5,8-tetracarboxylate selectively affords the core-substituted naphthalene-anhydride-ester (cNAE) in quantitative yield. This anhydride can be selectively converted into hetero-N-substituted core-functionalized naphthalene diimides (cNDIs) through sequential condensation reactions in the presence of the precursor amine with very high isolated yields over four steps. The approach can be applied to prepare a large variety of heterocyclic, aromatic, and aliphatic heterodiimides.

  19. Trace Amines and the Trace Amine-Associated Receptor 1: Pharmacology, Neurochemistry and Clinical Implications

    Directory of Open Access Journals (Sweden)

    Yue ePei

    2016-04-01

    Full Text Available Biogenic amines are a collection of endogenous molecules that play pivotal roles as neurotransmitters and hormones. In addition to the classical biogenic amines resulting from decarboxylation of aromatic acids, including dopamine (DA, norepinephrine, epinephrine, serotonin (5-HT and histamine, other biogenic amines, present at much lower concentrations in the central nervous system (CNS, and hence referred to as trace amines (TAs, are now recognized to play significant neurophysiological and behavioural functions. At the turn of the century, the discovery of the trace amine-associated receptor 1 (TAAR1, a phylogenetically conserved G protein-coupled receptor that is responsive to both TAs, such as β-phenylethylamine, octopamine and tyramine, and structurally-related amphetamines, unveiled mechanisms of action for TAs other than interference with aminergic pathways, laying the foundations for deciphering the functional significance of TAs and its mammalian CNS receptor, TAAR1. Although its molecular interactions and downstream targets have not been fully elucidated, TAAR1 activation triggers accumulation of intracellular cAMP, modulates PKA and PKC signalling and interferes with the β-arrestin2-dependent pathway via G protein-independent mechanisms. TAAR1 is uniquely positioned to exert direct control over DA and 5-HT neuronal firing and release, which has profound implications for understanding the pathophysiology of, and therefore designing more efficacious therapeutic interventions for, a range of neuropsychiatric disorders that involve aminergic dysregulation, including Parkinson’s disease, schizophrenia, mood disorders and addiction. Indeed, the recent development of novel pharmacological tools targeting TAAR1 has uncovered the remarkable potential of TAAR1-based medications as new generation pharmacotherapies in neuropsychiatry. This review summarizes recent developments in the study of TAs and TAAR1, their intricate neurochemistry and

  20. Intermolecular electron transfer between coumarin dyes and aromatic amines in Triton-X-100 micellar solutions: Evidence for Marcus inverted region

    Science.gov (United States)

    Kumbhakar, Manoj; Nath, Sukhendu; Mukherjee, Tulsi; Pal, Haridas

    2004-02-01

    Photoinduced electron transfer (ET) between coumarin dyes and aromatic amines has been investigated in Triton-X-100 micellar solutions and the results have been compared with those observed earlier in homogeneous medium. Significant static quenching of the coumarin fluorescence due to the presence of high concentration of amines around the coumarin fluorophore in the micelles has been observed in steady-state fluorescence studies. Time-resolved studies with nanosecond resolutions mostly show the dynamic part of the quenching for the excited coumarin dyes by the amine quenchers. A correlation of the quenching rate constants, estimated from the time-resolved measurements, with the free energy changes (ΔG0) of the ET reactions shows the typical bell shaped curve as predicted by Marcus outer-sphere ET theory. The inversion in the ET rates for the present systems occurs at an exergonicity (-ΔG0) of ~0.7-0.8 eV, which is unusually low considering the polarity of the Palisade layer of the micelles where the reactants reside. Present results have been rationalized on the basis of the two dimensional ET model assuming that the solvent relaxation in micellar media is much slower than the rate of the ET process. Detailed analysis of the experimental data shows that the diffusional model of the bimolecular quenching kinetics is not applicable for the ET reactions in the micellar solutions. In the present systems, the reactions can be better visualized as equivalent to intramolecular electron transfer processes, with statistical distribution of the donors and acceptors in the micelles. A low electron coupling (Vel) parameter is estimated from the correlation of the experimentally observed and the theoretically calculated ET rates, which indicates that the average donor-acceptor separation in the micellar ET reactions is substantially larger than for the donor-acceptor contact distance. Comparison of the Vel values in the micellar solution and in the donor-acceptor close

  1. Vapor pressures and sublimation enthalpies of novel bicyclic heterocycle derivatives

    International Nuclear Information System (INIS)

    Blokhina, Svetlana V.; Ol’khovich, Marina V.; Sharapova, Angelica V.; Perlovich, German L.; Proshin, Alexey N.

    2014-01-01

    Highlights: • The vapor pressures of novel bicyclo-derivatives of amine were measured. • Thermodynamic functions of sublimation were calculated. • The influence of substituent structure and chemical nature on the vapor pressure was studied. -- Abstract: The vapor pressures of five novel bicyclic heterocycle derivatives were measured over the temperature 341.15 to 396.15 K using the transpiration method by means of an inert gas carrier. From these results the standard enthalpies and Gibbs free energies of sublimation at the temperature 298.15 K were calculated. The effects of alkyl- and chloro-substitutions on changes in the thermodynamic functions have been investigated. Quantitative structure–property relationship on the basis HYBOT physico-chemical descriptors for biologically active compounds have been developed to predict the sublimation enthalpies and Gibbs free energies of the compounds studied

  2. Biotransformation of Trichoderma spp. and their tolerance to aromatic amines, a major class of pollutants.

    Science.gov (United States)

    Cocaign, Angélique; Bui, Linh-Chi; Silar, Philippe; Chan Ho Tong, Laetitia; Busi, Florent; Lamouri, Aazdine; Mougin, Christian; Rodrigues-Lima, Fernando; Dupret, Jean-Marie; Dairou, Julien

    2013-08-01

    Trichoderma spp. are cosmopolitan soil fungi that are highly resistant to many toxic compounds. Here, we show that Trichoderma virens and T. reesei are tolerant to aromatic amines (AA), a major class of pollutants including the highly toxic pesticide residue 3,4-dichloroaniline (3,4-DCA). In a previous study, we provided proof-of-concept remediation experiments in which another soil fungus, Podospora anserina, detoxifies 3,4-DCA through its arylamine N-acetyltransferase (NAT), a xenobiotic-metabolizing enzyme that enables acetyl coenzyme A-dependent detoxification of AA. To assess whether the N-acetylation pathway enables AA tolerance in Trichoderma spp., we cloned and characterized NATs from T. virens and T. reesei. We characterized recombinant enzymes by determining their catalytic efficiencies toward several toxic AA. Through a complementary approach, we also demonstrate that both Trichoderma species efficiently metabolize 3,4-DCA. Finally, we provide evidence that NAT-independent transformation is solely (in T. virens) or mainly (in T. reesei) responsible for the observed removal of 3,4-DCA. We conclude that T. virens and, to a lesser extent, T. reesei likely utilize another, unidentified, metabolic pathway for the detoxification of AA aside from acetylation. This is the first molecular and functional characterization of AA biotransformation in Trichoderma spp. Given the potential of Trichoderma for cleanup of contaminated soils, these results reveal new possibilities in the fungal remediation of AA-contaminated soil.

  3. The AHA Moment: Assessment of the Redox Stability of Ionic Liquids Based on Aromatic Heterocyclic Anions (AHAs) for Nuclear Separations and Electric Energy Storage.

    Science.gov (United States)

    Shkrob, Ilya A; Marin, Timothy W

    2015-11-19

    Because of their extended conjugated bond network, aromatic compounds generally have higher redox stability than less saturated compounds. We conjectured that ionic liquids (ILs) consisting of aromatic heterocyclic anions (AHAs) may exhibit improved radiation and electrochemical stability. Such properties are important in applications of these ILs as diluents in radionuclide separations and electrolytes in the electric energy storage devices. In this study, we systematically examine the redox chemistry of the AHAs. Three classes of these anions have been studied: (i) simple 5-atom ring AHAs, such as the pyrazolide and triazolides, (ii) AHAs containing an adjacent benzene ring, and (iii) AHAs containing electron-withdrawing groups that were introduced to reduce their basicity and interaction with metal ions. It is shown that fragmentation in the reduced and oxidized states of these AHAs does not generally occur, and the two main products, respectively, are the H atom adduct and the imidyl radical. The latter species occurs either as an N σ-radical or as an N π-radical, depending on the length of the N-N bond, and the state that is stabilized in the solid matrix is frequently different from that having the lowest energy in the gas phase. In some instances, the formation of the sandwich π-stack dimer radical anions has been observed. For trifluoromethylated anions, H adduct formation did not occur; instead, there was facile loss of fluoride from their fluorinated groups. The latter can be problematic in nuclear separations, but beneficial in batteries. Overall, our study suggests that AHA-based ILs are viable candidates for use as radiation-exposed diluents and electrolytes.

  4. The tert-Amino Effect in Heterocyclic Chemistry. Synthesis of Spiro Heterocycles

    Directory of Open Access Journals (Sweden)

    Y. Morzherin

    2005-09-01

    Full Text Available The tert-amino reaction effect was examined. A new method to synthesize spiro heterocycles is presented. It was shown that the “tert-amino effect” could be applied to the formation of spiro-fused heterocycles. The formation of spiro compounds proceeds in most cases in good yields in a one-pot reaction.

  5. Syntheses and structure characterization of ten acid-base hybrid crystals based on N-containing aromatic brønsted bases and mineral acids

    Science.gov (United States)

    Lin, Zhihao; Jin, Shouwen; Li, Xiaoliang; Xiao, Xiao; Hu, Kaikai; Guo, Ming; Chi, Xinchen; Liu, Hui; Wang, Daqi

    2017-10-01

    Cocrystallization of the aromatic brønsted bases with a series of mineral acids gave a total of ten hybrid salts with the compositions: (2-methylquinoline)2: (hydrochloride acid): 3H2O [(HL1)+. (L1)·· (Cl-) · (H2O)3] (1), (6-bromobenzo[d]thiazol-2-amine): (hydrochloride acid) [(HL2)+. (Cl-)] (2), (6-bromobenzo[d]thiazol-2-amine): (nitric acid) [(HL2)+. (NO3-)] (3), (6-bromobenzo[d]thiazol-2-amine): (sulfuric acid) [(HL2)+ · (HSO4)-] (4), (6-bromobenzo[d]thiazol-2-amine): (phosphoric acid) [(HL2)+ · (H2PO4)-] (5), (5,7-dimethyl-1,8-naphthyridine-2-amine): (hydrochloride acid): 3H2O [(HL3)+ · (Cl-) (H2O)3] (6), (5,7-dimethyl-1,8-naphthyridine-2-amine): (hydrobromic acid): CH3OH [(HL3)+ · (Br)- · CH3OH] (7), (5,7-dimethyl-1,8-naphthyridine-2-amine): (sulfuric acid): H2O [(HL3)+ · (HSO4)- · H2O] (8), (2-aminophenol): (phosphoric acid) [(HL4)+ · (H2PO4)-] (9), and (2-amino-4-chlorophenol): (phosphoric acid) [(HL5)+ · (H2PO4)-] (10). The ten salts have been characterized by X-ray diffraction analysis, IR, and elemental analysis, and the melting points of all the salts were also reported. And their structural and supramolecular aspects are fully analyzed. The result reveals that among the ten investigated crystals the ring N of the heterocycle or the NH2 in the aminophenol are protonated when the acids are deprotonated, and the crystal packing is interpreted in terms of the strong charge-assisted classical hydrogen bonds between the NH+/NH3+ and deprotonated acidic groups. Further analysis of the crystal packing of the salts indicated that a different family of additional CHsbnd O, CHsbnd Cl, CH3sbnd N, CH3sbnd O, CHsbnd Br, CH3sbnd Br, Brsbnd Cl, Clsbnd S, Osbnd S, Osbnd O, Brsbnd S, Hsbnd H, and π-π associations contribute to the stabilization and expansion of the total high-dimensional frameworks. For the coexistence of the various weak nonbonding interactions these structures adopted homo or hetero supramolecular synthons or both. Some classical

  6. Distributions of Polycyclic Aromatic Hydrocarbons, Aromatic Ketones, Carboxylic Acids, and Trace Metals in Arctic Aerosols: Long-Range Atmospheric Transport, Photochemical Degradation/Production at Polar Sunrise.

    Science.gov (United States)

    Singh, Dharmendra Kumar; Kawamura, Kimitaka; Yanase, Ayako; Barrie, Leonard A

    2017-08-15

    The distributions, correlations, and source apportionment of aromatic acids, aromatic ketones, polycyclic aromatic hydrocarbons (PAHs), and trace metals were studied in Canadian high Arctic aerosols. Nineteen PAHs including minor sulfur-containing heterocyclic PAH (dibenzothiophene) and major 6 carcinogenic PAHs were detected with a high proportion of fluoranthene followed by benzo[k]fluoranthene, pyrene, and chrysene. However, in the sunlit period of spring, their concentrations significantly declined likely due to photochemical decomposition. During the polar sunrise from mid-March to mid-April, benzo[a]pyrene to benzo[e]pyrene ratios significantly dropped, and the ratios diminished further from late April to May onward. These results suggest that PAHs transported over the Arctic are subjected to strong photochemical degradation at polar sunrise. Although aromatic ketones decreased in spring, concentrations of some aromatic acids such as benzoic and phthalic acids increased during the course of polar sunrise, suggesting that aromatic hydrocarbons are oxidized to result in aromatic acids. However, PAHs do not act as the major source for low molecular weight (LMW) diacids such as oxalic acid that are largely formed at polar sunrise in the arctic atmosphere because PAHs are 1 to 2 orders of magnitude less abundant than LMW diacids. Correlations of trace metals with organics, their sources, and the possible role of trace transition metals are explained.

  7. Heterocyclic Scaffolds: Centrality in Anticancer Drug Development.

    Science.gov (United States)

    Ali, Imran; Lone, Mohammad Nadeem; Al-Othman, Zeid A; Al-Warthan, Abdulrahman; Sanagi, Mohd Marsin

    2015-01-01

    Cancer has been cursed for human beings for long time. Millions people lost their lives due to cancer. Despite of the several anticancer drugs available, cancer cannot be cured; especially at the late stages without showing any side effect. Heterocyclic compounds exhibit exciting medicinal properties including anticancer. Some market selling heterocyclic anticancer drugs include 5-flourouracil, methortrexate, doxorubicin, daunorubicin, etc. Besides, some natural products such as vinblastine and vincristine are also used as anticancer drugs. Overall, heterocyclic moeities have always been core parts in the expansion of anticancer drugs. This article describes the importance of heterocyclic nuclei in the development of anticancer drugs. Besides, the attempts have been made to discuss both naturally occurring and synthetic heterocyclic compounds as anticancer agents. In addition, some market selling anticancer heterocyclic compounds have been described. Moreover, the efforts have been made to discuss the mechanisms of actions and recent advances in heterocyclic compounds as anticancer agents. The current challenges and future prospectives of heterocyclic compounds have also been discussed. Finally, the suggestions for syntheses of effective, selective, fast and human friendly anticancer agents are discussed into the different sections.

  8. Electronic bond tuning with heterocyclic carbenes

    KAUST Repository

    Falivene, Laura

    2013-01-01

    We discuss the impact of the nature of the heterocyclic carbene ring, when used as a complex forming ligand, on the relative stability of key intermediates in three typical Ru, Pd and Au promoted reactions. Results show that P-heterocyclic carbenes have a propensity to increase the bonding of the labile ligand and of the substrate in Ru-promoted olefin metathesis, whereas negligible impact is expected on the stability of the ruthenacycle intermediate. In the case of Pd cross-coupling reactions, dissociation of a P-heterocyclic carbene is easier than dissociation of the N-heterocyclic analogue. In the case of the Au-OH synthon, the Au-OH bond is weakened with the P-heterocyclic carbene ligands. A detailed energy decomposition analysis is performed to rationalize these results. © 2013 The Royal Society of Chemistry.

  9. Synthesis of heterocycles: Indolo (2,1-a) isoquinolines, renewables, and aptamer ligands for cellular imaging

    Energy Technology Data Exchange (ETDEWEB)

    Beasley, Jonathan [Ames Laboratory (AMES), Ames, IA (United States)

    2013-01-01

    In this thesis, we explore both total syntheses and methodologies of several aromatic heterocyclic molecules. Extensions of the Kraus indole synthesis toward 2-substituted and 2,3-disubstituted indoles, as well as biologically attractive indolo[2,1-a]isoquinolines are described. Recent renewable efforts directed to commodity maleic acid and the first reported furan-based ionic liquids are described. Our total synthesis of mRNA aptamer ligand PDC-Gly, and its dye coupled forms, plus aminoglycoside dye coupled ligands used in molecular imaging, are described.

  10. Quantum chemical modeling of the inhibition mechanism of monoamine oxidase by oxazolidinone and analogous heterocyclic compounds.

    Science.gov (United States)

    Erdem, Safiye Sağ; Özpınar, Gül Altınbaş; Boz, Ümüt

    2014-02-01

    Monoamine oxidase (MAO, EC 1.4.3.4) is responsible from the oxidation of a variety of amine neurotransmitters. MAO inhibitors are used for the treatment of depression or Parkinson's disease. They also inhibit the catabolism of dietary amines. According to one hypothesis, inactivation results from the formation of a covalent adduct to a cysteine residue in the enzyme. If the adduct is stable enough, the enzyme is inhibited for a long time. After a while, enzyme can turn to its active form as a result of adduct breakdown by β-elimination. In this study, the proposed inactivation mechanism was modeled and tested by quantum chemical calculations. Eight heterocyclic methylthioamine derivatives were selected to represent the proposed covalent adducts. Activation energies related to their β-elimination reactions were calculated using ab initio and density functional theory methods. Calculated activation energies were in good agreement with the relative stabilities of the hypothetical adducts predicted in the literature by enzyme inactivation measurements.

  11. Synthesis of heterocyclic chalcone derivatives and their radical scavenging ability toward 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radicals

    International Nuclear Information System (INIS)

    Hwang, Kijun; Kim, Hoseok; Kim, Beomtae; Han, Incheol

    2012-01-01

    A series of heterocyclic chalcone derivatives bearing heterocycles such as thiophene or furan ring as an isostere of benzene ring were carefully prepared, and the influence of heterocycles on 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging activities was systematically investigated. Structure-activity relationships (SAR) analysis showed that the activities of thiophene ring-containing chalcones were higher than those of furan ring containing chalcones, and the presence of methyl substituent of heterocyclic ring distinctly affected the activities compared with non-substituted heterocycles in an opposite manner, with the 4'-methyl group of thiophene ring increasing activity and the 3'-methyl group of the furan ring decreasing activity. The distinct isosteric effect of heterocycles (i.e., thiophene or furan ring) on radical scavenging activities of heterocyclic chalcones was distinctly demonstrated in our work

  12. Capturing Labile Sulfenamide and Sulfinamide Serum Albumin Adducts of Carcinogenic Arylamines by Chemical Oxidation

    Science.gov (United States)

    Peng, Lijuan; Turesky, Robert J.

    2013-01-01

    Aromatic amines and heterocyclic aromatic amines (HAAs) are a class of structurally related carcinogens that are formed during the combustion of tobacco or during the high temperature cooking of meats. These procarcinogens undergo metabolic activation by N-oxidation of the exocyclic amine group to produce N-hydroxylated metabolites, which are critical intermediates implicated in toxicity and DNA damage. The arylhydroxylamines and their oxidized arylnitroso derivatives can also react with cysteine (Cys) residues of glutathione or proteins to form, respectively, sulfenamide and sulfinamide adducts. However, sulfur-nitrogen linked adducted proteins are often difficult to detect because they are unstable and undergo hydrolysis during proteolytic digestion. Synthetic N-oxidized intermediates of 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), a carcinogenic HAA produced in cooked meats, and 4-aminobiphenyl, a carcinogenic aromatic amine present in tobacco smoke were reacted with human serum albumin (SA) and formed labile sulfenamide or sulfinamide adducts at the Cys34 residue. Oxidation of the carcinogen-modified SA with m-chloroperoxybenzoic acid (m-CPBA) produced the arylsulfonamide adducts, which were stable to heat and the chemical reduction conditions employed to denature SA. The sulfonamide adducts of PhIP and 4-ABP were identified, by liquid chromatography/mass spectrometry, in proteolytic digests of denatured SA. Thus, selective oxidation of arylamine-modified SA produces stable arylsulfonamide-SA adducts, which may serve as biomarkers of these tobacco and dietary carcinogens. PMID:23240913

  13. Thermodynamics of mixtures containing amines. IX. Application of the concentration-concentration structure factor to the study of binary mixtures containing pyridines

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez, Juan Antonio, E-mail: jagl@termo.uva.es [G.E.T.E.F. Dpto Termodinamica y Fisica Aplicada, Facultad de Ciencias, Universidad de Valladolid, Valladolid 47071 (Spain); Cobos, Jose Carlos; Garcia de la Fuente, Isaias; Mozo, Ismael [G.E.T.E.F. Dpto Termodinamica y Fisica Aplicada, Facultad de Ciencias, Universidad de Valladolid, Valladolid 47071 (Spain)

    2009-10-10

    Binary mixtures formed by a pyridine base and an alkane, or an aromatic hydrocarbon, or a 1-alkanol have been studied in the framework of the concentration-concentration structure factor, S{sub CC}(0), formalism. Deviations between experimental data and those provided by the DISQUAC model are discussed. Systems containing alkanes are characterized by homocoordination. In pyridine + alkane mixtures, S{sub CC}(0) decreases with the chain length of the longer alkanes, due to size effects. For a given alkane, S{sub CC}(0) also decreases with the number of CH{sub 3}- groups in the pyridine base. This has been interpreted assuming that the number of amine-amine interactions available to be broken upon mixing also decreases similarly, probably as steric hindrances exerted by the methyl groups of the aromatic amine increase with the number of these groups. Homocoordination is higher in mixtures with 3,5-dimethylpyridine than in those with 2,6-dimethylpyridine. That is, steric effects exerted by methyl groups in positions 3 and 5 are stronger than when they are in positions 2 and 6. Similarly, from the application of the DISQUAC (dispersive-quasichemical) model, it is possible to conclude that homocoordination is higher in systems with 3- or 4-methylpyridine than in those involving 2-methylpyridine. Systems including aromatic hydrocarbons are nearly ideal, which seems to indicate that there is no specific interaction in such solutions. Mixtures with 1-alkanols show heterocoordination. This reveals the existence of interactions between unlike molecules, characteristic of alkanol + amine mixtures. Methanol systems show the lowest S{sub CC}(0) values due, partially, to size effects. This explains the observed decrease of homocoordination in such solutions in the order: pyridine > 2-methylpyridine > 2,6-dimethylpyridine. Moreover, as the energies of the OH-N hydrogen bonds are practically independent of the pyridine base considered when mixed with methanol, it suggests that

  14. Suppression of autophagy enhances the cytotoxicity of the DNA-damaging aromatic amine p-anilinoaniline

    International Nuclear Information System (INIS)

    Elliott, Althea; Reiners, John J.

    2008-01-01

    p-Anilinoaniline (pAA) is an aromatic amine that is widely used in hair dying applications. It is also a metabolite of metanil yellow, an azo dye that is commonly used as a food coloring agent. Concentrations of pAA between 10 and 25 μM were cytostatic to cultures of the normal human mammary epithelia cell line MCF10A. Concentrations ≥ 50 μM were cytotoxic. Cytostatic concentrations induced transient G 1 and S cell cycle phase arrests; whereas cytotoxic concentrations induced protracted arrests. Cytotoxic concentrations of pAA caused DNA damage, as monitored by the alkaline single-cell gel electrophoresis (Comet) assay, and morphological changes consistent with cells undergoing apoptosis and/or autophagy. Enzymatic and western blot analyses, and binding analyses of fluorescent labeled VAD-FMK, suggested that caspase family members were activated by pAA. Western blot analyses documented the conversion of LC3-I to LC3-II, a post-translational modification involved in the development of the autophagosome. Suppression of autophagosome formation, via knockdown of ATG7 with shRNA, prevented pAA-induced vacuolization, enhanced the activation of pro-caspase-3, and increased susceptibility of ATG7-deficient cells to the cytostatic and cytotoxic activities of markedly lower concentrations of pAA. Cells stably transfected with a nonsense shRNA behaved like parental MCF10A cells. Collectively, these data suggest that MCF10A cultures undergo autophagy as a pro-survival response to concentrations of pAA sufficient to induce DNA damage

  15. C-H functionalization directed by transformable nitrogen heterocycles: synthesis of ortho-oxygenated arylnaphthalenes from arylphthalazines.

    Science.gov (United States)

    Rastogi, Shiva K; Medellin, Derek C; Kornienko, Alexander

    2014-01-21

    Two protocols for oxygenation of aromatic C-H bonds ortho-positioned to the phthalazine ring were developed. The transannulation of the phthalazine ring to a naphthalene moiety by an Inverse Electron Demand Diels-Alder (IEDDA) reaction led to the synthesis of naphtho[2,1-c]chromenes, 1-(ortho-hydroxyaryl)naphthalenes and 6,7-dihydrobenzo[b]naphtho[1,2-d]oxepine. This new strategy based on the utilization of transformable nitrogen heterocycles in C-H functionalization chemistry can be potentially applicable to the synthesis of a broad range of biaryl compounds.

  16. Synthesis and stereochemical investigation of potential saturated heterocyclic drugs Pt. 1

    International Nuclear Information System (INIS)

    Bernath, G.

    1982-01-01

    Studies of partially and fully saturated heterocyclic compounds with condensed skeleton containing two heteroatoms are presented. The synthesis, stereochemical and conformation analyses aimed at the synthesis of potential drugs. Dihydro- and tetrahydro-1,3-oxazines were prepared from alicyclic 1,3-amino-alcohols by ring closure with aldehydes or imide esters. 1,3-oxazine-4-one derivatives were prepared by reacting alicyclic cis- and trans-2-hydroxy-1-carboxamides with aliphatic or aromatic aldehides. The conformations of the compounds prepared were determined by means of NMR spectroscopy. The main results of the determination of the steric structure of some representatives of the above described families of compounds by means of X-ray diffraction analysis are also presented. (author)

  17. Tris[2-(2H-indazol-2-ylethyl]amine

    Directory of Open Access Journals (Sweden)

    Saúl Ovalle

    2012-06-01

    Full Text Available The title tertiary amine, C27H27N7, a potential tripodal ligand for coordination chemistry, crystallizes with the central N atom located on a threefold axis of a trigonal cell. The gauche conformation of the N(amime—CH2—CH2—N(indazole chain [torsion angle = −64.2 (2°] places the pendant 2H-indazole heterocycles surrounding the symmetry axis, affording a claw-like shaped molecule. Two symmetry-related indazole planes in the molecule make an acute angle of 60.39 (4°. The lone pair of the tertiary N atom is located inside the cavity, and should thus be inactive (as a ligand. In the crystal, neither significant π–π nor C—H...π interactions between molecules are found.

  18. A multi-purpose tool for food inspection: Simultaneous determination of various classes of preservatives and biogenic amines in meat and fish products by LC-MS.

    Science.gov (United States)

    Molognoni, Luciano; Daguer, Heitor; de Sá Ploêncio, Leandro Antunes; De Dea Lindner, Juliano

    2018-02-01

    This paper describes an innovative fast and multipurpose method for the chemical inspection of meat and fish products by liquid chromatography-tandem mass spectrometry. Solid-liquid extraction and low temperature partitioning were applied to 17 analytes, which included large bacteriocins (3.5kDa) and small molecules (organic acids, heterocyclic compounds, polyene macrolides, alkyl esters of the p-hydroxybenzoic acid, aromatic, and aliphatic biogenic amines and polyamines). Chromatographic separation was achieved in 10min, using stationary phase of di-isopropyl-3-aminopropyl silane bound to hydroxylated silica. Method validation was in accordance to Commission Decision 657/2002/CE. Linear ranges were among 1.25-10.0mgkg -1 (natamycin and parabens), 2.50-10.0mgkg -1 (sorbate and nisin), 25.0-200mgkg -1 (biogenic amines, hexamethylenetetramine, benzoic and lactic acids), and 50.0-400mgkg -1 (citric acid). Expanded measurement uncertainty (U) was estimated by single laboratory validation combined to modeling in two calculation approaches: internal (U = 5%) and external standardization (U = 24%). Method applicability was checked on 89 real samples among raw, cooked, dry fermented and cured products, yielding acceptable recoveries. Many regulatory issues were revealed, corroborating the need for enhancement of the current analytical methods. This simple execution method dispenses the use of additional procedures of extraction and, therefore, reduces costs over time. It is suitable for routine analysis as a screening or confirmatory tool for both qualitative and quantitative results, replacing many time consuming analytical procedures. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Synthesis and antimicrobial activity of new heterocyclic compounds containing thieno[3,2-c] coumarin and pyrazolo[4,3-c] coumarin frameworks.

    Science.gov (United States)

    El-Dean, Adel M Kamal; Zaki, Remon M; Geies, Ahmed A; Radwan, Shaban M; Tolba, Mahmoud S

    2013-01-01

    Reaction of 4-chlorocoumarin-3-carbonitrile with ethyl thioglycolate and ethyl glycinate hydrochloride leads to a series of title products. Hydrazinolysis of amino thienocoumarin carboxylate afforded the hydrazine derivative which underwent various reactions to build new heterocyclic rings containing thienocoumarin moiety. Chloro acetylation of aminoester compound afforded the chloro acetyl amino which underwent nucleophilic substitution reactions various amines. The following treatment with formaldehyde under Mannich conditions afforded the corresponding imidazo derivatives. Reaction of Ghloroacetylamino with potassium thiocyanate yielded ethylpyrimidothieno coumarin sulfanylacetate which was used as a versatile precursor for synthesis of other heterocycles. On the other hand, reaction of chloro coumarin carbo nitrile with hydrazine gave the aminopyrazolocoumaine which reacted with bifunctionally compounds to give the substituted pyrimido derivatives. Diazotization and coupling of aminopyrazole with ethylcyanoacetate yielded ethylaminotriazinopyrazolocoumarine carboxylate. Several of the compounds obtained demonstrated considerable antifungal and antibacterial activity in the in vitro test systems.

  20. Design and synthesis of novel diphenyl oxalamide and diphenyl acetamide derivatives as anticonvulsants.

    Science.gov (United States)

    Nikalje, Anna Pratima G; Ghodke, Mangesh; Girbane, Amol

    2012-01-01

    A series of novel N(1) -substituted-N(2) ,N(2) -diphenyl oxalamides 3a-l were synthesized in good yield by stirring diphenylcarbamoyl formyl chloride (2) and various substituted aliphatic, alicyclic, aromatic, heterocyclic amines in DMF and K(2) CO(3) . Also 2-substituted amino-N,N-diphenylacetamides 5a-m were designed by pharmacophore generation and synthesized by stirring 2-chloro-N,N-diphenylacetamide (4) and various substituted amines in acetone using triethyl amine as a catalyst. All the synthesized compounds were screened for anticonvulsant activity in Swiss albino mice by MES and ScPTZ induced seizure tests. Neurotoxicity screening and behavioral testing was also carried out. Some of the synthesized test compounds were found to be more potent than the standard drug. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Anomalous length dependence of conductance of aromatic nanoribbons with amine anchoring groups

    KAUST Repository

    Bilić, Ante; Sanvito, Stefano

    2012-01-01

    for longer members of the series. The oligoperylene nanoribbons, with dual amine groups at both terminals, show the potential to fully harness the highly conjugated system of π molecular orbitals across the junction. © 2012 American Physical Society.

  2. Stable and Inert Cobalt Catalysts for Highly Selective and Practical Hydrogenation of C≡N and C═O Bonds.

    Science.gov (United States)

    Chen, Feng; Topf, Christoph; Radnik, Jörg; Kreyenschulte, Carsten; Lund, Henrik; Schneider, Matthias; Surkus, Annette-Enrica; He, Lin; Junge, Kathrin; Beller, Matthias

    2016-07-20

    Novel heterogeneous cobalt-based catalysts have been prepared by pyrolysis of cobalt complexes with nitrogen ligands on different inorganic supports. The activity and selectivity of the resulting materials in the hydrogenation of nitriles and carbonyl compounds is strongly influenced by the modification of the support and the nitrogen-containing ligand. The optimal catalyst system ([Co(OAc)2/Phen@α-Al2O3]-800 = Cat. E) allows for efficient reduction of both aromatic and aliphatic nitriles including industrially relevant dinitriles to primary amines under mild conditions. The generality and practicability of this system is further demonstrated in the hydrogenation of diverse aliphatic, aromatic, and heterocyclic ketones as well as aldehydes, which are readily reduced to the corresponding alcohols.

  3. Flow chemistry and polymer-supported pseudoenantiomeric acylating agents enable parallel kinetic resolution of chiral saturated N-heterocycles

    Science.gov (United States)

    Kreituss, Imants; Bode, Jeffrey W.

    2017-05-01

    Kinetic resolution is a common method to obtain enantioenriched material from a racemic mixture. This process will deliver enantiopure unreacted material when the selectivity factor of the process, s, is greater than 1; however, the scalemic reaction product is often discarded. Parallel kinetic resolution, on the other hand, provides access to two enantioenriched products from a single racemic starting material, but suffers from a variety of practical challenges regarding experimental design that limit its applications. Here, we describe the development of a flow-based system that enables practical parallel kinetic resolution of saturated N-heterocycles. This process provides access to both enantiomers of the starting material in good yield and high enantiopurity; similar results with classical kinetic resolution would require selectivity factors in the range of s = 100. To achieve this, two immobilized quasienantiomeric acylating agents were designed for the asymmetric acylation of racemic saturated N-heterocycles. Using the flow-based system we could efficiently separate, recover and reuse the polymer-supported reagents. The amide products could be readily separated and hydrolysed to the corresponding amines without detectable epimerization.

  4. Molecular cloning, expression, and characterization of mouse amine N-sulfotransferases

    International Nuclear Information System (INIS)

    Takahashi, Saki; Sakakibara, Yoichi; Mishiro, Emi; Kouriki, Haruna; Nobe, Rika; Kurogi, Katsuhisa; Yasuda, Shin; Liu, M.-C.; Suiko, Masahito

    2008-01-01

    By searching the GenBank database, we recently identified a novel mouse cytosolic sulfotransferase (SULT) cDNA (IMAGE Clone ID 679629) and a novel mouse SULT gene (LOC 215895). Sequence analysis revealed that both mouse SULTs belong to the cytosolic SULT3 gene family. The recombinant form of these two newly identified SULTs, designated SULT3A1 and SULT3A2, were expressed using the pGEX-4T-1 glutathione S-transferase fusion system and purified from transformed BL21 Escherichia coli cells. Both purified SULT3A1 and SULT3A2 exhibited strong amine N-sulfonating activities toward 1-naphthylamine among a variety of endogenous and xenobiotic compounds tested as substrates. Kinetic constants of the sulfation of 1-naphthylamine and 1-naphthol by these two enzymes were determined. Collectively, these results imply that these two amine-sulfonating SULT3s may play essential roles in the metabolism and detoxification of aromatic amine compounds in the body

  5. Thermodynamics of mixtures containing amines

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez, Juan Antonio [G.E.T.E.F. Dpto Termodinamica y Fisica Aplicada, Facultad de Ciencias, Universidad de Valladolid, Valladolid 47071 (Spain)], E-mail: jagl@termo.uva.es; Mozo, Ismael; Garcia de la Fuente, Isaias; Cobos, Jose Carlos [G.E.T.E.F. Dpto Termodinamica y Fisica Aplicada, Facultad de Ciencias, Universidad de Valladolid, Valladolid 47071 (Spain); Riesco, Nicolas [Department of Chemical Engineering, Loughborough University, Loughborough, LE113TU Leicestershire (United Kingdom)

    2008-01-30

    Mixtures with dimethyl or trimethylpyridines and alkane, aromatic compound or 1-alkanol have been examined using different theories: DISQUAC, Flory, the concentration-concentration structure factor, S{sub CC}(0), or the Kirkwood-Buff formalism. DISQUAC represents fairly well the available experimental data, and improves theoretical calculations from Dortmund UNIFAC. Two important effects have been investigated: (i) the effect of increasing the number of methyl groups attached to the aromatic ring of the amine; (ii) the effect of modifying the position of the methyl groups in this ring. The molar excess enthalpy, H{sup E}, and the molar excess volume, V{sup E}, decrease in systems with alkane or methanol as follows: pyridine > 3-methylpyridine > 3,5-dimethylpyridine and pyridine > 2-methylpyridine > 2,4-dimethylpyridine > 2,4,6-trimethylpyridine, which has been attributed to a weakening of the amine-amine interactions in the same sequences. This is in agreement with the relative variation of the effective dipole moment, {mu}-bar, and of the differences between the boiling temperature of a pyridine base and that of the homomorphic alkane. For heptane solutions, the observed H{sup E} variation, H{sup E} (3,5-dimethylpyridine) > H{sup E} (2,4-dimethylpyridine) > H{sup E} (2,6-dimethylpyridine), is explained similarly. Calculations on the basis of the Flory model confirm that orientational effects become weaker in systems with alkane in the order: pyridine > methylpyridine > dimethylpyridine > trimethylpyridine. S{sub CC}(0) calculations show that steric effects increase with the number of CH{sub 3}- groups in the pyridine base, and that the steric effects exerted by methyl groups in positions 2 and 6 are higher than when they are placed in positions 3 and 5. The hydrogen bond energy in methanol mixtures is independent of the pyridine base, and it is estimated to be -35.2 kJ mol{sup -1}. Heterocoordination in these solutions is due in part to size effects. Their

  6. Radical C-H functionalization to construct heterocyclic compounds.

    Science.gov (United States)

    Yu, Jin-Tao; Pan, Changduo

    2016-02-07

    Heterocyclic compounds are widely present in natural products, pharmaceuticals and bioactive molecules. Thus, organic and pharmaceutical chemists have been making extensive efforts to construct those heterocyclic frameworks through developing versatile and efficient synthetic strategies. The direct C-H functionalization via the radical pathway has emerged as a promising and dramatic approach towards heterocycles with high atom- and step-economy. Heterocyclic compounds such as coumarins, furans, benzofurans, xanthones, benzothiazoles, indoles, indolines, oxindoles, quinolines, isoquinolines, quinoxaline, and phenanthridines have been successfully synthesized by C-H functionalization through the radical pathway. In this review, recent advances on radical C-H functionalization to construct heterocyclic compounds are highlighted with discussions.

  7. Kappa-receptor selective binding of opioid ligands with a heterocyclic bicyclo[3.3.1]nonan-9-one structure.

    Science.gov (United States)

    Benyhe, S; Márki, A; Nachtsheim, Corina; Holzgrabe, Ulrike; Borsodi, Anna

    2003-01-01

    Previous pharmacological results have suggested that members of the heterocyclic bicyclo[3.3.1]nonan-9-one-like compounds are potent kappa-opioid receptor specific agonists. One lead molecule of this series. called compound 1 (dimethyl 7-methyl-2,4-di-2-pyridyl-3.7-diazabicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate) exhibited high affinity for [3H]ethylketocyclazocine and [3H]U-69.593 binding sites in guinea pig cerebellar membranes which known to be a good source for kappa1 receptors. It was shown by molecular modelling that heterocyclic bicyclo[3.3.1]nonan-9-ones fit very well with the structure of ketazocine, a prototypic kappa-selective benzomorphan compound; when compared to the arylacetamide structure of U-69.593, a specific kappa1-receptor agonist, a similar geometry was found with a slightly different distribution of the charges. It is postulated, that the essential structural skeleton involved in the opioid activity is an aryl-propyl-amine element distributed along the N7-C6-C5-C4-aryl bonds.

  8. Solid-phase Synthesis of Combinatorial 2,4-Disubstituted-1,3,5-Triazine via Amine Nucleophilic Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Moon, Sung Won [KIST Gangneung Institute, Gangneung (Korea, Republic of); Ham, Jungyeob [Gangneung-Wonju National University, Gangneung (Korea, Republic of); Chang, Young-Tae [National University of Singapore, Singapore (Singapore); Lee, Jae Wook [University of Science and Technology, Daejon (Korea, Republic of)

    2015-01-15

    In combinatorial chemistry, solid-phase synthesis is a popular approach formass production of small molecules. Compared to solution-phase synthesis, it is easy to prepare and purify a large number of heterocyclic small molecules via solid-phase chemistry; the overall reaction time is decreased as well. 1,3,5-Triazine is a nitrogen-containing heterocyclic aromatic scaffold that was shown to be a druggable scaffold in recent studies. These structures have been reported as anticancer, antimicrobial, and antiretroviral compounds, as CDKs and p38 MAP kinase inhibitors, as estrogen receptor modulators, and as inosine monophosphate dehydrogenase inhibitors. we designed and synthesized disubstituted triazine compounds as an analog of disubstituted pyrimidine compounds. These disubstituted triazine compounds possess a linear structure which may have biological activity similar to that of disubstituted pyrimidine. Here we report the solid-phase synthesis of disubstituted triazine compounds.

  9. Solid-phase Synthesis of Combinatorial 2,4-Disubstituted-1,3,5-Triazine via Amine Nucleophilic Reaction

    International Nuclear Information System (INIS)

    Moon, Sung Won; Ham, Jungyeob; Chang, Young-Tae; Lee, Jae Wook

    2015-01-01

    In combinatorial chemistry, solid-phase synthesis is a popular approach formass production of small molecules. Compared to solution-phase synthesis, it is easy to prepare and purify a large number of heterocyclic small molecules via solid-phase chemistry; the overall reaction time is decreased as well. 1,3,5-Triazine is a nitrogen-containing heterocyclic aromatic scaffold that was shown to be a druggable scaffold in recent studies. These structures have been reported as anticancer, antimicrobial, and antiretroviral compounds, as CDKs and p38 MAP kinase inhibitors, as estrogen receptor modulators, and as inosine monophosphate dehydrogenase inhibitors. we designed and synthesized disubstituted triazine compounds as an analog of disubstituted pyrimidine compounds. These disubstituted triazine compounds possess a linear structure which may have biological activity similar to that of disubstituted pyrimidine. Here we report the solid-phase synthesis of disubstituted triazine compounds

  10. Crystal structure of bis-[(phenyl-methanamine-κN)(phthalocyaninato-κ(4) N)zinc] phenyl-methan-amine tris-olvate.

    Science.gov (United States)

    Shamsudin, Norzianah; Tan, Ai Ling; Wimmer, Franz L; Young, David J; Tiekink, Edward R T

    2015-09-01

    The asymmetric unit of the title compound, 2[Zn(C32H16N8)(C7H9N)]·3C7H9N, comprises two independent complex mol-ecules and three benzyl-amine solvent mol-ecules. Each complex mol-ecule features a penta-coordinated Zn(2+) ion within a square-pyramidal geometry, whereby the N5 donor set is defined by four atoms of the phthalocyaninate dianion (PC) and an N-bound benzyl-amine mol-ecule; it is the relative orientations of the latter that differentiate between the independent complex mol-ecules. The uncoordinated benzyl-amine mol-ecules display different conformations in the structure, with syn-Car-Car-Cm-N (ar = aromatic, m = methyl-ene) torsion angles spanning the range -28.7 (10) to 35.1 (14)°. In the crystal, N-H⋯N and N-H⋯π inter-actions lead to supra-molecular layers in the ab plane. The layers have a zigzag topology, have the coordinating and non-coordinating benzyl-amine mol-ecules directed to the inside, and present the essentially flat PC resides to the outside. This arrangement enables adjacent layers to associate via π-π inter-actions [inter-centroid distance between pyrrolyl and fused-benzene rings = 3.593 (2) Å] so that a three-dimensional architecture is formed.

  11. Determination of urinary aromatic amines in smokers and nonsmokers using a MIPs-SPE coupled with LC-MS/MS method.

    Science.gov (United States)

    Yu, Jingjing; Wang, Sheng; Zhao, Ge; Wang, Bing; Ding, Li; Zhang, Xiaobing; Xie, Jianping; Xie, Fuwei

    2014-05-01

    Urinary aromatic amines (AAs) could be used as biomarkers for human exposure to AAs in cigarette smoke. A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed for the determination of urinary AAs (i.e. 1-naphthylamine (1-NA), 2-naphthylamine (2-NA), 3-aminobiphenyl (3-ABP) and 4-aminobiphenyl (4-ABP)) in smokers and nonsmokers. A molecularly imprinted polymers (MIPs) solid phase extraction (SPE) cartridge was applied to purify urine samples and no derivatization reaction was involved. Each analytes used respective stable isotope internal standards, which could well compensate matrix effect. Lower limit of detections (LODs) for four AAs were obtained and in the range of 1.5-5ngL(-1). Recovery ranged from 87.7±4.5% to 111.3±6.4% and precision were less than 9.9%. The method was applied to analyze urine samples of 40 smokers and 10 nonsmokers. The 24h urinary excretion amounts of total AAs were higher for smokers compared with nonsmokers. What's more, 1-NA, 3-ABP and 4-ABP excretion amounts showed significant differences (p<0.05) between smokers and nonsmokers. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. Vinyl ester resin and process for curing same with ionizing radiation in the presence of amines

    International Nuclear Information System (INIS)

    Mani, I.

    1975-01-01

    The addition of about 1.5 to 5 weight percent of certain amines to a thermosettable mixture of an alkenyl aromatic monomer and a polymerizable vinyl ester resin reduces the dosage level of ionizing radiation required to cure the mixture. (U.S.)

  13. Formation of Sulfonyl Aromatic Alcohols by Electrolysis of a Bisazo Reactive Dye

    Directory of Open Access Journals (Sweden)

    María P. Elizalde-González

    2012-12-01

    Full Text Available Five sulfonyl aromatic alcohols, namely 4-((2-hydroxyethylsulfonylphenol, 4-((2-(2-((4-hydroxyphenylsulfonylethoxyvinylsulfonylphenol, 4-(ethylsulfonylphenol, 4-(vinylsulfonylphenol and 5-((4-aminophenylsulfonyl-2-penten-1-ol were identified by LC-ESI-Qq-TOF-MS as products formed by electrolysis of the bisazo reactive dye Reactive Black 5 (RB5. Since electrolyses were performed in an undivided cell equipped with Ni electrodes in alkaline medium, amines like 4-(2-methoxyethylsulfonylbenzene-amine (MEBA with m/z 216 were also suspected to be formed due to the plausible chemical reaction in the bulk or the cathodic reduction of RB5 and its oxidation by-products. Aiming to check this hypothesis, a method was used for the preparation of MEBA with 98% purity, via chemical reduction also of the dye RB5. The logP of the synthesized sulfonyl aromatic compounds was calculated and their logkw values were determined chromatographically. These data were discussed in regard to the relationship between hydrophobicity/lipophilicity and toxicity.

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

    Science.gov (United States)

    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 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.

  15. New Molecular Detections in TMC-1 with the Green Bank Telescope: Carbon-Chain and Aromatic Molecules

    Science.gov (United States)

    Burkhardt, Andrew Michael

    2018-01-01

    Polycyclic aromatic hydrocarbons (PAHs) and polycyclic aromatic nitrogen heterocycles PA(N)Hs are believed to be widespread throughout the Universe, and are likely responsible for the unidentified infrared bands. However, the individual detection of aromatic molecules has been limited to a single weak absorption feature of an infrared bending mode of benzene (c-C6H6). The cold core TMC-1 has long been a source of new molecular detections, particularly for unsaturated carbon-rich molecules that are appealing potential precursors of PA(N)Hs. Through deep observations with the Green Bank Telescope of TMC-1, we report the first rotational detection of an aromatic molecule, benzonitrile (c-C6H5CN), along with 8 new isotopologues of HC5N and HC7N and an entirely new molecular family (HC5O, HC7O). These new detections provide crucial insights to the formation of PAHs and the underlying carbon-chain chemistry of dark clouds.

  16. On the formation of protected gold nanoparticles from AuCl4- by the reduction using aromatic amines

    International Nuclear Information System (INIS)

    Subramaniam, Chandramouli; Tom, Renjis T.; Pradeep, T.

    2005-01-01

    Amines are used extensively as reductants and subsequent capping agents in the synthesis of metal nanoparticles, especially gold, due to its affinity to nitrogen. Taking 2-methyl aniline as an example, we show that metal reduction is followed by polymerization of the amine, while part of it covers the nanoparticle surface another fraction deposits in the solution. It is found that the oxidative polymerization of the amine goes in step with the formation of gold nanoparticles. The gold nanoparticles thus formed have a mean diameter of 20 nm. The polymerized amine encapsulates the gold nanoparticle forming a robust shell of about 5 nm thickness, making the gold core inert towards mineralizing agents such as chloroform, bromoform, sodium cyanide, benzylchloride, etc. which react with the naked gold nanoparticles. The deposited polymer is largely protonated, taking up protons from the medium during its formation. Similar results have been observed in the case of aniline also. The materials have been fully characterized by spectroscopy and microscopy

  17. Studies of interaction of amines with TOPO/TOP capped CdSe quantum dots: Role of crystallite size and oxidation potential

    International Nuclear Information System (INIS)

    Sharma, Shailesh N.; Sharma, Himani; Singh, Gurmeet; Shivaprasad, S.M.

    2008-01-01

    This work reports the interaction of aliphatic (triethyl amine, butyl amine) and aromatic amines (PPD, aniline) with CdSe quantum dots of varied sizes. The emission properties and lifetime values of CdSe quantum dots were found to be dependent on the oxidation potential of amines and crystallite sizes. Smaller CdSe quantum dots (size ∼5 nm) ensure better surface coverage of amines and hence higher quenching efficiency of amines could be realized as compared to larger CdSe quantum dots (size ∼14 nm). Heterogeneous quenching of amines due to the presence of accessible and inaccessible set of CdSe fluorophores is indicated. PPD owing to its lowest oxidation potential (∼0.26 V) has been found to have higher quenching efficiency as compared to other amines TEA and aniline having oxidation potentials ∼0.66 and >1.0 V, respectively. Butyl amine on the other hand, plays a dual role: its post-addition acts as a quencher for smaller and enhances emission for larger CdSe quantum dots, respectively. The beneficial effect of butyl amine in enhancing emission intensity could be attributed to enhance capping effect and better passivation of surface-traps

  18. Dose-dependent reduction of 3,2'-dimethyl-4-aminobiphenyl-derived DNA adducts in colon and liver of rats administered celecoxib

    Energy Technology Data Exchange (ETDEWEB)

    Ravoori, Srivani [James Graham Brown Cancer Center, University of Louisville School of Medicine, Louisville, KY 40202 (United States); Feng Yi; Neale, Jason R. [James Graham Brown Cancer Center, University of Louisville School of Medicine, Louisville, KY 40202 (United States); Department of Pharmacology and Toxicology, University of Louisville School of Medicine, Louisville, KY 40202 (United States); Jeyabalan, Jeyaprakash [James Graham Brown Cancer Center, University of Louisville School of Medicine, Louisville, KY 40202 (United States); Srinivasan, Cidambi [Department of Statistics, University of Kentucky, Lexington, KY 40502 (United States); Hein, David W. [James Graham Brown Cancer Center, University of Louisville School of Medicine, Louisville, KY 40202 (United States); Department of Pharmacology and Toxicology, University of Louisville School of Medicine, Louisville, KY 40202 (United States); Gupta, Ramesh C. [James Graham Brown Cancer Center, University of Louisville School of Medicine, Louisville, KY 40202 (United States); Department of Pharmacology and Toxicology, University of Louisville School of Medicine, Louisville, KY 40202 (United States)], E-mail: rcgupta@louisville.edu

    2008-02-01

    Colon cancer is second leading cause of cancer-related deaths in Western countries. Diet and smoking, which contain aromatic and heterocyclic amines, are major risk factors for colon cancer. Colorectal cancers have a natural history of long latency and therefore provide ample opportunities for effective chemoprevention. 3,2'-Dimethyl-4-aminobiphenyl (DMABP) is an experimental aromatic amine that causes cancer in rat colon and serves as an experimental model for arylamine and heterocyclic amine mutagens derived from diet and smoking. In this study, we investigated the effects of celecoxib, a selective cyclooxygenase-2 (COX-2) inhibitor on DMABP-induced DNA adduct formation in rat liver and colon. Male F-344 rats (5-week old) were provided free access to modified AIN-76A rat chow containing 0 (control), 500, 1000, or 1500 ppm celecoxib. Two weeks later, the rats received a subcutaneous injection of 100 mg/kg DMABP in peanut oil. Two days after DMABP treatment, the rats were killed and DMABP-derived adducts were analyzed in colon and liver DNA by butanol extraction-mediated {sup 32}P-postlabeling. Two major DNA adducts, identified as dG-C8-DMABP and dG-N{sup 2}-DMABP, were detected in liver and colon of rats treated with DMABP. These DNA adducts were diminished approximately 35-40% with 500 ppm and 65-70% with 1,000 ppm celecoxib. In the colon, no further decline in DNA adducts was observed at 1500 ppm. The same DMABP-DNA adducts also were detected in the liver and were also diminished by celecoxib treatment. The reduction in DMABP-DNA adduct levels in celecoxib-treated animals provides further support for celecoxib as a chemopreventive agent for colorectal cancer.

  19. Dose-dependent reduction of 3,2'-dimethyl-4-aminobiphenyl-derived DNA adducts in colon and liver of rats administered celecoxib

    International Nuclear Information System (INIS)

    Ravoori, Srivani; Feng Yi; Neale, Jason R.; Jeyabalan, Jeyaprakash; Srinivasan, Cidambi; Hein, David W.; Gupta, Ramesh C.

    2008-01-01

    Colon cancer is second leading cause of cancer-related deaths in Western countries. Diet and smoking, which contain aromatic and heterocyclic amines, are major risk factors for colon cancer. Colorectal cancers have a natural history of long latency and therefore provide ample opportunities for effective chemoprevention. 3,2'-Dimethyl-4-aminobiphenyl (DMABP) is an experimental aromatic amine that causes cancer in rat colon and serves as an experimental model for arylamine and heterocyclic amine mutagens derived from diet and smoking. In this study, we investigated the effects of celecoxib, a selective cyclooxygenase-2 (COX-2) inhibitor on DMABP-induced DNA adduct formation in rat liver and colon. Male F-344 rats (5-week old) were provided free access to modified AIN-76A rat chow containing 0 (control), 500, 1000, or 1500 ppm celecoxib. Two weeks later, the rats received a subcutaneous injection of 100 mg/kg DMABP in peanut oil. Two days after DMABP treatment, the rats were killed and DMABP-derived adducts were analyzed in colon and liver DNA by butanol extraction-mediated 32 P-postlabeling. Two major DNA adducts, identified as dG-C8-DMABP and dG-N 2 -DMABP, were detected in liver and colon of rats treated with DMABP. These DNA adducts were diminished approximately 35-40% with 500 ppm and 65-70% with 1,000 ppm celecoxib. In the colon, no further decline in DNA adducts was observed at 1500 ppm. The same DMABP-DNA adducts also were detected in the liver and were also diminished by celecoxib treatment. The reduction in DMABP-DNA adduct levels in celecoxib-treated animals provides further support for celecoxib as a chemopreventive agent for colorectal cancer

  20. Photocatalytic Hydrogen-Evolution Cross-Couplings: Benzene C-H Amination and Hydroxylation.

    Science.gov (United States)

    Zheng, Yi-Wen; Chen, Bin; Ye, Pan; Feng, Ke; Wang, Wenguang; Meng, Qing-Yuan; Wu, Li-Zhu; Tung, Chen-Ho

    2016-08-17

    We present a blueprint for aromatic C-H functionalization via a combination of photocatalysis and cobalt catalysis and describe the utility of this strategy for benzene amination and hydroxylation. Without any sacrificial oxidant, we could use the dual catalyst system to produce aniline directly from benzene and ammonia, and phenol from benzene and water, both with evolution of hydrogen gas under unusually mild conditions in excellent yields and selectivities.

  1. Biosynthesised ZnO : Dy3+ nanoparticles: Biodiesel properties and reusable catalyst for N-formylation of aromatic amines with formic acid

    Science.gov (United States)

    Reddy Yadav, L. S.; Raghavendra, M.; Sudheer Kumar, K. H.; Dhananjaya, N.; Nagaraju, G.

    2018-04-01

    ZnO nanoparticles doped with trivalent dysprosium ions (Dy3+) were prepared through the green combustion technique using E. tirucalli plant latex as a fuel. The fundamental and optical properties of the samples are examined via the X-ray diffraction, FTIR, UV-visible analytical methods and morphology by scanning electron microscope and transmission electron microscope. Rietveld refinement results show that the ZnO : Dy3+ were crystallized in the wurtzite hexagonal structure with space group P63mc (No. 186). The average particle size of ZnO : Dy3+ prepared with the different concentration of latex was found to be in the range 30-38nm, which is also confirmed by TEM analysis. A rapid and convenient method for the one-pot preparation of N-formamide derivatives aromatic amines and amino acid esters has been developed using Dy3+ doped ZnO as a catalytic agent. This method provides an efficient and much improved modification over reported protocols regarding yield, clean and work-up procedure milder reaction conditions. In this work, Pongamiapinnata oil was recycled for the preparation of biodiesel via Dy3+ doped ZnO as a catalytic agent.

  2. Combinatorial Libraries of Bis-Heterocyclic Compounds with Skeletal Diversity

    OpenAIRE

    Soural, Miroslav; Bouillon, Isabelle; Krchňák, Viktor

    2008-01-01

    Combinatorial solid-phase synthesis of bis-heterocyclic compounds, characterized by the presence of two heterocyclic cores connected by a spacer of variable length/structure, provided structurally heterogeneous libraries with skeletal diversity. Both heterocyclic rings were assembled on resin in a combinatorial fashion.

  3. Combinatorial Libraries of Bis-Heterocyclic Compounds with Skeletal Diversity

    Science.gov (United States)

    Soural, Miroslav; Bouillon, Isabelle; Krchňák, Viktor

    2009-01-01

    Combinatorial solid-phase synthesis of bis-heterocyclic compounds, characterized by the presence of two heterocyclic cores connected by a spacer of variable length/structure, provided structurally heterogeneous libraries with skeletal diversity. Both heterocyclic rings were assembled on resin in a combinatorial fashion. PMID:18811208

  4. Aspects and prospects of the chemistry of organic heterocycles (review)

    International Nuclear Information System (INIS)

    Schroth, W.

    1986-01-01

    The systematics of heterocycles, their place in organic chemistry, and their significance for theory and practice are discussed. Problems of the chemistry of heterocycles are discussed on the examples of systems with various types of conjugation and ring sizes. The focus is on the principles of synthesis of heterocycles, in particular, those based on acetylene, various C 3 fragments, carbon disulfide, and maleic anhydride. Individual sections of the survey are devoted to the role of heterocycles in biosynthesis, as well as certain problems common to the chemistry of heterocycles, biochemistry, and macromolecular chemistry

  5. Antioxidant evaluation of heterocyclic compounds by cytokinesis-block micronucleus assay.

    Science.gov (United States)

    Godevac, Dejan; Tesević, Vele; Vajs, Vlatka; Milosavljević, Slobodan; Stanković, Miroslava

    2013-03-01

    This article summarizes the results of using cytokinesis-block micronucleus (CBMN) assay to evaluate the antioxidant potential of heterocyclic compounds. Most studies were carried out with naturally occurring heterocyclic compounds such as plant polyphenols: flavonoids, xanthones, coumarins, and ellagitannins, or plant derived products (juices, extracts, supplements) rich in bioactive heterocyclic compounds. There are also some studies dealing with synthetic heterocyclic antioxidants. CBMN assay is an in vitro study that has been used to evaluate antioxidant and protective effects of heterocyclic compounds on induced chromosome aberration in human lymphocytes.

  6. Phase I and phase II reductive metabolism simulation of nitro aromatic xenobiotics with electrochemistry coupled with high resolution mass spectrometry.

    Science.gov (United States)

    Bussy, Ugo; Chung-Davidson, Yu-Wen; Li, Ke; Li, Weiming

    2014-11-01

    Electrochemistry combined with (liquid chromatography) high resolution mass spectrometry was used to simulate the general reductive metabolism of three biologically important nitro aromatic molecules: 3-trifluoromethyl-4-nitrophenol (TFM), niclosamide, and nilutamide. TFM is a pesticide used in the Laurential Great Lakes while niclosamide and nilutamide are used in cancer therapy. At first, a flow-through electrochemical cell was directly connected to a high resolution mass spectrometer to evaluate the ability of electrochemistry to produce the main reduction metabolites of nitro aromatic, nitroso, hydroxylamine, and amine functional groups. Electrochemical experiments were then carried out at a constant potential of -2.5 V before analysis of the reduction products by LC-HRMS, which confirmed the presence of the nitroso, hydroxylamine, and amine species as well as dimers. Dimer identification illustrates the reactivity of the nitroso species with amine and hydroxylamine species. To investigate xenobiotic metabolism, the reactivity of nitroso species to biomolecules was also examined. Binding of the nitroso metabolite to glutathione was demonstrated by the observation of adducts by LC-ESI(+)-HRMS and the characteristics of their MSMS fragmentation. In conclusion, electrochemistry produces the main reductive metabolites of nitro aromatics and supports the observation of nitroso reactivity through dimer or glutathione adduct formation.

  7. Determination of Aromatic Amines Using Solid-Phase Microextraction Based on an Ionic Liquid-Mediated Sol–Gel Technique

    Science.gov (United States)

    Abbasi, Vajihe; Sarafraz-Yazdi, Ali; Amiri, Amirhassan; Vatani, Hossein

    2016-01-01

    A headspace solid-phase microextraction (HS-SPME) method was developed for isolation of monocyclic aromatic amines from water samples followed by gas chromatography–flame ionization detector (GC–FID). In this work, the effect of the presence of ionic liquid (namely, 1-hexyl-3-methyl-imidazolium hexafluorophosphate [C6MIM][PF6]) was investigated in the sol–gel coating solutions on the morphology and extraction behavior of the resulting hybrid organic–inorganic sol–gel sorbents utilized in SPME. Hydroxy-terminated poly(dimethylsiloxane) (PDMS) was used as the sol–gel active organic component for sol–gel hybrid coatings. Two different coated fibers that were prepared are PDMS and PDMS-IL ([C6MIM][PF6]) fibers. Under the optimal conditions, the method detection limits (S/N = 3) with PDMS-IL were in the range of 0.001–0.1 ng/mL and the limits of quantification (S/N = 10) between 0.005 and 0.5 ng/mL. The relative standard deviations for one fiber (n = 5) were obtained from 3.1 up to 8.5% and between fibers or batch to batch (n = 3) in the range of 5.3–10.1%. The developed method was successfully applied to real water and juice fruits samples while the relative recovery percentages obtained for the spiked water samples at 0.1 ng/mL were from 83.3 to 95.0%. PMID:26759488

  8. YCl3-Catalyzed Highly Selective Ring Opening of Epoxides by Amines at Room Temperature and under Solvent-Free Conditions

    Directory of Open Access Journals (Sweden)

    Wuttichai Natongchai

    2017-11-01

    Full Text Available A simple, efficient, and environmentally benign approach for the synthesis of β-amino alcohols is herein described. YCl3 efficiently carried out the ring opening of epoxides by amines to produce β-amino alcohols under solvent-free conditions at room temperature. This catalytic approach is very effective, with several aromatic and aliphatic oxiranes and amines. A mere 1 mol % concentration of YCl3 is enough to deliver β-amino alcohols in good to excellent yields with high regioselectivity.

  9. Density Functional Investigation of Graphene Doped with Amine-Based Organic Molecules

    Directory of Open Access Journals (Sweden)

    Yeun Hee Hwang

    2015-01-01

    Full Text Available To improve the electronic properties of graphene, many doping techniques have been studied. Herein, we investigate the electronic and molecular structure of doped graphene using density functional theory, and we report the effects of amine-based benzene dopants adsorbed on graphene. Density functional theory (DFT calculations were performed to determine the role of amine-based aromatic compounds in graphene doping. These organic molecules bind to graphene through long-range interactions such as π-π interactions and C-H⋯π hydrogen bonding. We compared the electronic structures of pristine graphene and doped graphene to understand the electronic structure of doped graphene at the molecular level. Also, work functions of doped graphene were obtained from electrostatic potential calculations. A decrease in the work function was observed when the amine-based organic compounds were adsorbed onto graphene. Because these systems are based on physisorption, there was no obvious band structure change at point K at the Fermi level after doping. However, the amine-based organic dopants did change the absolute Fermi energy levels. In this study, we showed that the Fermi levels of the doped graphene were affected by the HOMO energy level of the dopants and by the intermolecular charge transfer between the adsorbed molecules and graphene.

  10. Chain radiation-chemical oxidation of aromatic amines in polyvinylchloride films

    International Nuclear Information System (INIS)

    Kolninov, O.V.; Lisovskaya, I.A.; Milinchuk, V.K.

    1983-01-01

    Radiation-chemical oxidation of tetramethyldiaminediphenylmethane in polyvinylchloride (PVC) and polystyrene (PS) films was investigated in the presence of CBr 4 at 300 K. Radiation yields (G) of 70 and 1 were obtained for an oxidized amine form (Am + ) in PVC and PS, resp. High yields of Am + in PVC matrix indicate the chain character of an oxidation reaction. Triplet states, which form exciplexes with CBr 4 were established to participate in oxidation reactions. The kinetic scheme suggested for the chain radiation oxidation of Am takes into account energy transfer, formation and degradation of the excited states of molecules resulting in the initiation and propagation of the chain on the account of active particles. (author)

  11. A simple, convenient, and one pot synthetic route for the preparation of 1,3,5-thiadiazines-2-thione heterocyclic compounds and their antifungal activity

    Directory of Open Access Journals (Sweden)

    Sohail Saeed

    2015-12-01

    Full Text Available A series of new heterocyclic 1,3,5-thiadiazines-2-thione with aroyl/aryl substituents (3a-c were synthesized by reacting isothiocyanates with N- (propan-2-ylpropan-2- amine in the presence of tetrabutylammonium bromide as phase transfer catalyst. The structures of these novel compounds were characterized by IR, mass spectrometry, and elemental analysis. The crystal structures were determined from single-crystal X-ray diffraction data. The synthesized compounds were tested in vitro against Fusarium solani, A. fumigatus, and Aspergillus flavus using standard drugs.

  12. Thermodynamics of organic mixtures containing amines

    International Nuclear Information System (INIS)

    Gonzalez, Juan Antonio; Mozo, Ismael; Fuente, Isaias Garcia de la; Cobos, Jose Carlos

    2006-01-01

    Binary mixtures containing pyridine (PY), or 2-methylpyridine (2MPY) or 3-methylpyridine (3MPY) or 4-methylpyridine (4MPY) and an organic solvent as benzene, toluene, alkane, or 1-alkanol are investigated in the framework of DISQUAC. The corresponding interaction parameters are reported. The model describes accurately a whole set of thermodynamic properties: vapor-liquid equilibria (VLE), liquid-liquid equilibria (LLE), solid-liquid equilibria (SLE), molar excess Gibbs energies (G E ), molar excess enthalpies (H E ), molar excess heat capacities at constant pressure (C P E ) and the concentration-concentration structure factor (S CC (0)). It is remarkable that DISQUAC correctly predicts the W-shaped curve of the C P E of the pyridine + n-hexadecane system. The model can be applied successfully to mixtures with strong positive or negative deviations from the Raoult's law. DISQUAC improves the theoretical results from UNIFAC (Dortmund version). The replacement of pyridine by a methylpyridine leads to a weakening of the amine-amine interactions, ascribed to the steric effect caused by the methyl group attached to the aromatic ring. This explains that for a given solvent (alkane, 1-alkanol) H E (pyridine)>H E (methylpyridine)

  13. Conformation-induced remote meta-C-H activation of amines

    Science.gov (United States)

    Tang, Ri-Yuan; Li, Gang; Yu, Jin-Quan

    2014-03-01

    Achieving site selectivity in carbon-hydrogen (C-H) functionalization reactions is a long-standing challenge in organic chemistry. The small differences in intrinsic reactivity of C-H bonds in any given organic molecule can lead to the activation of undesired C-H bonds by a non-selective catalyst. One solution to this problem is to distinguish C-H bonds on the basis of their location in the molecule relative to a specific functional group. In this context, the activation of C-H bonds five or six bonds away from a functional group by cyclometallation has been extensively studied. However, the directed activation of C-H bonds that are distal to (more than six bonds away) functional groups has remained challenging, especially when the target C-H bond is geometrically inaccessible to directed metallation owing to the ring strain encountered in cyclometallation. Here we report a recyclable template that directs the olefination and acetoxylation of distal meta-C-H bonds--as far as 11 bonds away--of anilines and benzylic amines. This template is able to direct the meta-selective C-H functionalization of bicyclic heterocycles via a highly strained, tricyclic-cyclophane-like palladated intermediate. X-ray and nuclear magnetic resonance studies reveal that the conformational biases induced by a single fluorine substitution in the template can be enhanced by using a ligand to switch from ortho- to meta-selectivity.

  14. Tris{2-[4-(2-pyridylpyrimidin-2-ylsulfanyl]ethyl}amine

    Directory of Open Access Journals (Sweden)

    Jian-Quan Wang

    2009-08-01

    Full Text Available The tripodal character of the title compound, C33H30N10S3, arises from the three thioether arms surrounding a central amine N atom. The three arms have approximately the same conformation but distinct geometries in a trans–trans–cis conformation, resulting in a short pyridine–sulfanyl N...S distance of 4.320 (7 Å. The distances of the central N atom to the N atoms of three pyridine rings in the arms are 8.305 (7, 8.032 (7 and 5.076 (9Å. In the crystal, molecules are joined into a three-dimensional supramolecular network via effective π–π stacking between adjacent heterocycles [centroid–centroid distances of 3.700 (3–4.118 (4 Å between adjacent interlayer pyrimidine rings and 3.676 (4 Å between the pyridine rings].

  15. Certification of polycyclic aromatic compounds. Pt. 6. CRM Nos. 152, 265, 266, 267, 268, 269, 270, 271, 272

    Energy Technology Data Exchange (ETDEWEB)

    Jacob, J; Belliardo, J J; Wagstaffe, P J

    1985-01-01

    The purity of samples of seven polycyclic aromatic hydrocarbons and two nitrogen-containing heterocyclics has been determined in an interlaboratory exercise, involving eleven laboratories of the EC member countries. The purity measurements were carried out using independent analytical methods (gas liquid chromatography, high performance liquid chromatography and mass spectrometry). This report describes the certification procedure and experimental details of the interlaboratory analyses of standard materials for environmental pollutants.

  16. Non-aromatic hydrocarbons in surface sediments near the Pearl River estuary in the South China Sea

    International Nuclear Information System (INIS)

    Gao Xuelu; Chen Shaoyong; Xie Xueliang; Long Aimin; Ma Fujun

    2007-01-01

    Surface sediment samples at 4 sites along an offshore transect from outer continental shelf off the Pearl River estuary to the shelf slope region of the northern South China Sea, have been analyzed for total organic carbon (TOC), total nitrogen (TN), solvent extractable organic matter (EOM) and non-aromatic hydrocarbons. TOC, TN and EOM show distinct spatial variations. Their highest values are all recorded at the shelf slope region. EOM varies from 18.70-38.58 μg g -1 dry sediment and accounts for 0.20-0.72% of the TOC contents. The non-aromatic hydrocarbons are an important fraction of EOM. Their contents range from 3.43-7.06 μg g -1 dry sediment. n-Alkanes with carbon number ranging from 15-38 are identified. They derive from both biogenic and petrogenic sources in different proportions. Results of isoprenoid hydrocarbons, hopanes and steranes also suggest possible petroleum contamination. - Anthropogenic activities have influences on the composition of non-aromatic hydrocarbons in the surface sediments of the northern South China Sea outer continental shelf

  17. Recent advances in the electrochemical construction of heterocycles

    Directory of Open Access Journals (Sweden)

    Robert Francke

    2014-12-01

    Full Text Available Due to the fact that the major portion of pharmaceuticals and agrochemicals contains heterocyclic units and since the overall number of commercially used heterocyclic compounds is steadily growing, heterocyclic chemistry remains in the focus of the synthetic community. Enormous efforts have been made in the last decades in order to render the production of such compounds more selective and efficient. However, most of the conventional methods for the construction of heterocyclic cores still involve the use of strong acids or bases, the operation at elevated temperatures and/or the use of expensive catalysts and reagents. In this regard, electrosynthesis can provide a milder and more environmentally benign alternative. In fact, numerous examples for the electrochemical construction of heterocycles have been reported in recent years. These cases demonstrate that ring formation can be achieved efficiently under ambient conditions without the use of additional reagents. In order to account for the recent developments in this field, a selection of representative reactions is presented and discussed in this review.

  18. Role of aromaticity in humic substances degradation kinetics using non-arrhenius temperature functions

    Czech Academy of Sciences Publication Activity Database

    Kislinger, J.; Novák, František; Kučerík, J.

    2008-01-01

    Roč. 102, č. 15 (2008), s1086-s1088 ISSN 0009-2770 Institutional research plan: CEZ:AV0Z60660521 Keywords : aromaticity * humic substances degradation kinetics * non-arrhenius temperature Subject RIV: EH - Ecology, Behaviour Impact factor: 0.593, year: 2008

  19. Reaction of acid esters of methylenebis(phosphonous acid) with carbonyl compounds

    International Nuclear Information System (INIS)

    Novikova, Z.S.; Odinets, I.L.; Lutsenko, I.F.

    1987-01-01

    The reaction of methylenebis(phosphonites) containing two hydrophosphoryl groupings with aliphatic and aromatic aldehydes and ketones in the presence of alkali metal fluorides leads to methylenebis(α-hydroxyalkylphosphinates). The reaction of methylenebis(phosphonites) containing one hydrophosphoryl groupings with carbonyl compounds in the presence of alkali metal fluorides proceeds with the formation of a new type of heterocyclic phosphorus compound, viz., 1,2λ 3 ,4λ 5 -oxadiphospholanes. The reaction of acid esters of methylenebis(phosphonous) acid with carbonyl compounds in the presence of alkali metal alkoxides or a tertiary amine is accompanied by phosphinate-phosphonate rearrangement of the intermediately formed α-hydroxylalkylphosphinates

  20. Heterocyclic amine content in beef cooked by different methods to varying degrees of doneness and gravy made from meat drippings.

    Science.gov (United States)

    Sinha, R; Rothman, N; Salmon, C P; Knize, M G; Brown, E D; Swanson, C A; Rhodes, D; Rossi, S; Felton, J S; Levander, O A

    1998-04-01

    Meats cooked at high temperatures sometimes contain heterocyclic amines (HCAs) that are known mutagens and animal carcinogens, but their carcinogenic potential in humans has not been established. To investigate the association between HCAs and cancer, sources of exposure to these compounds need to be determined. Beef is the most frequently consumed meat in the United States and for this study we determined HCA values in beef samples cooked in ways to represent US cooking practices, the results of which can be used in epidemiological studies to estimate HCA exposure from dietary questionnaires. We measured five HCAs [2-amino-3-methylimidazo[4,5-f]quinoline (IQ), 2-amino-3,4-dimethylimidazo[4,5-f]quinoline (MeIQ), 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx), 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline (DiMeIQx) and 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP)] in different types of cooked beef using solid-phase extraction and HPLC. Steak and hamburger patties were pan-fried, oven-broiled, and grilled/barbecued to four levels of doneness (rare, medium, well done or very well done), while beef roasts were oven cooked to three levels of doneness (rare, medium or well done). The measured values of the specific HCAs varied with the cut of beef, cooking method, and doneness level. In general, MeIQx content increased with doneness under each cooking condition for steak and hamburger patties, up to 8.2 ng/g. PhIP was the predominant HCA produced in steak (1.9 to 30 ng/g), but was formed only in very well done fried or grilled hamburger. DiMeIQx was found in trace levels in pan-fried steaks only, while IQ and MeIQ were not detectable in any of the samples. Roast beef did not contain any of the HCAs, but the gravy made from the drippings from well done roasts had 2 ng/g of PhIP and 7 ng/g of MeIQx. Epidemiological studies need to consider the type of meat, cooking method and degree of doneness/surface browning in survey questions to adequately assess

  1. Sensitive electrochemical sensing for polycyclic aromatic amines based on a novel core-shell multiwalled carbon nanotubes@ graphene oxide nanoribbons heterostructure.

    Science.gov (United States)

    Zhu, Gangbing; Yi, Yinhui; Han, Zhixiang; Wang, Kun; Wu, Xiangyang

    2014-10-03

    Being awfully harmful to the environment and human health, the qualitative and quantitative determinations of polycyclic aromatic amines (PAAs) are of great significance. In this paper, a novel core-shell heterostructure of multiwalled carbon nanotubes (MWCNTs) as the core and graphene oxide nanoribbons (GONRs) as the shell (MWCNTs@GONRs) was produced from longitudinal partially unzipping of MWCNTs side walls using a simple wet chemical strategy and applied for electrochemical determination of three kinds of PAAs (1-aminopyrene (1-AP), 1-aminonaphthalene and 3,3'-diaminobiphenyl). Scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, thermogravimetric analysis and electrochemical methods were used to characterize the as-prepared MWCNTs@GONRs. Due to the synergistic effects from MWCNTs and GONRs, the oxidation currents of PAAs at the MWCNTs@GONRs modified glassy carbon (GC) electrode are much higher than that at the MWCNTs/GC, graphene/GC and bare GC electrodes. 1-AP was used as the representative analyte to demonstrate the sensing performance of the MWCNTs@GONRs/GC electrode, and the proposed modified electrode has a linear response range of 8.0-500.0 nM with a detection limit of 1.5 nM towards 1-AP. Copyright © 2014 Elsevier B.V. All rights reserved.

  2. Metal Monolithic Amine-grafted Zeolite for CO{sub 2} Capture

    Energy Technology Data Exchange (ETDEWEB)

    Chuang, Steven

    2011-03-31

    The solid amine sorbent for CO{sub 2} capture process has advantages of simplicity and low operating cost compared to the MEA (monoethanolamine) process. Solid amine sorbents reported so far suffered from either low CO{sub 2} capture capacity or low stability. The solid amine sorbent developed in this project exhibited more than 3.2 mmol/g and degraded less than 10% even after 500 cycles of heating and cooling in absence of steam. The presence of steam further enhanced CO{sub 2} capture capacity. The cost of the sorbent is estimated to be less than $7.00/lb. This sorbent was developed using the results of in situ infrared spectroscopic study. Infrared results showed that CO{sub 2} adsorbs on TEPA (tetraethylenepentamine)/PEG (polyethylene glycol) as carbamates and bicarbonates. The CO{sub 2} adsorption capacity and oxidation resistance of the amine sorbent can be enhanced by the interactions between NH{sub 2} of TEPA molecules with the OH group of PEG molecules. PEG was also found to be effectively disperse and immobilize the aromatic amines for SO{sub 2} adsorption. The infrared study also showed that SiO{sub 2} is a significantly better support than zeolites due to its proper hydrophobicity. The results of this study led to the development of a high performance solid amine sorbent under simulated gas flow condition in a fixed bed, a fluidized bed, and a metal monolith unit. This study showed heat transfer could become a major technical issue in scaling up a fixed bed adsorber. The use of the fluidized bed and metal monoliths can alleviate the heat transfer issue. The metal monolith could be suitable for small scale applications due to the high cost of manufacturing; the fluidized bed mode would be most suitable for large scale applications. Preliminary economic analysis suggested that the Akron solid amine process would cost 45% less than that of MEA process.

  3. Use of the Wilkinson catalyst for the ortho-C-H heteroarylation of aromatic amines: facile access to highly extended π-conjugated heteroacenes for organic semiconductors.

    Science.gov (United States)

    Huang, Yumin; Wu, Di; Huang, Jingsheng; Guo, Qiang; Li, Juan; You, Jingsong

    2014-11-03

    An unprecedented catalytic system composed of the Wilkinson catalyst [Rh(PPh3)3Cl] and CF3COOH enabled the highly regioselective cross-coupling of aromatic amines with a variety of heteroarenes through dual C-H bond cleavage. This protocol provided a facile and rapid route from readily available substrates to (2-aminophenyl)heteroaryl compounds, which may be conveniently transformed into highly extended π-conjugated heteroacenes. The experimental studies and calculations showed that thianaphtheno[3,2-b]indoles have large HOMO-LUMO energy gaps and low-lying HOMO levels, and could therefore potentially be high-performance organic semiconductors. Herein we report the first use of a rhodium(I) catalyst for oxidative C-H/C-H coupling reactions. The current innovative catalyst system is much less expensive than [RhCp*Cl2]2/AgSbF6 and could open the door for the application of this approach to other types of C-H activation processes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. OMS-2-Supported Cu Hydroxide-Catalyzed Benzoxazoles Synthesis from Catechols and Amines via Domino Oxidation Process at Room Temperature.

    Science.gov (United States)

    Meng, Xu; Wang, Yanmin; Wang, Yuanguang; Chen, Baohua; Jing, Zhenqiang; Chen, Gexin; Zhao, Peiqing

    2017-07-07

    In the presence of manganese oxide octahedral molecular sieve (OMS-2) supported copper hydroxide Cu(OH) x /OMS-2, aerobic synthesis of benzoxazoles from catechols and amines via domino oxidation/cyclization at room temperature is achieved. This heterogeneous benzoxazoles synthesis initiated by the efficient oxidation of catechols over Cu(OH) x /OMS-2 tolerates a variety of substrates, especially amines containing sensitive groups (hydroxyl, cyano, amino, vinyl, ethynyl, ester, and even acetyl groups) and heterocycles, which affords functionalized benzoxazoles in good to excellent yields by employing low catalyst loading (2 mol % Cu). The characterization and plausible catalytic mechanism of Cu(OH) x /OMS-2 are described. The notable features of our catalytic protocol such as the use of air as the benign oxidant and EtOH as the solvent, mild conditions, ease of product separation, being scalable up to the gram level, and superior reusability of catalyst (up to 10 cycles) make it more practical and environmentally friendly for organic synthesis.

  5. Target analysis of primary aromatic amines combined with a comprehensive screening of migrating substances in kitchen utensils by liquid chromatography-high resolution mass spectrometry.

    Science.gov (United States)

    Sanchis, Yovana; Coscollà, Clara; Roca, Marta; Yusà, Vicent

    2015-06-01

    An analytical strategy including both the quantitative target analysis of 8 regulated primary aromatic amines (PAAs), as well as a comprehensive post-run target screening of 77 migrating substances, was developed for nylon utensils, using liquid chromatography-orbitrap-high resolution mass spectrometry (LC-HRMS) operating in full scan mode. The accurate mass data were acquired with a resolving power of 50,000 FWHM (scan speed, 2 Hz), and by alternating two acquisition events, ESI+ with and without fragmentation. The target method was validated after statistical optimization of the main ionization and fragmentation parameters. The quantitative method presented appropriate performance to be used in official monitoring with recoveries ranging from 78% to 112%, precision in terms of Relative Standard Deviation (RSD) was less than 15%, and the limits of quantification were between 2 and 2.5 µg kg(-1). For post-target screening, a customized theoretical database was built for food contact material migrants, including bisphenols, phthalates, and other amines. For identification purposes, accurate exact mass (<5 ppm) and some diagnostic ions including fragments were used. The strategy was applied to 10 real samples collected from different retailers in the Valencian Region (Spain) during 2014. Six out of eight target PAAs were detected in at least one sample in the target analysis. The most frequently detected compounds were 4,4'-methylenedianiline and aniline, with concentrations ranging from 2.4 to 19,715 µg kg(-1) and 2.5 to 283 µg kg(-1), respectively. Two phthalates were identified and confirmed in the post-run target screening analysis. Copyright © 2015 Elsevier B.V. All rights reserved.

  6. Rapid estimation of organic nitrogen in oil shale waste waters

    Energy Technology Data Exchange (ETDEWEB)

    Jones, B.M.; Daughton, C.G.; Harris, G.J.

    1984-04-01

    Many of the characteristics of oil shale process waste waters (e.g., malodors, color, and resistance to biotreatment) are imparted by numerous nitrogenous heterocycles and aromatic amines. For the frequent performance assessment of waste treatment processes designed to remove these nitrogenous organic compounds, a rapid and colligative measurement of organic nitrogen is essential. Quantification of organic nitrogen in biological and agricultural samples is usually accomplished using the time-consuming, wet-chemical Kjeldahl method. For oil shale waste waters, whose primary inorganic nitorgen constituent is amonia, organic Kjeldahl nitrogen (OKN) is determined by first eliminating the endogenous ammonia by distillation and then digesting the sample in boiling H/sub 2/SO/sub 4/. The organic material is oxidized, and most forms of organically bound nitrogen are released as ammonium ion. After the addition of base, the ammonia is separated from the digestate by distillation and quantified by acidimetric titrimetry or colorimetry. The major failings of this method are the loss of volatile species such as aliphatic amines (during predistillation) and the inability to completely recover nitrogen from many nitrogenous heterocycles (during digestion). Within the last decade, a new approach has been developed for the quantification of total nitrogen (TN). The sample is first combusted, a

  7. Chitosan supported bimetallic Pd/Co nanoparticles as a heterogeneous catalyst for the reduction of nitroaromatics to amines

    Directory of Open Access Journals (Sweden)

    Sajjad Keshipour

    2017-01-01

    Full Text Available A new bimetallic nanocomposite of chitosan was prepared. Pd and Co nanoparticles were deposited on chitosan to produce a new heterogeneous recyclable catalyst for use in the bimetallic catalytic reduction reaction. The catalyst was characterized with common analysis methods for nanocomposites including Energy Dispersive X-Ray Spectroscopy, X-Ray Diffraction pattern, Thermal Gravimetric Analysis, Flame Atomic Absorption Spectroscopy and Scanning Electron Microscopy, and applied in the reduction reaction of nitroaromatics using NaBH4 at room temperature. The bimetallic system gave good results compared to each of the applied metals. Various aromatic amines and diamines were used in the reduction reaction. The aromatic amines were obtained as the sole product of the reduction reaction with 15 mol% Pd and 12 mol% Co during 2h. This reaction had some advantages such as mild reaction conditions, high yield, green solvent, and a recyclable catalyst. Also, the recovered catalyst was applicable in the reduction reaction without a significant decrease in the activity for up to six times.

  8. Determination of aromatic fragment content in phenol-containing fractions of solid fuel conversion products using nuclear magnetic resonance spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kanitskaya, L.V.; Kushnarev, D.F.; Polonov, V.M.; Kalabin, G.A.

    1986-03-01

    Optimum conditions are determined for obtaining quantitative nuclear magnetic resonance /sup 13/C spectra of fragments in phenol-containing fraction of coal products. Causes are analyzed of residual signals in spectra of un-protonized carbon atoms. The tests were carried out on: low-temperature carbonization tar and phenol fraction obtained during medium-temperature coking of Cherenkhovskii coal (which contains 84.13% C; 9.68% H; 1.23% S; 4.96% O); products of tar hydrogenation with various phenol content; standard phenol mixture. It was found that quantitative determination of aromatic fraction content in coal conversion products and other phenol- and amine-containing complex mixtures, using NMR spectroscopy requires the addition of dimethylsulfide or acetone in order to suppress specific interactions of phenols (amines) with relaxants and obtain quantitative subspectra of Tertiary and Quaternary aromatic carbon atoms. 16 references.

  9. Palladium-catalyzed allylation of tautomerizable heterocycles with alkynes.

    Science.gov (United States)

    Lu, Chuan-Jun; Chen, Dong-Kai; Chen, Hong; Wang, Hong; Jin, Hongwei; Huang, Xifu; Gao, Jianrong

    2017-07-21

    A method for the allylic amidation of tautomerizable heterocycles was developed by a palladium catalyzed allylation reaction with 100% atom economy. A series of structurally diverse N-allylic substituted heterocycles can be synthesized in good yields with high chemo-, regio-, and stereoselectivities under mild conditions.

  10. Mild and Efficient Oxidation of Aromatic Alcohols and Other Substrates Using NiO2/CH3COOH System

    Directory of Open Access Journals (Sweden)

    Mohammad Kooti

    2008-01-01

    Full Text Available A variety of aromatic alcohols were efficiently oxidized to their corresponding aldehydes and ketones in good to excellent yields using nickel peroxide activated by acetic acid. Some thiols and amines were also readily oxidized by this oxidant under mild conditions.

  11. Vanadium-substituted heteropolyacids immobilized on amine- functionalized mesoporous MCM-41: A recyclable catalyst for selective oxidation of alcohols with H2O2

    International Nuclear Information System (INIS)

    Dong, Xinbo; Wang, Danjun; Li, Kebin; Zhen, Yanzhong; Hu, Huaiming; Xue, Ganglin

    2014-01-01

    Graphical abstract: Vanadium-substituted phosphotungstic acids are immobilized on amine- functionalized mesoporous MCM-41 and the hybrid catalyst is proved to be a highly efficient solid catalyst for the oxidation of aromatic alcohols to the corresponding carbonyl compounds with H 2 O 2 , featured by the high conversion and selectivity, easy recovery, and quite steady reuse. - Highlights: • Vanadium-substituted phosphotungstic acid immobilized on amine-functionalized mesoporous MCM-41 are prepared. • HPAs were fixed on the inner surface of mesoporous MCM-41 by chemical bonding to aminosilane groups. • The hybrid catalyst showed much higher catalytic activity than the pure HPAs. • The hybrid catalyst is a highly efficient recyclable solid catalyst for the selective oxidation of aromatic alcohols. - Abstract: New hybrid materials of vanadium-substituted phosphotungstic acids (VHPW) immobilized on amine-functionalized mesoporous MCM-41 (VHPW/MCM-41/NH 2 ) are prepared and characterized by FT-IR, XRD, N 2 adsorption, elemental analysis, SEM and TEM for their structural integrity and physicochemical properties. It is found that the structure of the heteropolyacids is retained upon immobilization over mesoporous materials. The catalytic activities of these hybrid materials are tested in the selective oxidation of alcohols to the carbonyl products with 30% aqueous H 2 O 2 as oxidant in toluene. The catalytic activities of different number of vanadium-substituted phosphotungstic acid are investigated, and among the catalysts, H 5 [PV 2 W 10 O 40 ] immobilized on amine-functionalized MCM-41 exhibits the highest activity with 97% conversion and 99% selectivity in the oxidation of benzyl alcohol to benzaldehyde. The hybrid catalyst is proved to be a highly efficient recyclable solid catalyst for the selective oxidation of aromatic alcohols to the corresponding aldehydes with H 2 O 2

  12. The roles of tertiary amine structure, background organic matter and chloramine species on NDMA formation.

    Science.gov (United States)

    Selbes, Meric; Kim, Daekyun; Ates, Nuray; Karanfil, Tanju

    2013-02-01

    N-nitrosodimethylamine (NDMA), a probable human carcinogen, is a disinfection by-product that has been detected in chloraminated and chlorinated drinking waters and wastewaters. Formation mechanisms and precursors of NDMA are still not well understood. The main objectives of this study were to systematically investigate (i) the effect of tertiary amine structure, (ii) the effect of background natural organic matter (NOM), and (iii) the roles of mono vs. dichloramine species on the NDMA formation. Dimethylamine (DMA) and 20 different tertiary aliphatic and aromatic amines were carefully examined based on their functional groups attached to the basic DMA structure. The wide range (0.02-83.9%) of observed NDMA yields indicated the importance of the structure of tertiary amines, and both stability and electron distribution of the leaving group of tertiary amines on NDMA formation. DMA associated with branched alkyl groups or benzyl like structures having only one carbon between the ring and DMA structure consistently gave higher NDMA yields. Compounds with electron withdrawing groups (EWG) reacted preferentially with monochloramine, whereas compounds with electron donating group (EDG) showed tendency to react with dichloramine to form NDMA. When the selected amines were present in NOM solutions, NDMA formation increased for compounds with EWG while decreased for compounds with EDG. This impact was attributed to the competitions between NOM and amines for chloramine species. The results provided additional information to the commonly accepted mechanism for NDMA formation including chloramine species reacting with tertiary amines and the role of the leaving group on overall NDMA conversion. Copyright © 2012 Elsevier Ltd. All rights reserved.

  13. Conditions allowing the formation of biogenic amines in cheese

    NARCIS (Netherlands)

    Joosten, H.M.L.J.

    1988-01-01

    A study was undertaken to reveal the conditions that allow the formation of biogenic amines in cheese.

    The starters most commonly used in the Dutch cheese industry do not have decarboxylative properties. Only if the milk or curd is contaminated with non-starter bacteria, amine

  14. Sulfur-Kβ /sub emission studies on sulfur-bearing heterocycles

    International Nuclear Information System (INIS)

    Phillips, D.R.; Andermann, G.G.; Fujiwara, F.

    1986-01-01

    Sulfur-K/β /sub x-ray fluorescence spectroscopy (XFS) has been used to study the electronic structure and bonding in sulfur-bearing heterocycles. XFS not only has the capability of experimentally measuring valence electron energies in molecular species, but can also provide intensity data which can help define the nature of the molecular orbitals defined by the electrons. This report discusses the feasibility of using XFS as an analytical tool for the determination of total and specific sulfur heterocycle content in samples. A variety of compounds were studied. These include thiophene, thiophene derivatives, tetranydrothiophene, several more complex saturated and unsaturated sulfur heterocycles, and heterocycles containing both sulfur and nitrogen. The sulfur-K/β /sub spectra were obtained using a double crystal spectrometer which provided an instrumental resolution of about 0.7 eV

  15. Does the Intramolecular Hydrogen Bond Affect the Spectroscopic Properties of Bicyclic Diazole Heterocycles?

    Directory of Open Access Journals (Sweden)

    Paweł Misiak

    2018-01-01

    Full Text Available The formation of an intramolecular hydrogen bond in pyrrolo[1,2-a]pyrazin-1(2H-one bicyclic diazoles was analyzed, and the influence of N-substitution on HB formation is discussed in this study. B3LYP/aug-cc-pVDZ calculations were performed for the diazole, and the quantum theory of atoms in molecules (QTAIM approach as well as the natural bond orbital (NBO method was applied to analyze the strength of this interaction. It was found that the intramolecular hydrogen bond that closes an extra ring between the C=O proton acceptor group and the CH proton donor, that is, C=O⋯H–C, influences the spectroscopic properties of pyrrolopyrazine bicyclic diazoles, particularly the carbonyl frequencies. The influence of N-substitution on the aromaticity of heterocyclic rings is also discussed in this report.

  16. Synthesis of some Heterocyclic Compounds Derived from 2-Chloro-N-p-Tolylacetamide

    Directory of Open Access Journals (Sweden)

    Hanan Gh Shaaban

    2017-02-01

    Full Text Available This research includes preparation of (2-chloro-N-p-tolylacetamide (1 from the reaction of (p-aminotoluene with chloro acetyl chloride. Compound (1 reacted with thiosemi carbazide and gave compound (2, and when compound (1 reacted with semicarbazide gave compound (3. While when compound (1 reacted with thiourea it produced compound (4. Compounds (2-4 when reacted with appropriate aromatic aldehydes or ketones produced Shiff bass (5-16, which in turn reacted with chloro acetyl chloride in the present of tri ethyl amine and dioxin gave β-lactam derivatives (14-22. The structures of these compounds were characterized from their melting points, FT-IR, and NMR.

  17. A Bioinspired Organocatalytic Cascade for the Selective Oxidation of Amines under Air.

    Science.gov (United States)

    Largeron, Martine; Fleury, Maurice-Bernard

    2017-05-17

    A bioinspired organocatalytic cascade reaction for the selective aerobic oxidative cross-coupling of primary amines to imines is described. This approach takes advantages of commercially available pyrogallol monomeric precursor to deliver low loadings of natural purpurogallin in situ, under air. This is further engaged in a catalytic process with the amine substrate affording, under single turnover, the active biomimetic quinonoid organocatalyst and the homocoupled imine intermediate, which is then converted into cross-coupled imine after dynamic transimination. This organocatalytic cascade inspired by both purpurogallin biosynthesis and copper amine oxidases allows the aerobic oxidation of non-activated primary amines that non-enzymatic organocatalysts were not able to accomplish alone. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Thermodynamic functions of hydrogen bonding of amines in methanol derived from solution calorimetry data and headspace analysis

    International Nuclear Information System (INIS)

    Zaitseva, Ksenia V.; Varfolomeev, Mikhail A.; Solomonov, Boris N.

    2012-01-01

    Highlights: ► Solution enthalpies and activity coefficients of amines in methanol were measured. ► Thermodynamic functions of H-bonding of amines with methanol were determined. ► Specific interaction entropy of amines in methanol can be about zero or positive. ► Cooperativity of H-bonds in methanol media is smaller than in water solutions. ► A new view on analysis of specific interaction of solute with methanol is presented. - Abstract: Reactivity and equilibrium properties of organic molecules in self-associated liquids greatly depend on the hydrogen bonding with solvent. This work contains comprehensive thermodynamic analysis of hydrogen bonding of aliphatic and aromatic amines in self-associated solvent methanol. Enthalpies of solution at infinite dilution and limiting activity coefficients for the studied systems were measured experimentally. Enthalpies and Gibbs energies of hydrogen bonding of amines with neat methanol were determined. These values were found to be decreased compared with hydrogen bond energy in equimolar complexes “methanol–amine” determined in inert solvent or base media. A linear dependence between enthalpies and Gibbs energies of hydrogen bonding of amines with neat methanol was observed. It was firstly revealed that the entropy of specific interactions of amines with neat methanol can be about zero or positive. Disruption of solvent–solvent hydrogen bonds can be regarded as the most important step during dissolution of amine in methanol. It was found that the cooperative effect influences on the Gibbs energies of hydrogen bonding of amines in methanol, but in a lesser extent than in aqueous solutions. The new results show that the hydrogen bonding process in the self-associated solvents differs significantly from equimolar complexation in aprotic media.

  19. Heterocyclic Schiff bases as non toxic antioxidants: Solvent effect, structure activity relationship and mechanism of action

    Science.gov (United States)

    Shanty, Angamaly Antony; Mohanan, Puzhavoorparambil Velayudhan

    2018-03-01

    Phenolic heterocyclic imine based Schiff bases from Thiophene-2-carboxaldehyde and Pyrrole-2-carboxaldehyde were synthesized and characterized as novel antioxidants. The solvent effects of these Schiff bases were determined and compared with standard antioxidants, BHA employing DPPH assay and ABTS assay. Fixed reaction time and Steady state measurement were used for study. IC50 and EC50 were calculated. Structure-activity relationship revealed that the electron donating group in the phenolic ring increases the activity where as the electron withdrawing moiety decreases the activity. The Schiff base derivatives showed antioxidant property by two different pathways namely SPLET and HAT mechanisms in DPPH assay. While in ABTS method, the reaction between ABTS radical and Schiff bases involves electron transfer followed by proton transfer (ET-PT) mechanism. The cytotoxicity of these compounds has been evaluated by MTT assay. The results showed that all these compounds are non toxic in nature.

  20. Iridium-Catalyzed Condensation of Primary Amines To Form Secondary Amines

    DEFF Research Database (Denmark)

    Lorentz-Petersen, Linda Luise Reeh; Jensen, Paw; Madsen, Robert

    2009-01-01

    Symmetric secondary amines are readily obtained by heating a neat primary amine with 0.5 mol% of bis(dichloro[eta(5)-pentamethylcyclopentadienyl]iridium). The products are isolated by direct distillation in good yields.......Symmetric secondary amines are readily obtained by heating a neat primary amine with 0.5 mol% of bis(dichloro[eta(5)-pentamethylcyclopentadienyl]iridium). The products are isolated by direct distillation in good yields....

  1. Application of the cubic-plus-association (CPA) equation of state to complex mixtures with aromatic hydrocarbons

    DEFF Research Database (Denmark)

    Folas, Georgios; Kontogeorgis, Georgios; Michelsen, Michael Locht

    2006-01-01

    The cubic-plus-association (CPA) equation of state is applied to phase equilibria of mixtures containing alcohols, glycols, water, and aromatic or olefinic hydrocarbons. Previously, CPA has been successfully used for mixtures containing various associating compounds (alcohols, glycols, amines......, organic acids, and water) and aliphatic hydrocarbons. We show in this work that the model can be satisfactorily extended to complex vapor-liquid-liquid equilibria with aromatic or olefinic hydrocarbons. The solvation between aromatics/olefinics and polar compounds is accounted for. This is particularly...... important for mixtures containing water and glycols, but less so for mixtures with alcohols. For water/hydrocarbons, a single binary interaction parameter which accounts for the solvation is fitted to the experimental liquid-liquid equilibria (LLE) data. The interaction parameter of the physical term...

  2. Thermodynamic functions of hydrogen bonding of amines in methanol derived from solution calorimetry data and headspace analysis

    Energy Technology Data Exchange (ETDEWEB)

    Zaitseva, Ksenia V., E-mail: zaitseva.ksenia@gmail.com [Chemical Institute, Kazan (Volga Region) Federal University, Kremlevskaya 18, Kazan 420008 (Russian Federation); Varfolomeev, Mikhail A., E-mail: vma.ksu@gmail.com [Chemical Institute, Kazan (Volga Region) Federal University, Kremlevskaya 18, Kazan 420008 (Russian Federation); Solomonov, Boris N., E-mail: boris.solomonov@ksu.ru [Chemical Institute, Kazan (Volga Region) Federal University, Kremlevskaya 18, Kazan 420008 (Russian Federation)

    2012-05-10

    Highlights: Black-Right-Pointing-Pointer Solution enthalpies and activity coefficients of amines in methanol were measured. Black-Right-Pointing-Pointer Thermodynamic functions of H-bonding of amines with methanol were determined. Black-Right-Pointing-Pointer Specific interaction entropy of amines in methanol can be about zero or positive. Black-Right-Pointing-Pointer Cooperativity of H-bonds in methanol media is smaller than in water solutions. Black-Right-Pointing-Pointer A new view on analysis of specific interaction of solute with methanol is presented. - Abstract: Reactivity and equilibrium properties of organic molecules in self-associated liquids greatly depend on the hydrogen bonding with solvent. This work contains comprehensive thermodynamic analysis of hydrogen bonding of aliphatic and aromatic amines in self-associated solvent methanol. Enthalpies of solution at infinite dilution and limiting activity coefficients for the studied systems were measured experimentally. Enthalpies and Gibbs energies of hydrogen bonding of amines with neat methanol were determined. These values were found to be decreased compared with hydrogen bond energy in equimolar complexes 'methanol-amine' determined in inert solvent or base media. A linear dependence between enthalpies and Gibbs energies of hydrogen bonding of amines with neat methanol was observed. It was firstly revealed that the entropy of specific interactions of amines with neat methanol can be about zero or positive. Disruption of solvent-solvent hydrogen bonds can be regarded as the most important step during dissolution of amine in methanol. It was found that the cooperative effect influences on the Gibbs energies of hydrogen bonding of amines in methanol, but in a lesser extent than in aqueous solutions. The new results show that the hydrogen bonding process in the self-associated solvents differs significantly from equimolar complexation in aprotic media.

  3. Activation of trans geometry in bifunctional mononuclear platinum complexes by a non-bulky methylamine ligand

    Czech Academy of Sciences Publication Activity Database

    Frýbortová, M.; Nováková, Olga; Štěpánková, Jana; Novohradský, Vojtěch; Gibson, D.; Kašpárková, Jana; Brabec, Viktor

    2013-01-01

    Roč. 126, SEP2013 (2013), s. 46-54 ISSN 0162-0134 R&D Projects: GA ČR(CZ) GAP301/10/0598; GA ČR(CZ) GA13-08273S Institutional research plan: CEZ:AV0Z50040702 Institutional support: RVO:68081707 Keywords : HETEROCYCLIC AMINE LIGAND * INTERSTRAND CROSS-LINKS * DNA-BINDING MODE Subject RIV: BO - Biophysics Impact factor: 3.274, year: 2013

  4. Science and technology review, September 1995

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1995-09-01

    This report describes efforts to identify the metabolic pathways of heterocyclic amines in animals and humans. These heterocyclic amines are potent mutagens when foods derived from muscle and other protein sources are cooked. Attempts have been made to study the effects of these toxic compounds on DNA. Attention is focused on the potential cancer risks associated with their intake as food.

  5. An insight into the biological activities of heterocyclic-fatty acid hybrid molecules.

    Science.gov (United States)

    Venepally, Vijayendar; Reddy Jala, Ram Chandra

    2017-12-01

    Heterocyclic compounds are the interesting core structures for the development of new bioactive compounds. Fatty acids are derived from renewable raw materials and exhibit various biological activities. Several researchers are amalgamating these two bioactive components to yield bioactive hybrid molecules with some desirable features. Heterocyclic-fatty acid hybrid derivatives are a new class of heterocyclic compounds with a broad range of biological activities and significance in the field of medicinal chemistry. Over the last few years, many research articles emphasized the significance of heterocyclic-fatty acid hybrid derivatives. The present review article focuses the developments in designing and biological evaluation of heterocyclic-fatty acid hybrid molecules. Copyright © 2017. Published by Elsevier Masson SAS.

  6. METHODS OF SYNTHESIS EIGHT-TELLURIUM-CONTAINING HETEROCYCLES WITH MORE HETEROATOMS

    Directory of Open Access Journals (Sweden)

    G. M. Abakarov

    2013-01-01

    Full Text Available In this article systematized and summarized data on the synthesis of neweight-embered tellurium-containing heterocycles and new preparative methods described above produce heterocyclic tellurium.

  7. Vanadium-substituted heteropolyacids immobilized on amine- functionalized mesoporous MCM-41: A recyclable catalyst for selective oxidation of alcohols with H{sub 2}O{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Xinbo [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); Wang, Danjun [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); College of Chemistry Chemical Engineering, Yanan University, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan' an 716000 (China); Li, Kebin [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); Zhen, Yanzhong [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); College of Chemistry Chemical Engineering, Yanan University, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan' an 716000 (China); Hu, Huaiming [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); Xue, Ganglin, E-mail: xglin707@163.com [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China)

    2014-09-15

    Graphical abstract: Vanadium-substituted phosphotungstic acids are immobilized on amine- functionalized mesoporous MCM-41 and the hybrid catalyst is proved to be a highly efficient solid catalyst for the oxidation of aromatic alcohols to the corresponding carbonyl compounds with H{sub 2}O{sub 2}, featured by the high conversion and selectivity, easy recovery, and quite steady reuse. - Highlights: • Vanadium-substituted phosphotungstic acid immobilized on amine-functionalized mesoporous MCM-41 are prepared. • HPAs were fixed on the inner surface of mesoporous MCM-41 by chemical bonding to aminosilane groups. • The hybrid catalyst showed much higher catalytic activity than the pure HPAs. • The hybrid catalyst is a highly efficient recyclable solid catalyst for the selective oxidation of aromatic alcohols. - Abstract: New hybrid materials of vanadium-substituted phosphotungstic acids (VHPW) immobilized on amine-functionalized mesoporous MCM-41 (VHPW/MCM-41/NH{sub 2}) are prepared and characterized by FT-IR, XRD, N{sub 2} adsorption, elemental analysis, SEM and TEM for their structural integrity and physicochemical properties. It is found that the structure of the heteropolyacids is retained upon immobilization over mesoporous materials. The catalytic activities of these hybrid materials are tested in the selective oxidation of alcohols to the carbonyl products with 30% aqueous H{sub 2}O{sub 2} as oxidant in toluene. The catalytic activities of different number of vanadium-substituted phosphotungstic acid are investigated, and among the catalysts, H{sub 5}[PV{sub 2}W{sub 10}O{sub 40}] immobilized on amine-functionalized MCM-41 exhibits the highest activity with 97% conversion and 99% selectivity in the oxidation of benzyl alcohol to benzaldehyde. The hybrid catalyst is proved to be a highly efficient recyclable solid catalyst for the selective oxidation of aromatic alcohols to the corresponding aldehydes with H{sub 2}O{sub 2}.

  8. Structural mechanisms of photoeffect in polyimide structures containing heterocyclic fragments

    International Nuclear Information System (INIS)

    Aleksandrova, E. L.

    2006-01-01

    Trends in the variation in the quantum yields of charge-carrier photogeneration in polyimide structures containing heterocyclic fragments are studied. It is shown that the efficiency of sensitization of polyimides depends on the donor and acceptor properties of the fragments of monomeric units of the polyimide. It is established that the range of spectral sensitivity for heterocyclic fragments representing intramolecular complexes with charge transport is wider than that for heterocycles that do not represent such complexes

  9. Rapid Microwave-Assisted Copper-Catalyzed Nitration of Aromatic Halides with Nitrite Salts

    Energy Technology Data Exchange (ETDEWEB)

    Paik, Seung Uk; Jung, Myoung Geun [Keimyung University, Daegu (Korea, Republic of)

    2012-02-15

    A rapid and efficient copper-catalyzed nitration of aryl halides has been established under microwave irradiation. The catalytic systems were found to be the most effective with 4-substituted aryl iodides leading to nearly complete conversions. Nitration of aromatic compounds is one of the important industrial processes as underlying intermediates in the manufacture of a wide range of chemicals such as dyes, pharmaceuticals, agrochemicals and explosives. General methods for the nitration of aromatic compounds utilize strongly acidic conditions employing nitric acid or a mixture of nitric and sulfuric acids, sometimes leading to problems with poor regioselectivity, overnitration, oxidized byproducts and excess acid waste in many cases of functionalized aromatic compounds. Several other nitrating agents or methods avoiding harsh reaction conditions have been explored using metal nitrates, nitrite salts, and ionic liquid-mediated or microwave-assisted nitrations. Recently, copper or palladium compounds have been successfully used as efficient catalysts for the arylation of amines with aryl halides under mild conditions.

  10. Rapid Microwave-Assisted Copper-Catalyzed Nitration of Aromatic Halides with Nitrite Salts

    International Nuclear Information System (INIS)

    Paik, Seung Uk; Jung, Myoung Geun

    2012-01-01

    A rapid and efficient copper-catalyzed nitration of aryl halides has been established under microwave irradiation. The catalytic systems were found to be the most effective with 4-substituted aryl iodides leading to nearly complete conversions. Nitration of aromatic compounds is one of the important industrial processes as underlying intermediates in the manufacture of a wide range of chemicals such as dyes, pharmaceuticals, agrochemicals and explosives. General methods for the nitration of aromatic compounds utilize strongly acidic conditions employing nitric acid or a mixture of nitric and sulfuric acids, sometimes leading to problems with poor regioselectivity, overnitration, oxidized byproducts and excess acid waste in many cases of functionalized aromatic compounds. Several other nitrating agents or methods avoiding harsh reaction conditions have been explored using metal nitrates, nitrite salts, and ionic liquid-mediated or microwave-assisted nitrations. Recently, copper or palladium compounds have been successfully used as efficient catalysts for the arylation of amines with aryl halides under mild conditions

  11. Transformation of saturated nitrogen-containing heterocyclic compounds by microorganisms.

    Science.gov (United States)

    Parshikov, Igor A; Silva, Eliane O; Furtado, Niege A J C

    2014-02-01

    The saturated nitrogen-containing heterocyclic compounds include many drugs and compounds that may be used as synthons for the synthesis of other pharmacologically active substances. The need for new derivatives of saturated nitrogen-containing heterocycles for organic synthesis, biotechnology and the pharmaceutical industry, including optically active derivatives, has increased interest in microbial synthesis. This review provides an overview of microbial technologies that can be valuable to produce new derivatives of saturated nitrogen-containing heterocycles, including hydroxylated derivatives. The chemo-, regio- and enantioselectivity of microbial processes can be indispensable for the synthesis of new compounds. Microbial processes carried out with fungi, including Beauveria bassiana, Cunninghamella verticillata, Penicillium simplicissimum, Aspergillus niger and Saccharomyces cerevisiae, and bacteria, including Pseudomonas sp., Sphingomonas sp. and Rhodococcus erythropolis, biotransform many substrates efficiently. Among the biological activities of saturated nitrogen-containing heterocyclic compounds are antimicrobial, antitumor, antihypertensive and anti-HIV activities; some derivatives are effective for the treatment and prevention of malaria and trypanosomiasis, and others are potent glycosidase inhibitors.

  12. Heterocyclic Naphthalimides as New Skeleton Structure of Compounds with Increasingly Expanding Relational Medicinal Applications.

    Science.gov (United States)

    Gong, Huo-Hui; Addla, Dinesh; Lv, Jing-Song; Zhou, Cheng-He

    2016-01-01

    Naphthalimide compounds are an important type of nitrogen-containing aromatic heterocycles with cyclic double imides and the naphthalene framework. This π-deficient large conjugated planar structure enables naphthalimide derivatives to readily interact with various biological cations, anions, small molecules and macromolecules such as DNAs, enzymes and recetors in living organism via noncovalent bonds, therefore exhibiting extensive potentiality in relatively medicinal applications. Currently, some naphthalimides as anticancer agents have entered into clinical trials and other naphthalimide-based medicinal developments as potential drugs for treatment of various diseases are actively and unprecedentedly expanding. Naphthalimide-derived artificial ion receptors, fluorescent probes and cell imaging agents are being overwhelmingly investigated and have a diversity of potential applications in real-time detecting ions and biomolecules, understanding biological processes and determining pharmacological and pharmacokinetic properties. All the above mentions have strongly implied that naphthalimide-based derivatives as new skeleton structure of compounds possess increasingly expanding relational medicinal applications, and the related research is becoming a quite attractive active topic and newly rising highlight. Combining with our research and referring other works from literature, this work systematically reviews the current research and development of heterocyclic naphthalimides as anticancer, antibacterial, antifungal, antiviral, anti-inflammatory, antidepressant agents as well as artificial cation and anion receptors, diagnostic agents and pathologic probes, and cell imaging agents for biologically important species. Some rational design strategies, structure-activity relationships and action mechanisms are discussed. The perspectives of the future development of naphthalimide-based medicinal chemistry are also presented.

  13. synthesis and characterization of some poly functionalized heterocyclic derivatives of expected biological activity

    International Nuclear Information System (INIS)

    El-sayed, M.S.

    2001-01-01

    The present work was aimed and designed to fulfil The following objectives : 1- Continuation of the effort done by our research group in the field of chemistry of pyridinethione derivatives and their biological activities. 2- Synthesis of several new heterocyclic derivatives containing N and/or S using the laboratory available reagents. 3- Establishment of the structures of the newly synthesized heterocyclic compounds by the data of IR, 1 H-NMR, mass spectra in addition to the elemental analysis. 4- Synthesis of some of these heterocyclic derivatives via alternative routs and this used as a tool to confirm the structures of the newly synthesized heterocyclic derivatives. 5- study of the most probable mechanisms leading to the formation of the new heterocyclic derivatives. 6- The antimicrobial activity of some of the newly synthesized heterocyclic derivatives was tested against several types of organisms

  14. Microwave-assisted synthesis of bio-active heterocycles in aqueous media

    KAUST Repository

    Polshettiwar, Vivek; Varma, Rajender S.

    2010-01-01

    Synthesis of bio-active heterocycles and fine chemicals in aqueous media are one of the best solutions for the development of green and sustainable protocols. To illustrate the advantages of aqueous MW chemistry in heterocycle synthesis

  15. Sensitive electrochemical sensing for polycyclic aromatic amines based on a novel core–shell multiwalled carbon nanotubes@ graphene oxide nanoribbons heterostructure

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Gangbing, E-mail: zhgb1030@ujs.edu.cn [School of the Environment and Safety Engineering, Jiangsu University, Zhenjiang 212013 (China); Yi, Yinhui; Han, Zhixiang [School of the Environment and Safety Engineering, Jiangsu University, Zhenjiang 212013 (China); Wang, Kun [School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013 (China); Wu, Xiangyang, E-mail: wuxy@ujs.edu.cn [School of the Environment and Safety Engineering, Jiangsu University, Zhenjiang 212013 (China)

    2014-10-03

    Highlights: • A core–shell heterostructure MWCNTs@GONRs was produced from unzipping MWCNTs. • A new electrochemical sensor for PAAs was developed based on MWCNTs@GONRs hybrids. • The sensor shows good analytical performance for PAAs detection. - Abstract: Being awfully harmful to the environment and human health, the qualitative and quantitative determinations of polycyclic aromatic amines (PAAs) are of great significance. In this paper, a novel core–shell heterostructure of multiwalled carbon nanotubes (MWCNTs) as the core and graphene oxide nanoribbons (GONRs) as the shell (MWCNTs@GONRs) was produced from longitudinal partially unzipping of MWCNTs side walls using a simple wet chemical strategy and applied for electrochemical determination of three kinds of PAAs (1-aminopyrene (1-AP), 1-aminonaphthalene and 3,3′-diaminobiphenyl). Scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, thermogravimetric analysis and electrochemical methods were used to characterize the as-prepared MWCNTs@GONRs. Due to the synergistic effects from MWCNTs and GONRs, the oxidation currents of PAAs at the MWCNTs@GONRs modified glassy carbon (GC) electrode are much higher than that at the MWCNTs/GC, graphene/GC and bare GC electrodes. 1-AP was used as the representative analyte to demonstrate the sensing performance of the MWCNTs@GONRs/GC electrode, and the proposed modified electrode has a linear response range of 8.0–500.0 nM with a detection limit of 1.5 nM towards 1-AP.

  16. Sensitive electrochemical sensing for polycyclic aromatic amines based on a novel core–shell multiwalled carbon nanotubes@ graphene oxide nanoribbons heterostructure

    International Nuclear Information System (INIS)

    Zhu, Gangbing; Yi, Yinhui; Han, Zhixiang; Wang, Kun; Wu, Xiangyang

    2014-01-01

    Highlights: • A core–shell heterostructure MWCNTs@GONRs was produced from unzipping MWCNTs. • A new electrochemical sensor for PAAs was developed based on MWCNTs@GONRs hybrids. • The sensor shows good analytical performance for PAAs detection. - Abstract: Being awfully harmful to the environment and human health, the qualitative and quantitative determinations of polycyclic aromatic amines (PAAs) are of great significance. In this paper, a novel core–shell heterostructure of multiwalled carbon nanotubes (MWCNTs) as the core and graphene oxide nanoribbons (GONRs) as the shell (MWCNTs@GONRs) was produced from longitudinal partially unzipping of MWCNTs side walls using a simple wet chemical strategy and applied for electrochemical determination of three kinds of PAAs (1-aminopyrene (1-AP), 1-aminonaphthalene and 3,3′-diaminobiphenyl). Scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, thermogravimetric analysis and electrochemical methods were used to characterize the as-prepared MWCNTs@GONRs. Due to the synergistic effects from MWCNTs and GONRs, the oxidation currents of PAAs at the MWCNTs@GONRs modified glassy carbon (GC) electrode are much higher than that at the MWCNTs/GC, graphene/GC and bare GC electrodes. 1-AP was used as the representative analyte to demonstrate the sensing performance of the MWCNTs@GONRs/GC electrode, and the proposed modified electrode has a linear response range of 8.0–500.0 nM with a detection limit of 1.5 nM towards 1-AP

  17. Interaction of amines with native aluminium oxide layers in non-aqueous environment: Application to the understanding of the formation of epoxy-amine/metal interphases

    International Nuclear Information System (INIS)

    Mercier, D.; Rouchaud, J.-C.; Barthes-Labrousse, M.-G.

    2008-01-01

    Interaction of propylamine (PA), 1,2-diaminoethane (DAE) or 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophorone diamine, IPDA) with native aluminium oxide layers in non-aqueous environment has been studied using time-resolved inductively coupled plasma optical emission spectroscopy (ICP-OES) and X-ray photoelectron spectroscopy (XPS). The formation of several surface complexes has been evidenced. Monodentate and bidentate metal-bond surface complexes (MBSC) result from interactions between the amine terminations of the molecule and aluminium cations by donation of the N lone electron pair to the metal ion (Lewis-like mechanism leading to O-Al...N bonds). Monodentate and bidentate hydrogen-bond surface complexes (HBSC) are due to interaction of the amino group with surface hydroxyl groups by protonation of the amine termination (Bronsted-like mechanism leading to the formation of Al-OH...N bonds) or interaction with carbonaceous contamination (C x O y H z ...N bonds). Diamines can also form mixed complexes with one amino group forming an O-Al...N bond and the other group forming an Al-OH...N or C x O y H z ...N bond. Al-OH...N and C x O y H z ...N bonds are less stable under vacuum than O-Al...N bonds, leading to partial desorption of the DAE molecules in vacuum and modification of the interaction modes. Only DAE and IPDA can lead to partial dissolution of the aluminium native (hydr)oxide films. A detailed mechanism of dissolution has been proposed based on the formation of mononuclear bidentate (chelate) MBSC by ligand exchange between the terminal η 1 -OH and bridged μ 2 -OH surface sites and the amino terminations of the molecule. The detachment of this complex from the surface is likely to be the precursor step to the formation of the interphase in epoxy-amine/metal systems

  18. Batch and Flow Photochemical Benzannulations Based on the Reaction of Ynamides and Diazo Ketones. Application to the Synthesis of Polycyclic Aromatic and Heteroaromatic Compounds

    Science.gov (United States)

    Willumstad, Thomas P.; Haze, Olesya; Mak, Xiao Yin; Lam, Tin Yiu; Wang, Yu-Pu; Danheiser*, Rick L.

    2013-01-01

    Highly substituted polycyclic aromatic and heteroaromatic compounds are produced via a two-stage tandem benzannulation/cyclization strategy. The initial benzannulation step proceeds via a pericyclic cascade mechanism triggered by thermal or photochemical Wolff rearrangement of a diazo ketone. The photochemical process can be performed using a continuous flow reactor which facilitates carrying out reactions on a large scale and minimizes the time required for photolysis. Carbomethoxy ynamides as well as more ketenophilic bissilyl ynamines and N-sulfonyl and N-phosphoryl ynamides serve as the reaction partner in the benzannulation step. In the second stage of the strategy, RCM generates benzofused nitrogen heterocycles, and various heterocyclization processes furnish highly substituted and polycyclic indoles of types that were not available by using the previous cyclobutenone-based version of the tandem strategy. PMID:24116731

  19. Parsing of the free energy of aromatic-aromatic stacking interactions in solution

    Energy Technology Data Exchange (ETDEWEB)

    Kostjukov, Viktor V.; Khomytova, Nina M. [Department of Physics, Sevastopol National Technical University, Sevastopol 99053, Crimea (Ukraine); Hernandez Santiago, Adrian A.; Tavera, Anna-Maria Cervantes; Alvarado, Julieta Salas [Faculty of Chemical Sciences, Autonomous University of Puebla, Puebla (Mexico); Evstigneev, Maxim P., E-mail: max_evstigneev@mail.ru [Department of Physics, Sevastopol National Technical University, Sevastopol 99053, Crimea (Ukraine)

    2011-10-15

    Graphical abstract: Highlights: > A protocol for decomposition of the free energy of aromatic stacking is developed. > The factors stabilizing/destabilizing stacking of aromatic molecules are defined. > Hydrophobic contribution is found to be dominant. - Abstract: We report an analysis of the energetics of aromatic-aromatic stacking interactions for 39 non-covalent reactions of self- and hetero-association of 12 aromatic molecules with different structures and charge states. A protocol for computation of the contributions to the total energy from various energetic terms has been developed and the results are consistent with experiment in 92% of all the systems studied. It is found that the contributions from hydrogen bonds and entropic factors are always unfavorable, whereas contributions from van-der-Waals, electrostatic and/or hydrophobic effects may lead to stabilizing or destabilizing factors depending on the system studied. The analysis carried out in this work provides an answer to the questions 'What forces stabilize/destabilize the stacking of aromatic molecules in aqueous-salt solution and what are their relative importance?'

  20. Parsing of the free energy of aromatic-aromatic stacking interactions in solution

    International Nuclear Information System (INIS)

    Kostjukov, Viktor V.; Khomytova, Nina M.; Hernandez Santiago, Adrian A.; Tavera, Anna-Maria Cervantes; Alvarado, Julieta Salas; Evstigneev, Maxim P.

    2011-01-01

    Graphical abstract: Highlights: → A protocol for decomposition of the free energy of aromatic stacking is developed. → The factors stabilizing/destabilizing stacking of aromatic molecules are defined. → Hydrophobic contribution is found to be dominant. - Abstract: We report an analysis of the energetics of aromatic-aromatic stacking interactions for 39 non-covalent reactions of self- and hetero-association of 12 aromatic molecules with different structures and charge states. A protocol for computation of the contributions to the total energy from various energetic terms has been developed and the results are consistent with experiment in 92% of all the systems studied. It is found that the contributions from hydrogen bonds and entropic factors are always unfavorable, whereas contributions from van-der-Waals, electrostatic and/or hydrophobic effects may lead to stabilizing or destabilizing factors depending on the system studied. The analysis carried out in this work provides an answer to the questions 'What forces stabilize/destabilize the stacking of aromatic molecules in aqueous-salt solution and what are their relative importance?'

  1. Gas phase radiolysis and vacuum ultraviolet photolysis of heterocyclic organic compounds. Progress report, February 1, 1974--February 1, 1975

    International Nuclear Information System (INIS)

    Scala, A.A.; Salomon, D.; Colon, I.; D'Angona, J.

    1975-01-01

    In the γ radiolysis of tetrahydrofuran there are pronounced density effects in the pressure range from 0 to 50 Torr with the most important ion-pair yields decreasing as the pressure increases. The relative product yields of the radiolysis is compared with that of xenon photolysis. Possible mechanisms to explain the results obtained are discussed. The ion-pair yields from the γ radiolysis of the heterocyclic amines, ethylenimine, azetidine, pyrrolidine, and piperidine, are determined, and the pressure effects are evaluated. Reactions mechanisms are discussed. The vacuum ultraviolet photolysis products of thietane and tetrahydrothiophene are studied and compared with the γ radiolysis products. Reaction mechanisms are discussed. The status of the construction of a photoionization mass spectrometer and the measurement of the ionization efficiencies and extinction coefficients of organic compounds is reported. (U.S.)

  2. Enhanced natural attenuation of heterocyclic hydrocarbons: biodegradation under anaerobic conditions and in the presence of H2O2

    International Nuclear Information System (INIS)

    Sagner, A.; Tiehm, A.

    2005-01-01

    Heterocyclic aromatic compounds containing nitrogen, sulfur, or oxygen (NSO-HET) are highly mobile due to their high water solubility and low anaerobic degradation rates. In addition some of them are highly toxic and also carcinogenic. However, this class of pollutants is not included in standard risk assessment protocols. In our study, NSO-HET were analyzed in tar oil polluted groundwater plumes originating from (i) a small landfill and (ii) an abandoned manufactured gas plant site. A similar composition of the NSO-HET benzofuran, dibenzo-furan, benzo-thiophene, dibenzo-thiophene, quinoline, and carbazole was found at the two sites. In the polluted groundwater plume, the two ring NSO-HET decreased more rapidly as compared to the three ring NSO-HET. In anaerobic microcosm studies, only benzofuran was degraded under sulfate reducing conditions. In the presence of Fe(III) or nitrate, benzo-thiophene and dibenzo-thiophene were degraded within 400 days. Under aerobic conditions, the degradation of all NSO-HET was observed. In conclusion, the addition of oxygen or hydrogen peroxide is a suitable measure to stimulate biodegradation of hetero-aromatic compounds. (authors)

  3. STUDIES ON RADICAL POLYMERIZATION OF METHYL METHACRYLATE INITIATED WITH ORGANIC PEROXIDE-AMINE SYSTEMS

    Institute of Scientific and Technical Information of China (English)

    QIU Kunyuan; SHUI Li; FENG Xinde

    1984-01-01

    Radical polymerization of methyl methacrylate (MMA) initiated with various diacyl peroxideamine systems was studied. Benzoyl peroxide (BPO) and lauroyl peroxide (LPO) were used as diacyl peroxide component, N,N-dimethyl aniline (DMA) and its para substituted derivatives, i.e., N,N-dimethyl-p-toluidine (DMT), p-hydroxymethyl-N,N-dimethyl aniline (HDMA), p-nitro-N,N-dimethyl aniline (NDMA) and p-dimethylamino benzaldehyde (DMAB) were used as amine components. It was found that the peroxide-DMT systems give higher rates of bulk polymerization Rp of MMA than the organic hydroperoxide-DMT systems with the following descending order BPO-DMT>LPO-DMT>CHP (cumene hydroperoxide)-DMT>TBH (tert-butyl hydroperoxide)-DMT.The aromatic tertiary amines possess obvious structural effect on the Rp values in the diacyl peroxideamine system. The overall activation energy of MMA polymerization was determined and the kinetics of polymerization of MMA initiated with BPO-DMT system was investigated.

  4. 2035-IJBCS-Article-J O Otutu

    African Journals Online (AJOL)

    hp

    the heterocyclic amines in the synthesis of azo dyes, has come under focus. The attraction of the heterocycles stems from their significance in medicine, agriculture, industry and academic research and teaching. The interesting and often intriguing structural and electronic properties of heterocyclic compounds often naturally ...

  5. Novel proton-type ionic liquid doped polyaniline for the headspace solid-phase microextraction of amines

    Energy Technology Data Exchange (ETDEWEB)

    Ai, Youhong [Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China); Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials & Key Laboratory for the Synthesis and Application of Organic Functional Molecules (Ministry of Education), College of Chemistry & Chemical Engineering, Hubei University, Wuhan 430062 (China); Zhao, Faqiong [Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China); Zeng, Baizhao, E-mail: bzzeng@whu.edu.cn [Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China)

    2015-06-23

    Graphical abstract: The novel proton-type ionic liquid (1-sulfobutyl-3-methylimidazolium hydrosulfate) doped polyaniline coating showed granular porous nanostructure and it had high self-EF values and extraction efficiency for amines. - Highlights: • A proton-type ionic liquid-doped polyaniline was fabricated by electrodeposition. • It showed porous granular nanostructure and had large specific surface. • It had high extraction capacity to aromatic amines. • A reasonable self-enrichment factor of SPME fiber has been proposed. - Abstract: A novel proton-type ionic liquid doped polyaniline (HIL-doped PANI) coating was presented, which was prepared on a stainless steel wire by electrodeposition in an aqueous solution containing aniline and 1-sulfobutyl-3-methylimidazolium hydrosulfate. The HIL-doped PANI coating showed granular nanostructure and had large specific surface. When it was applied to the headspace solid-phase microextraction of several amines (i.e., aniline, N-methylaniline, 3-methylaniline, 2-chloroaniline and 3-chloroaniline), it showed high extraction efficiency. The enrichment factors were 191.8–343.9 for different amines, much higher than those of common PANI and commercial polydimethylsiloxane/divinylbenzene coatings. Coupled with gas chromatographic analysis, the linear ranges were 0.097–100 μg/L with correlation coefficients above 0.9942, and the detection limits were 0.012–0.048 μg/L (S/N = 3) for different amines. The relative standard deviations (RSD) were smaller than 8.1% for five successive measurements with single fiber and the fiber-to-fiber RSDs were 8.6–13.8% (n = 5) for these amines. The proposed method was successfully applied to the extraction and determination of amines in organic waste water samples, and the recoveries were 78.3–112.8% for different analytes.

  6. Novel proton-type ionic liquid doped polyaniline for the headspace solid-phase microextraction of amines

    International Nuclear Information System (INIS)

    Ai, Youhong; Zhao, Faqiong; Zeng, Baizhao

    2015-01-01

    Graphical abstract: The novel proton-type ionic liquid (1-sulfobutyl-3-methylimidazolium hydrosulfate) doped polyaniline coating showed granular porous nanostructure and it had high self-EF values and extraction efficiency for amines. - Highlights: • A proton-type ionic liquid-doped polyaniline was fabricated by electrodeposition. • It showed porous granular nanostructure and had large specific surface. • It had high extraction capacity to aromatic amines. • A reasonable self-enrichment factor of SPME fiber has been proposed. - Abstract: A novel proton-type ionic liquid doped polyaniline (HIL-doped PANI) coating was presented, which was prepared on a stainless steel wire by electrodeposition in an aqueous solution containing aniline and 1-sulfobutyl-3-methylimidazolium hydrosulfate. The HIL-doped PANI coating showed granular nanostructure and had large specific surface. When it was applied to the headspace solid-phase microextraction of several amines (i.e., aniline, N-methylaniline, 3-methylaniline, 2-chloroaniline and 3-chloroaniline), it showed high extraction efficiency. The enrichment factors were 191.8–343.9 for different amines, much higher than those of common PANI and commercial polydimethylsiloxane/divinylbenzene coatings. Coupled with gas chromatographic analysis, the linear ranges were 0.097–100 μg/L with correlation coefficients above 0.9942, and the detection limits were 0.012–0.048 μg/L (S/N = 3) for different amines. The relative standard deviations (RSD) were smaller than 8.1% for five successive measurements with single fiber and the fiber-to-fiber RSDs were 8.6–13.8% (n = 5) for these amines. The proposed method was successfully applied to the extraction and determination of amines in organic waste water samples, and the recoveries were 78.3–112.8% for different analytes

  7. Occupational exposure to rubber vulcanization products during repair of rubber conveyor belts in a brown coal mine

    Energy Technology Data Exchange (ETDEWEB)

    Gromiec, J.P.; Wesolowski, W.; Brzeznicki, S.; Wroblewska-Jakubowska, K.; Kucharska, M. [Nofer Institute of Occupational Medicine, Lodz (Poland)

    2002-12-01

    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 C{sub 12}, 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, and 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.

  8. Pro-aromatic and anti-aromatic π-conjugated molecules: an irresistible wish to be diradicals

    KAUST Repository

    Zeng, Zebing

    2015-01-01

    © 2015 The Royal Society of Chemistry. Aromaticity is an important concept to understand the stability and physical properties of π-conjugated molecules. Recent studies on pro-aromatic and anti-aromatic molecules revealed their irresistible tendency to become diradicals in the ground state. Diradical character thus becomes another very important concept and it is fundamentally correlated to the physical (optical, electronic and magnetic) properties and chemical reactivity of most of the organic optoelectronic materials. Molecules with distinctive diradical character show unique properties which are very different from those of traditional closed-shell π-conjugated systems, and thus they have many potential applications in organic electronics, spintronics, non-linear optics and energy storage. This critical review first introduces the fundamental electronic structure of Kekulé diradicals within the concepts of anti-aromaticity and pro-aromaticity in the context of Hückel aromaticity and diradical character. Then recent research studies on various stable/persistent diradicaloids based on pro-aromatic and anti-aromatic compounds are summarized and discussed with regard to their synthetic chemistry, physical properties, structure-property relationships and potential material applications. A summary and personal perspective is given at the end.

  9. Novel non-viral vectors for gene delivery: synthesis of a second-generation library of mono-functionalized poly-(guanidinium)amines and their introduction into cationic lipids.

    Science.gov (United States)

    Byk, G; Soto, J; Mattler, C; Frederic, M; Scherman, D

    1998-01-01

    The development of new gene delivery technologies is a prerequisite towards gene therapy clinical trials. Because gene delivery mediated by viral vectors remains of limited scope due to immunological and propagation risks, the development of new non-viral gene delivery systems is of crucial importance. We have synthesized a secondary library of mono-functionalized poly-(guanidinium)amines generated from a library of mono-functionalized polyamines applying the concept of "libraries from libraries." The method allows a quick and easy access to mono-functionalized geometrically varied poly-(guanidinium)amines. The new building blocks were introduced into cationic lipids to obtain novel poly-(guanidinium)amine lipids, which are potential DNA vectors for gene delivery. Copyright 1998 John Wiley & Sons, Inc.

  10. Novel bioreducible poly(amido amine)s for highly efficient gene delivery

    NARCIS (Netherlands)

    Lin, C.; Zhong, Zhiyuan; Lok, Martin C.; Jiang, Xulin; Hennink, Wim E.; Feijen, Jan; Engbersen, Johannes F.J.

    2007-01-01

    A series of novel bioreducible poly(amido amine)s containing multiple disulfide linkages (SS-PAAs) were synthesized and evaluated as nonviral gene vectors. These linear SS-PAAs could be easily obtained by Michael-type polyaddition of various primary amines to the disulfide-containing cystamine

  11. Alkyne Benzannulation Reactions for the Synthesis of Novel Aromatic Architectures.

    Science.gov (United States)

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

    2017-11-21

    - 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.

  12. Heterocyclic aramid nanoparticle-assisted graphene exfoliation for fabrication of pristine graphene-based composite paper

    Energy Technology Data Exchange (ETDEWEB)

    Mo, Yao; Liu, Qi; Fan, Jinchen, E-mail: Jinchen.fan@shiep.edu.cn; Shi, Penghui; Min, Yulin, E-mail: ahaqmylin@126.com; Xu, Qunjie [Shanghai University of Electric Power, Shanghai Key Laboratory of Materials Protection and Advanced Materials in Electric Power, College of Environmental and Chemical Engineering (China)

    2015-07-15

    Mechanically strong, electrically conductive, and flexible pristine graphene-based composite paper was prepared based on heterocyclic aramid nanoparticle-assisted liquid-phase exfoliation of graphite. The macroscopic heterocyclic aramid yarns were split and assembled into heterocyclic aramid nanoparticles with the size of ∼30 nm by deprotonation in dimethylsulfoxide in the presence of potassium hydroxide. The obtained heterocyclic aramid nanoparticles dimethylsulfoxide dispersion was used as good medium solvent for highly efficiency liquid-phase exfoliation of graphite. The results demonstrated that the concentration of exfoliated graphene can facile reaches ∼2.72 mg/mL after direct sonication of 7 h with assist of heterocyclic aramid nanoparticles. After exfoliation, the self-assembled pristine graphene-based composite paper was fabricated by vacuum-assisted filtration. Due to the introduction of heterocyclic aramid nanoparticles, the self-assembled pristine graphene/heterocyclic aramid nanoparticles composite paper exhibited good mechanical property with tensile strength of ∼129.7 MPa, meantime, has a high electrical conductivity of ∼1.42 × 10{sup 4} S/m.

  13. Heterocyclic aramid nanoparticle-assisted graphene exfoliation for fabrication of pristine graphene-based composite paper

    International Nuclear Information System (INIS)

    Mo, Yao; Liu, Qi; Fan, Jinchen; Shi, Penghui; Min, Yulin; Xu, Qunjie

    2015-01-01

    Mechanically strong, electrically conductive, and flexible pristine graphene-based composite paper was prepared based on heterocyclic aramid nanoparticle-assisted liquid-phase exfoliation of graphite. The macroscopic heterocyclic aramid yarns were split and assembled into heterocyclic aramid nanoparticles with the size of ∼30 nm by deprotonation in dimethylsulfoxide in the presence of potassium hydroxide. The obtained heterocyclic aramid nanoparticles dimethylsulfoxide dispersion was used as good medium solvent for highly efficiency liquid-phase exfoliation of graphite. The results demonstrated that the concentration of exfoliated graphene can facile reaches ∼2.72 mg/mL after direct sonication of 7 h with assist of heterocyclic aramid nanoparticles. After exfoliation, the self-assembled pristine graphene-based composite paper was fabricated by vacuum-assisted filtration. Due to the introduction of heterocyclic aramid nanoparticles, the self-assembled pristine graphene/heterocyclic aramid nanoparticles composite paper exhibited good mechanical property with tensile strength of ∼129.7 MPa, meantime, has a high electrical conductivity of ∼1.42 × 10 4  S/m.

  14. Student Science Research Associates (SSRA) 1996 Research Journal

    Energy Technology Data Exchange (ETDEWEB)

    Knezovich, J. [ed.

    1996-12-01

    The following student projects are reported: SSRA water research projects, various effects on polliwogs` growth and development, effects of Willow Park Golf Course on nitrate and phosphate levels in San Leandro Creek, water quality evaluation using color infrared photography, biochemical analysis of aquatic insects, effects of miracid/calcium chloride/liquid plant food on stringless bush beans, effects of vegetable oil on bean growth, effect of river water on lima beans, effect of storm water runoff on pH and phosphate levels of Dry Creek, acid rain in Modesto, use of random amplified polymorphic DNA to study Egeria Densa, and effect of marination on formation of heterocyclic aromatic amines in cooked chicken meat.

  15. Gold-catalyzed heterocyclizations in alkynyl- and allenyl-β-lactams

    Directory of Open Access Journals (Sweden)

    Pedro Almendros

    2011-05-01

    Full Text Available New gold-catalyzed methods using the β-lactam scaffold have been recently developed for the synthesis of different sized heterocycles. This overview focuses on heterocyclization reactions of allenic and alkynic β-lactams which rely on the activation of the allene and alkyne component. The mechanism as well as the regio- and stereoselectivity of the cyclizations are also discussed.

  16. Recent advances in the ruthenium-catalyzed hydroarylation of alkynes with aromatics: synthesis of trisubstituted alkenes.

    Science.gov (United States)

    Manikandan, Rajendran; Jeganmohan, Masilamani

    2015-11-14

    The hydroarylation of alkynes with substituted aromatics in the presence of a metal catalyst via chelation-assisted C-H bond activation is a powerful method to synthesize trisubstituted alkenes. Chelation-assisted C-H bond activation can be done by two ways: (a) an oxidative addition pathway and (b) a deprotonation pathway. Generally, a mixture of cis and trans stereoisomeric as well as regioisomeric trisubstituted alkenes was observed in an oxidative addition pathway. In the deprotonation pathway, the hydroarylation reaction can be done in a highly regio- and stereoselective manner, and enables preparation of the expected trisubstituted alkenes in a highly selective manner. Generally, ruthenium, rhodium and cobalt complexes are used as catalysts in the reaction. In this review, a ruthenium-catalyzed hydroarylation of alkynes with substituted aromatics is covered completely. The hydroarylation reaction of alkynes with amide, azole, carbamate, phosphine oxide, amine, acetyl, sulfoxide and sulphur directed aromatics is discussed.

  17. Regio- and Enantioselective N-Allylations of Imidazole, Benzimidazole, and Purine Heterocycles Catalyzed by Single-Component Metallacyclic Iridium Complexes

    Science.gov (United States)

    Stanley, Levi M.

    2010-01-01

    Highly regio- and enantioselective iridium-catalyzed N-allylations of benzimidazoles, imidazoles, and purines have been developed. N-Allylated benzimidazoles and imidazoles were isolated in high yields (up to 97%) with high branched-to-linear selectivity (up to 99:1) and enantioselectivity (up to 98% ee) from the reactions of benzimidazole and imidazole nucleophiles with unsymmetrical allylic carbonates in the presence of single component, ethylene-bound, metallacyclic iridium catalysts. N-Allylated purines were also obtained in high yields (up to 91%) with high N9:N7 selectivity (up to 96:4), high branched-to-linear selectivity (98:2), and high enantioselectivity (up to 98% ee) under similar conditions. The reactions encompass a range of benzimidazole, imidazole, and purine nucleophiles, as well as a variety of unsymmetrical aryl, heteroaryl, and aliphatic allylic carbonates. Competition experiments between common amine nucleophiles and the heterocyclic nitrogen nucleophiles studied in this work illustrate the effect of nucleophile pKa on the rate of iridium-catalyzed N-allylation reactions. Kinetic studies on the allylation of benzimidazole catalyzed by metallacyclic iridium-phosphoramidite complexes, in combination with studies on the deactivation of these catalysts in the presence of heterocyclic nucleophiles, provide insight into the effects of the structure of the phosphoramidite ligands on the stability of the metallacyclic catalysts. The data obtained from these studies has led to the development of N-allylations of benzimidazoles and imidazoles in the absence of an exogenous base. PMID:19480431

  18. Thiosemicarbazides in the synthesis of five- and six-membered heterocyclic compounds

    International Nuclear Information System (INIS)

    Gazieva, Galina A; Kravchenko, Angelina N

    2012-01-01

    Data on key chemical transformations of thiosemicarbazides resulting in heterocyclic compounds are generalized and described systematically. Methods for the synthesis of five- and six-membered heterocycles with two and three heteroatoms are considered. The bibliography includes 190 references.

  19. Novel organometallic aromatic polyester based on ferrocene

    Institute of Scientific and Technical Information of China (English)

    Wei

    2010-01-01

    A novel polyester containing ferrocenyl was prepared by low-temperature interface polycondensation of 1,1'-ferrocenedi-carboxylic acid chloride with 4-(4-hydroxyphenyl)-2,3-phthalazin-l-one(DHPZ), which is a twisted non-coplanar heterocyclic bisphenol-like monomer. The newly generated polymer was evaluated based on characterization of its solubility, viscosity measurements, elemental analysis, FTIR spectroscopy, differential scanning calorimetric and thermogravimetric studies.

  20. Influence of red wine pomace seasoning and high-oxygen atmosphere storage on carcinogens formation in barbecued beef patties.

    Science.gov (United States)

    García-Lomillo, Javier; Viegas, Olga; Gonzalez-SanJose, Maria L; Ferreira, Isabel M P L V O

    2017-03-01

    Polycyclic aromatic hydrocarbons (PAHs) and heterocyclic aromatic amines (HAs) are carcinogenic compounds formed in barbecued meat. Conditions that reduce their formation are of major interest. This study aims to evaluate the influence of red wine pomace seasoning (RWPS) and high-oxygen atmosphere storage on the formation of PAHs and HAs in barbecued beef patties. In general, the levels of PAHs and HAs quantified were low. The storage (9days) promoted higher formation of PAHs in control patties without increase of HAs. RWPS patties cooked at preparation day presented higher levels of PAHs and HAs than control. Nevertheless, RWPS patties cooked after storage presented lower levels of PAHs and HAs than control. ABTS assay pointed out that higher radical scavenging activity may be related to with lower PAHs or HAs formation. In conclusion, RWPS can be an interesting ingredient to inhibit the formation of cooking carcinogens in barbecued patties stored at high-oxygen atmosphere. Copyright © 2016 Elsevier Ltd. All rights reserved.

  1. Crystal structure of bis(azido-κNbis(quinolin-8-amine-κ2N,N′iron(II

    Directory of Open Access Journals (Sweden)

    Fatima Setifi

    2016-10-01

    Full Text Available The search for new molecular materials with interesting magnetic properties using the pseudohalide azide ion and quinolin-8-amine (aqin, C9H8N2 as a chelating ligand, led to the synthesis and structure determination of the title complex, [Fe(N32(C9H8N22]. The complex shows an octahedral geometry, with the FeII atom surrounded by six N atoms; the two N3− anions coordinate in a cis configuration, while the remaining N atoms originate from the two quinolin-8-amine ligands with the quinoline N atoms lying on opposite sides of the Fe atom. The crystal packing is dominated by layers of hydrophilic and aromatic regions parallel to the ac plane, stabilized by a two-dimensional hydrogen-bonded network and π–π stacking.

  2. Carbon-14 labelled nitrogen heterocycles; the syntheses of three phosphodiesterase inhibitors

    International Nuclear Information System (INIS)

    Lawrie, K.W.M.; Novelli, C.E.A.; Saunders, David

    1995-01-01

    The syntheses of three heterocyclic phosphodiesterase inhibitors are described from a common radiolabelled precursor, namely 2-propoxybenzo[cyano- 14 C] nitrile. Conversion of the nitrile to the corresponding methyl ketone or amidine allows elaboration of the heterocycles radiolabelled within the ring systems. (Author)

  3. Microwave-assisted synthesis of bio-active heterocycles in aqueous media

    KAUST Repository

    Polshettiwar, Vivek

    2010-01-01

    Synthesis of bio-active heterocycles and fine chemicals in aqueous media are one of the best solutions for the development of green and sustainable protocols. To illustrate the advantages of aqueous MW chemistry in heterocycle synthesis, in this chapter, various synthetic pathways developed in recent years in aqueous reaction media using microwave irradiation are described.

  4. Synthesis of heterocyclic compounds through palladium-catalyzed C-H cyclization processes.

    Science.gov (United States)

    Inamoto, Kiyofumi

    2013-01-01

    Herein, we describe our development of synthetic methods for heterocyclic compounds based on the palladium-catalyzed carbon-hydrogen bond (C-H) functionalization/intramolecular carbon-heteroatom (nitrogen or sulfur) bond formation process. By this C-H cyclization method, we efficiently prepared various N-heterocycles, including indazoles, indoles, and 2-quinolinones, as well as S-heterocycles such as benzothiazoles and benzo[b]thiophenes. Yields are typically good to high and good functional-group tolerance is observed for each process, thereby indicating that the method provides a novel, highly applicable synthetic route to the abovementioned biologically important heterocyclic frameworks. As an application of this approach, an auto-tandem-type, one-pot process involving the oxidative Heck reaction and subsequent C-H cyclization using cinnamamides and arylboronic acids as starting materials in the presence of a palladium catalyst was also developed for the rapid construction of the 2-quinolinone nucleus.

  5. Comparative chronic toxicity of homo- and heterocyclic aromatic compounds to benthic and terrestrial invertebrates: Generalizations and exceptions.

    NARCIS (Netherlands)

    Leon Paumen, M.; de Voogt, P.; van Gestel, C.A.M.; Kraak, M.H.S.

    2009-01-01

    The aim of the present study was to elucidate consistent patterns in chronic polycyclic aromatic compound (PAC) toxicity to soil and sediment inhabiting invertebrates. Therefore we examined our experimental dataset, consisting of twenty-one chronic effect concentrations for two soil invertebrates

  6. Comparative chronic toxicity of homo- and heterocyclic aromatic compounds to benthic and terrestrial invertebrates: Generalizations and exceptions

    NARCIS (Netherlands)

    León Paumen, M.; de Voogt, P.; van Gestel, C.A.M.; Kraak, M.H.S.

    2009-01-01

    The aim of the present study was to elucidate consistent patterns in chronic polycyclic aromatic compound (PAC) toxicity to soil and sediment inhabiting invertebrates. Therefore we examined our experimental dataset, consisting of twenty-one chronic effect concentrations for two soil invertebrates

  7. The role of hydrogen bonding on kinetics of rearrangement of heterocyclic aldoximes in perchloric acide

    International Nuclear Information System (INIS)

    Azzouz, A.S.; Abdullah, K.A.; Al-Niemi, I.

    1995-01-01

    Four paris of syn and anti aromatic heterocyclic aldoximes as 2-thiophenealdoxime, 2- furfuraladoxime, 2-pyridinealdoxime and 2-pyrrolealdoxime are prepared. The strcutures of these geometrical isomers are confirmed by the meaasurements of their U.V. I, R and melting points. Experiments show the existence of these aldoximers in an intramolecular hy-drogen bonding with variable strength depending on the hetero ztoms in the aldoximes. The first order rate constants of the rearrangement of syn aldoximes follow the order of hetero S>O>N, while the anti aldoximes show irregular order, Factors governing the aniti constants of the rearrangement of syn and anti aldoximes are analysed. Activation parameters are estimated and discussed on the basis of isokinetic relation-ship. The differences in physical and spectroscpic behavior of aldoximes lead to an important suggestion regarding the configuration of oxime. (author). 27 refs., 2 figs., 2 tabs

  8. Heterocyclic N-Oxides – An Emerging Class of Therapeutic Agents

    Science.gov (United States)

    Mfuh, Adelphe M.; Larionov, Oleg V.

    2016-01-01

    Heterocyclic N-oxides have emerged as potent compounds with anticancer, antibacterial, antihypertensive, antiparasitic, anti-HIV, anti-inflammatory, herbicidal, neuroprotective, and procognitive activities. The N-oxide motif has been successfully employed in a number of recent drug development projects. This review surveys the emergence of this scaffold in the mainstream medicinal chemistry with a focus on the discovery of the heterocyclic N-oxide drugs, N-oxide-specific mechanisms of action, drug-receptor interactions and synthetic avenues to these compounds. As the first review on this subject that covers the developments since 1950s to date, it is expected that it will inspire wider implementation of the heterocyclic N-oxide motif in the rational design of new medicinal agents. PMID:26087764

  9. Identification and quantification of phthalates, PAHs, amines, phenols, and metals in tattoo

    Energy Technology Data Exchange (ETDEWEB)

    Shin, Ho Sang; Lim, Hyun Hee [Kongju National University, Kongju (Korea, Republic of)

    2015-08-15

    The determination methods of polycyclic aromatic hydrocarbons (PAHs), phthalates, primary amines, phenols, and metals in tattoo dyes have been optimized and validated using gas chromatography-mass spectrometry, liquid chromatography-tandem mass spectrometry, and inductively coupled plasma-mass spectrometry. Twelve PAHs, 3 phthalates, 4 amines, and 15 metals were identified and quantified in 16 different tattoo dyes purchased from shops in the Republic of Korea. Phenols were not detected in any sample. The total PAHs in six inks and benzo(a)pyrene in one tattoo ink exceeded the legal limit set by the Council of Europe, and their maximum detected concentrations were about 10 and 5 times the limits of the compounds, respectively. 3,3′-Dichlorobenzidine and o-anisidine, which should not be present in tattoo inks by Resolution ResAP (2008) of the Council of Europe, were detected in tattoo inks. Also, Cd, Pb, Cu, Ba, Ni, Sb, Zn, and As exceeded the limits. These hazardous compounds should be controlled to the lowest possible concentrations in the raw materials and the production procedure of tattoo ink.

  10. Identification and quantification of phthalates, PAHs, amines, phenols, and metals in tattoo

    International Nuclear Information System (INIS)

    Shin, Ho Sang; Lim, Hyun Hee

    2015-01-01

    The determination methods of polycyclic aromatic hydrocarbons (PAHs), phthalates, primary amines, phenols, and metals in tattoo dyes have been optimized and validated using gas chromatography-mass spectrometry, liquid chromatography-tandem mass spectrometry, and inductively coupled plasma-mass spectrometry. Twelve PAHs, 3 phthalates, 4 amines, and 15 metals were identified and quantified in 16 different tattoo dyes purchased from shops in the Republic of Korea. Phenols were not detected in any sample. The total PAHs in six inks and benzo(a)pyrene in one tattoo ink exceeded the legal limit set by the Council of Europe, and their maximum detected concentrations were about 10 and 5 times the limits of the compounds, respectively. 3,3′-Dichlorobenzidine and o-anisidine, which should not be present in tattoo inks by Resolution ResAP (2008) of the Council of Europe, were detected in tattoo inks. Also, Cd, Pb, Cu, Ba, Ni, Sb, Zn, and As exceeded the limits. These hazardous compounds should be controlled to the lowest possible concentrations in the raw materials and the production procedure of tattoo ink

  11. Cytotoxic, antibacterial activity and physico-chemical properties of ...

    African Journals Online (AJOL)

    ... aromatic aldehydes and aromatic amine in ethanol under acidic conditions. The geometry of these Schiff bases was established using various spectroscopic methods like infrared (IR), nuclear magnetic resonance (NMR) and mass spectrometry. The conductivity studies reveal the non electrolytic behavior of Schiff bases.

  12. Carbon-14 labelled nitrogen heterocycles; the syntheses of three phosphodiesterase inhibitors

    Energy Technology Data Exchange (ETDEWEB)

    Lawrie, K.W.M.; Novelli, C.E.A.; Saunders, David [SmithKline Beecham Pharmaceuticals Research and Development, Harlow (United Kingdom). Synthetic Isotope Chemistry Dept.; Coates, W.J. [SmithKline Beecham Pharmaceuticals Research and Development, Welwyn (United Kingdom)

    1995-09-01

    The syntheses of three heterocyclic phosphodiesterase inhibitors are described from a common radiolabelled precursor, namely 2-propoxybenzo[cyano-{sup 14}C] nitrile. Conversion of the nitrile to the corresponding methyl ketone or amidine allows elaboration of the heterocycles radiolabelled within the ring systems. (Author).

  13. Azobisisobutyronitrile initiated aerobic oxidative transformation of amines: coupling of primary amines and cyanation of tertiary amines.

    Science.gov (United States)

    Liu, Lianghui; Wang, Zikuan; Fu, Xuefeng; Yan, Chun-Hua

    2012-11-16

    In the presence of a catalytic amount of radical initiator AIBN, primary amines are oxidatively coupled to imines and tertiary amines are cyanated to α-aminonitriles. These "metal-free" aerobic oxidative coupling reactions may find applications in a wide range of "green" oxidation chemistry.

  14. The thermochromic behavior of aromatic amine-SO2 charge transfer complexes

    Science.gov (United States)

    Monezi, Natália M.; Borin, Antonio C.; Santos, Paulo S.; Ando, Rômulo A.

    2017-02-01

    The distinct thermochromism observed in solutions containing N,N-dimethylaniline (DMA) and N,N-diethylaniline (DEA) and SO2 was investigated by resonance Raman spectroscopy in a wide range of temperatures. The results indicate in addition to the charge transfer (CT) complexes DMA-SO2 and DEA-SO2, the presence of collision complexes involving the CT complexes and excess DMA and DEA molecules. The latter in fact is the chromophore responsible for the long wavelength absorption originating the color. The Raman signature of the collision complex was attributed to the distinct enhancement of a band at 1140 cm- 1 assigned to νs(SO2), in contrast to the same mode in the 1:1 complex at 1115 cm- 1. The intensity of such band, assigned to the collision complex is favored at high temperatures and depends on the steric hindrance associated to amines, as well as the SO2 molar fraction. Quantum chemical calculations based on time-dependent density functional theory (TDDFT) support the proposed interpretation.

  15. [Synthetic Studies of Bioactive Heterocyclic Natural Products and Fused Heterocyclic Compounds Based on the Thermal Electrocyclic or Azaelectocyclic Reaction of 6π-Electron or Aza-6π-electron Systems].

    Science.gov (United States)

    Hibino, Satoshi

    2016-01-01

    Since 1979, synthetic studies of bioactive heterocyclic natural products and condensed heteroaromatic compounds based on the thermal electrocyclic reaction of 6π-electron or aza-6π-electron systems incorporating the double bond of the principal aromatic or heteroaromatic ring have been conducted by our research group. In this review, five types of electrocyclic and azaelectrocyclic reaction are described: 1) the synthesis of the carbazole alkaloids hyellazole and 6-chlorohyellazole through the electrocyclic reaction of 2,3-bisalkenylindoles; 2) synthetic studies of the pyridocarbazole alkaloids ellipticine and olivacine through the electrocyclic reactions of the indole-2,3- and pyridine-3,4-quinodimethane intermediates; 3) synthetic studies of polysubstituted carbazole alkaloids through the allene-mediated electrocyclic reactions involving the indole 2,3-bond; 4) synthetic studies of fused pyridine rings through the azaelectrocyclic reaction of the 1-aza-6π-electron system using the oxime or oxime ether; and 5) synthetic studies of fused pyridine rings through the azaelectrocyclic reaction of the 2-aza-6π-electron system using a carbodiimide or isocyanate.

  16. Azomesogens with a heterocyclic moiety

    Indian Academy of Sciences (India)

    Unknown

    Azomesogens with a heterocyclic moiety. †. JAYRANG S DAVE and MEERA MENON*. Department of Applied Chemistry, Faculty of Technology and Engineering, MS University of Baroda,. Baroda 390 001, India. Abstract. Azobenzene derivatives were among the first ten liquid crystalline compounds. But there have been.

  17. Devulcanization of Waste Tire Rubber Using Amine Based Solvents and Ultrasonic Energy

    Directory of Open Access Journals (Sweden)

    Walvekar Rashmi

    2018-01-01

    Full Text Available This research project focuses on an alternative pathway of devulcanizing waste tire rubber by using amine based chemicals. Waste tire rubbers are known to be as toxic, non-degradable material due to their vulcanized crosslink carbon structure, and disposing of such waste could impose hazardous impacts on the environment. The current rubber recycling methods that are practiced today are rather uneconomical, non-environmentally friendly, and also producing recycled rubber with low quality due to the alteration in the main polymeric chains of waste rubber. This project aims to answer the question of whether the usage of amine can produce high quality rubber, where the properties of recycled rubber is almost the same as new/virgin rubber. With known potential of amine, it is a challenge for the chemical to selectively cleave the sulfur bonds without affecting the main carbon backbone chain in the rubber structure and diminishing much of the rubber properties. To study this research, amine-treated rubber must undergo devulcanisation process by applying heat and sonication energy. Then, the properties of the amine-treated rubber were determined through a set of characterization tests and analysis which are: gel content test to determine the weight of rubber before and after devulcanization, the thermogravimetric analysis (TGA to determine the thermal degradation and stability of rubber, and Fourier Transform Infrared Spectroscopy (FTIR to determine any structural change of the rubber. In this research so far, the first two preliminary analysis tests have been performed. The gel content test has shown that tertiary amine samples possessed a lower gel content (% of (77 – 63 %, compared to primary amine samples (falls within the range of 80%, as well as the TGA test in which tertiary amine samples degrade faster than primary amine samples (suggesting a higher degree of rubber structure breakdown. For each type of amine, the concertation of amine did

  18. Inhibitory profiles of spices against free and protein-bound heterocyclic amines of roast beef patties as revealed by ultra-performance liquid chromatography-tandem mass spectrometry and principal component analysis.

    Science.gov (United States)

    Chen, Jing; He, Zhiyong; Qin, Fang; Chen, Jie; Cao, Dongsheng; Guo, Fengxian; Zeng, Maomao

    2017-11-15

    The effects of various levels of chili pepper, Sichuan pepper, and black pepper on the amounts of 17 heterocyclic amines (HAs) from seven categories of both free and protein-bound states in roast beef patties were assessed by ultra-performance liquid chromatography-tandem mass spectrometry combined with principal component analysis. Three groups of HA, including imidazopyridines (DMIP), imidazoquinoxalines (MeIQx and 4,8-MeIQx), and β-carbolines (norharman and harman), were detected and quantified in both their free and protein-bound states, whereas PhIP was detected only in its free state, and imidazoquinolines (IQ, IQ[4,5-b], and MeIQ), α-carbolines (AαC and MeAαC), and phenylpyridines (Phe-P-1) were detected only in their protein-bound states. The results demonstrate that the peppers at all three levels had significant inhibitory effects on free PhIP, DMIP, MeIQx, and 4,8-DiMeIQx and could promote free norharman. Harman was significantly suppressed by chili pepper and black pepper, but enhanced by Sichuan pepper. All 11 protein-bound HAs, with the exception of IQ, IQ[4,5-b], and MeIQx with added chili pepper, were significantly reduced by the three peppers. The total amounts of the free and protein-bound states of all 11 HAs (1692.4 ± 78.9 ng g -1 ), imidazopyridines (5.5 ± 0.2 ng g -1 ), imidazoquinolines (7.2 ± 0.2 ng g -1 ), imidazoquinoxalines (6.9 ± 0.2 ng g -1 ), α-carbolines (20.1 ± 0.4 ng g -1 ), and β-carbolines (1651.7 ± 79.5 ng g -1 ) were suppressed by each level of all of the three peppers except for 0.5% and 1.0% chili pepper. Our findings may facilitate the inhibition of HA formation in the processing of meat products.

  19. Combinatorial synthesis of oxazol-thiazole bis-heterocyclic compounds.

    Science.gov (United States)

    Murru, Siva; Nefzi, Adel

    2014-01-13

    A combinatorial library of novel oxazol-thiazole bis-heterocycles was synthesized in good to excellent overall yields with high purity using a solution and solid-phase parallel synthesis approach. Oxazole amino acids, prepared from serine methyl ester and amino acids via coupling and cyclodehydration, were treated with Fmoc-NCS and α-haloketones for the parallel synthesis of diverse bis-heterocycles. Fmoc-isothiocyanate is used as a traceless reagent for thiazole formation. Oxazole diversity can be achieved by using variety of amino acids, whereas thiazole diversity is produced with various haloketones.

  20. Synthesis and antiacetylcholinesterase activity of new D-glyceraldehyde heterocyclic derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Scorzo, Cecilia M.; Fascio, Mirta L.; D' Accorso, Norma B. [Universidad de Buenos Aires, Buenos Aires (Argentina). Facultad de Ciencias Exactas y Naturales. Dept. de Quimica Organica; Cabrera, Margarita Gutierrez; Saavedra, Luis Astudillo [Universidad de Talca (Chile). Inst. de Quimica de Productos Naturales. Lab. de Sintesis Organica

    2010-07-01

    We report herein the convenient procedures for the syntheses of different heterocyclic compounds from 2,3-O-isopropylidene-D-glyceraldehyde using intramolecular cyclization, 1,3-dipolar cycloaddition or bimolecular coupling reactions. The products were characterized by {sup 1}H and {sup 13}C NMR spectroscopy and elemental analysis. The new heterocycles and their derivatives were evaluated as inhibitors of acetylcholinesterase enzyme. (author)

  1. Synthesis and antiacetylcholinesterase activity of new D-glyceraldehyde heterocyclic derivatives

    International Nuclear Information System (INIS)

    Scorzo, Cecilia M.; Fascio, Mirta L.; D'Accorso, Norma B.; Cabrera, Margarita Gutierrez; Saavedra, Luis Astudillo

    2010-01-01

    We report herein the convenient procedures for the syntheses of different heterocyclic compounds from 2,3-O-isopropylidene-D-glyceraldehyde using intramolecular cyclization, 1,3-dipolar cycloaddition or bimolecular coupling reactions. The products were characterized by 1 H and 13 C NMR spectroscopy and elemental analysis. The new heterocycles and their derivatives were evaluated as inhibitors of acetylcholinesterase enzyme. (author)

  2. Analysis of aromatic amines in water samples by liquid-liquid-liquid microextraction with hollow fibers and high-performance liquid chromatography.

    Science.gov (United States)

    Zhao, Limian; Zhu, Lingyan; Lee, Hian Kee

    2002-07-19

    Liquid-liquid-liquid microextraction (LLLME) with hollow fibers in high-performance liquid chromatography (HPLC) has been applied as a rapid and sensitive quantitative method for the detection of four aromatic amines (3-nitroaniline, 4-chloroaniline, 4-bromoaniline and 3,4-dichloroaniline) in environmental water samples. The preconcentration procedure was induced by the pH difference inside and outside the hollow fiber. The target compounds were extracted from 4-ml aqueous sample (donor solution, pH approximately 13) through a microfilm of organic solvent (di-n-hexyl ether), immobilized in the pores of a hollow fiber (1.5 cm length x 0.6 mm I.D.), and finally into 4 microl of acid acceptor solution inside the fiber. After a prescribed period of time, the acceptor solution inside the fiber was withdrawn into the microsyringe and directly injected into the HPLC system for analysis. Factors relevant to the extraction procedure were studied. Up to 500-fold enrichment of analytes could be obtained under the optimized conditions (donor solution: 0.1 M sodium hydroxide solution with 20% sodium chloride and 2% acetone; organic phase: di-n-hexyl ether; acceptor solution: 0.5 M hydrochloric acid and 500 mM 18-crown-6 ether; extraction time of 30 min; stirring at 1,000 rev./min). The procedure also served as a sample clean-up step. The influence of humic acid on the extraction efficiency was also investigated, and more than 85% relative recoveries of the analytes at two different concentrations (20 and 100 microg/l) were achieved at various concentration of humic acid. This technique is a low cost, simple and fast approach to the analysis of polar compounds in aqueous samples.

  3. Palladium-Catalyzed Formal Cross-Coupling of Diaryl Ethers with Amines: Slicing the 4-O-5 Linkage in Lignin Models.

    Science.gov (United States)

    Zeng, Huiying; Cao, Dawei; Qiu, Zihang; Li, Chao-Jun

    2018-03-26

    Lignin is the second most abundant organic matter on Earth, and is an underutilized renewable source for valuable aromatic chemicals. For future sustainable production of aromatic compounds, it is highly desirable to convert lignin into value-added platform chemicals instead of using fossil-based resources. Lignins are aromatic polymers linked by three types of ether bonds (α-O-4, β-O-4, and 4-O-5 linkages) and other C-C bonds. Among the ether bonds, the bond dissociation energy of the 4-O-5 linkage is the highest and the most challenging to cleave. To date, 4-O-5 ether linkage model compounds have been cleaved to obtain phenol, cyclohexane, cyclohexanone, and cyclohexanol. The first example of direct formal cross-coupling of diaryl ether 4-O-5 linkage models with amines is reported, in which dual C(Ar)-O bond cleavages form valuable nitrogen-containing derivatives. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. 1H NMR analysis of complexation of hydrotropic agents nicotinamide and caffeine with aromatic biologically active molecules in aqueous solution

    Science.gov (United States)

    Lantushenko, Anastasia O.; Mukhina, Yulia V.; Veselkov, Kyrill A.; Davies, David B.; Veselkov, Alexei N.

    2004-07-01

    NMR spectroscopy has been used to elucidate the molecular mechanism of solubilization action of hydrotropic agents nicotinamide (NA) and caffeine (CAF). Hetero-association of NA with riboflavine-mononucleotide (FMN) and CAF with low soluble in aqueous solution synthetic analogue of antibiotic actinomycin D, actinocyl-bis-(3-dimethylaminopropyl) amine (Actill), has been investigated by 500 MHz 1H NMR spectroscopy. Concentration and temperature dependences of proton chemical shifts have been analysed in terms of a statistical-thermodynamic model of indefinite self- and heteroassociation of aromatic molecules. The obtained results enable to conclude that NA-FMN and CAF-Actill intermolecular complexes are mainly stabilized by the stacking interactions of the aromatic chromophores. Hetero-association of the investigated molecules plays an important role in solubilization of aromatic drugs by hydrotropic agents nicotinamide and caffeine.

  5. Pyridoxylamine reactivity kinetics as an amine based nucleophile for screening electrophilic dermal sensitizers

    Science.gov (United States)

    Chipinda, Itai; Mbiya, Wilbes; Adigun, Risikat Ajibola; Morakinyo, Moshood K.; Law, Brandon F.; Simoyi, Reuben H.; Siegel, Paul D.

    2015-01-01

    Chemical allergens bind directly, or after metabolic or abiotic activation, to endogenous proteins to become allergenic. Assessment of this initial binding has been suggested as a target for development of assays to screen chemicals for their allergenic potential. Recently we reported a nitrobenzenethiol (NBT) based method for screening thiol reactive skin sensitizers, however, amine selective sensitizers are not detected by this assay. In the present study we describe an amine (pyridoxylamine (PDA)) based kinetic assay to complement the NBT assay for identification of amine-selective and non-selective skin sensitizers. UV-Vis spectrophotometry and fluorescence were used to measure PDA reactivity for 57 chemicals including anhydrides, aldehydes, and quinones where reaction rates ranged from 116 to 6.2 × 10−6 M−1 s−1 for extreme to weak sensitizers, respectively. No reactivity towards PDA was observed with the thiol-selective sensitizers, non-sensitizers and prohaptens. The PDA rate constants correlated significantly with their respective murine local lymph node assay (LLNA) threshold EC3 values (R2 = 0.76). The use of PDA serves as a simple, inexpensive amine based method that shows promise as a preliminary screening tool for electrophilic, amine-selective skin sensitizers. PMID:24333919

  6. Development of a GC-MS-SPME Method for the Determination of Amines in Meteorites

    Science.gov (United States)

    Hilts, R. W.; Skelhorne, A. W.; Simkus, D.; Herd, C. D. K.

    2016-08-01

    A GC-MS-SPME analytical method for the direct determination of amines in aqueous solution has been developed. The key step in the procedure is the conversion of the amines into their non-volatile ammonium salts by protonation with HCl.

  7. Spectroscopic Evidence for Covalent Binding of Sulfadiazine to Natural Soils via 1,4-nucleophilic addition (Michael Type Addition) studied by Spin Labeling ESR

    Science.gov (United States)

    Aleksandrova, Olga

    2015-04-01

    with different polarity. As shown by the spin labeling ESR experiment, molecules modeling SDZ were promptly bound to non-hydrolysable network of soil organic matter only via the aromatic amines that was accompanied by a prompt enlargement of humic particles binding aromatic amines, whereas binding of decomposition products of SDZ to humic acids of soil via the aliphatic amines was not observable. The ESR spectra obviously showed a single-phase process of covalent binding of the aromatic amines. Repeated washouts of labeled soil samples using distil water and ultrafiltration through the membrane of 5000 MWCO PES confirmed irreversible binding of the aromatic amines, and showed that via the aliphatic amines, binding of SDZ or decomposition products of SDZ to soil might also occur but reversibly and only to small soil molecules, which don't enter into the composition of non-hydrolysable part of soil organic matter. SL ESR experiments of different soils at the presence of Laccase highlighted that covalent binding of the aromatic amines to humic particles occurred in the specific hydrophobic areas of soil found as depleted in oxygen. All measured data evidenced that first, SDZ might be decomposed that allowed for measuring the same change of a paramagnetic signal of soil organic matter influenced by both aromatic and aliphatic amines as in the experiment of the interaction of soil with SDZ. Second, a decomposition product of SDZ with the aromatic amine might be bound to non-hydrolysable parts of soil organic matter under specific anaerobic conditions only via 1,4 - nucleophilic addition, Michael-type addition. Gulkowska, A., Thalmann, B., D., Hollender, J., & Krauss, M. (2014). Chemosphere, 107, 366 - 372. Müller, T., Rosendahl, I., Focks, A., Siemens, J., Klasmeier, J., & Matthies. (2013). Environmental Pollution, 172,180 - 185. Nowak, K.M., Miltner, A., Gehre, M., Schaeffer, A., & Kaestner, M. (2011). Environmental Science & Technology 45, 999 - 1006. Weber, E.J., Spidle

  8. Oxidative cleavage of non-phenolic β-O-4 lignin model dimers by an extracellular aromatic peroxygenase

    Science.gov (United States)

    Matthias Kinne; Marzena Poraj-Kobielska; Rene Ullrich; Paula Nousiainen; Jussi Sipilä; Katrin Scheibner; Kenneth E. Hammel; Martin Hofrichter

    2011-01-01

    The extracellular aromatic peroxygenase of the agaric fungus Agrocybe aegerita catalyzed the H2O2-dependent cleavage of non-phenolic arylgiycerol-ß-aryl ethers (ß-O-4 ethers). For instance 1-(3,4-dimethoxyphenyl)-2-(2-methoxy-phenoxy)propane-1,3-diol, a recalcitrant dimeric lignin model compound that represents the major...

  9. Polymorphisms in the xenobiotic transporter Multidrug Resistance 1 (MDR1) and interaction with meat intake in relation to risk of colorectal cancer in a Danish prospective case-cohort study

    DEFF Research Database (Denmark)

    Andersen, Vibeke; Østergaard, Mette; Christensen, Jane

    2009-01-01

    (rs5275) polymorphisms in the 3'-untranslated region. The polymorphisms were assessed together with lifestyle factors in a nested case-cohort study of 359 cases and a random cohort sample of 765 participants from the Danish prospective Diet, Cancer and Health study. Results Carriers of the variant......Background The xenobiotic transporters, Multidrug Resistance 1 (MDR1/ABCB1) and Breast Cancer Resistance Protein (BCRP/ABCG2) may restrict intestinal absorption of various carcinogens, including heterocyclic amines (HCA) and polycyclic aromatic hydrocarbons (PAH). Cyclooxygenase-2 (COX-2) derived...... prostaglandins promote gastrointestinal carcinogenesis, affecting angiogenesis, apoptosis, and invasiveness. The aim of this study was to investigate if polymorphisms in these genes were associated with risk of colorectal cancer (CRC), and to investigate possible interactions with lifestyle factors...

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

    Science.gov (United States)

    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.

  11. Fusion of heterocyclic polymerogenic units onto a central ring: a fruitful approach to the investigation and specific tailoring of the dependence of electrical properties on monomer structure in conductive polyheterocycles

    Energy Technology Data Exchange (ETDEWEB)

    Berlin, A.; Brenna, E.; Pagani, G.A.; Sannicolo, F. (Dipt. di Chimica Organica e Industriale, Univ. di Milano (Italy) Centro CNR Speciali Sistemi Organici, Milan (Italy)); Zotti, G.; Schiavon, G. (CNR, Ist. di Polarografia ed Elettrochimica Preparativa, Padua (Italy))

    1992-09-01

    In this review the ''spacer'' strategy is described and evaluated in detail. According to this principle, the monomer contains, as terminal units, two polymerogenic rings (pyrrole or thiophene) linked to a central [pi]-conjugatively-active frame; as spacers, we have investigated ethenylic, sulphide, and aromatic moieties. In this way the redox potentials, E[sup 0], of the polymers derived from such monomers can be calibrated by the substituent effect exerted by the spacer. This control is beneficial because it is possible to increase the E[sup 0] value of polypyrrole-type systems and decrease the E[sup 0] value of polythiophene-type systems. Also, the ''spacer'' may be further functionalised and, being remote from the polymerisation site, cannot alter the conductivity characteristics typical of the polymer derived from the parent heterocycle (pyrrole or thiophene): such a functionalisation may provide the final, tailored, conductive polymer with special properties (e.g., solubility). If the central ring, acting as a ''spacer'', is formed linking two positions of a di-heterocycle with a saturated chain, it is possible partially to control the twist angle between the heterocyclic units. Crystal and molecular structures have shown that dipyrrole units, further linked through the nitrogen atoms, are quite sensitive to the central ring size. With regard to the conductivity of unsubstituted polypyrrole, the conductivity of the polymers derived from such monomers is dependent upon the twist angle between the rings. This result is relevant to a description of conjugation conditions between the heterocyclic units of a monomer required to produce a conductive polymer on doping. (orig.).

  12. Impact of thiol and amine functionalization on photoluminescence properties of ZnO films

    International Nuclear Information System (INIS)

    Jayalakshmi, G.; Saravanan, K.; Balasubramanian, T.

    2013-01-01

    In the present study, we have investigated surface functionalization of ZnO films with dodecanethiol (Thiol) and trioctylamine (amine) by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), contact angle (CA) and photoluminescence (PL) measurements. The chemical bondings of thiol and amine with ZnO have been confirmed via the formation of Zn–S and Zn–N bonds by XPS measurements. AFM measurements on ZnO films before and after surface functionalization with thiol and amine provide evidence for the successful functionalization of thiol and amine on ZnO surfaces without any island formation. The CA measurements on ZnO films before and after surface functionalization with thiol and amine show the hydrophobic nature. PL measurements of thiol and amine functionalized ZnO show enhancements of UV emission and quenching of visible emission. The enhanced UV emissions in thiol and amine functionalized ZnO films suggest that the surface defects such as oxygen vacancies are passivated by thiol and amine functionalization. -- Highlights: ► Surface functionalization is a new approach to reduce surface dependent non-radiative process. ► Oxygen vacancies are passivated on surface functionalization. ► Thiol and amine functionalized ZnO show enhancements of UV emission

  13. The reactions of anthronylidene carbene with some heterocyclic compounds

    International Nuclear Information System (INIS)

    Divisia, Bernadette

    1970-01-01

    The action of the anthronylidene carbene, generated by photochemical decomposition of 9-diazo 10-anthron, on four heterocyclic compounds (furan, thiophene, 1-methyl-pyrrole and 2,5-dihydrofuran) has been examined. Two classical carbene reactions have been observed: the addition on double bond (furan, thiophene, 1-methylpyrrole) and hydrogen atom abstraction of the heterocyclic compound (2,5-dihydrofuran). In the case of furan and thiophene, the cyclo-propanic compound resulting from the addition is spontaneously transformed into an ethylenic derivative by valence isomerization. The furan derivative undergoes a cis-trans isomerization, while the thiophene one undergoes an extra carbene attack. In the case of 1-methylpyrrole, the corresponding cyclo-propanic compound undergoes a ring cleavage, followed by a hydrogen atom migration leading to the formation of a substituted anthron. Only an allylic hydrogen atom selective abstraction of heterocyclic compound takes place in the reaction of anthronylidene carbene with 2,5-dihydrofuran. The asymmetrical coupling of radicals so obtained yields the corresponding substituted anthron. (author) [fr

  14. Microwave Assisted Synthesis of Some New Heterocyclic Spiro-Derivatives with Potential Antimicrobial and Antioxidant Activity

    Directory of Open Access Journals (Sweden)

    Mohamed Mohamed Youssef

    2010-12-01

    Full Text Available Homophthalic anhydride reacts with different aromatic amines to produce N-substituted homophthalimides. Bromination of the latter produces 4,4-dibromo-homophthalimide derivatives that can be used as precursors for spiro-derivatives. The dibromo derivatives react with different binucleophilic reagents to produce several spiro-isoquinoline derivatives. Reaction of the dibromo derivatives with malononitrile produces dicyanomethylene derivatives which react with different binucleophiles to produce new spiro-derivatives. Structures of the newly synthesized compounds are proved using spectroscopic methods such as IR, 1H-NMR and 13C-NMR. The newly synthesized compounds were tested for their antimicrobial and antioxidant activities, showing weak or no antimicrobial activity. On the other hand select compounds showed promising antioxidant activities.

  15. Electron beam induced electronic transport in alkyl amine-intercalated VOx nanotubes

    International Nuclear Information System (INIS)

    O'Dwyer, C.; Lavayen, V.; Clavijo-Cedeno, C.; Torres, C.M.S.

    2008-01-01

    The electron beam induced electronic transport in primary alkyl amine-intercalated V 2 O 5 nanotubes is investigated where the organic amine molecules are employed as molecular conductive wires to an aminosilanized substrate surface and contacted to Au interdigitated electrode contacts. The results demonstrate that the high conductivity of the nanotubes is related to the non-resonant tunnelling through the amine molecules and a reduced polaron hopping conduction through the vanadium oxide itself. Both nanotube networks and individual nanotubes exhibit similarly high conductivities where the minority carrier transport is bias dependent and nanotube diameter invariant. (copyright 2008 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  16. Alkylselenite-catalyzed Oxidative Carbonylation of Amines: Density Functional Theory Study

    Energy Technology Data Exchange (ETDEWEB)

    Hwang, Sun; Kim, Hoon Sik; Cheong, Minserk [Kyung Hee Univ., Seoul (Korea, Republic of)

    2012-11-15

    Ureas and carbamates have been conventionally produced by the reaction of amines with phosgene. However, phosgenation processes raise severe environmental concerns, which are attributed to the toxicity of phosgene and the formation of corrosive hydrogen chloride as a co-product. The considerable industrial interest in replacing current phosgene-based processes prompted several methods using non-phosgene routes including carbonylation of amines or nitro compounds and carbomethoxylation of amines with dialkylcarbonates. Among these, catalytic oxidative carbonylation of an amine in the presence of alcohol has been studied most extensively. Catalytic systems based on precious metals such as Rh and Pd are commonly used for this purpose, but most of these catalytic systems suffer from either low reactivity or severe reaction conditions such as high temperature and pressures. In conclusion, the facile change of selenium oxidation state by CO and O{sub 2} might be the main reason for the activity of the selenium catalyst for this reaction.

  17. Alkylselenite-catalyzed Oxidative Carbonylation of Amines: Density Functional Theory Study

    International Nuclear Information System (INIS)

    Hwang, Sun; Kim, Hoon Sik; Cheong, Minserk

    2012-01-01

    Ureas and carbamates have been conventionally produced by the reaction of amines with phosgene. However, phosgenation processes raise severe environmental concerns, which are attributed to the toxicity of phosgene and the formation of corrosive hydrogen chloride as a co-product. The considerable industrial interest in replacing current phosgene-based processes prompted several methods using non-phosgene routes including carbonylation of amines or nitro compounds and carbomethoxylation of amines with dialkylcarbonates. Among these, catalytic oxidative carbonylation of an amine in the presence of alcohol has been studied most extensively. Catalytic systems based on precious metals such as Rh and Pd are commonly used for this purpose, but most of these catalytic systems suffer from either low reactivity or severe reaction conditions such as high temperature and pressures. In conclusion, the facile change of selenium oxidation state by CO and O 2 might be the main reason for the activity of the selenium catalyst for this reaction

  18. Exciplex fluorescence emission from simple organic intramolecular constructs in non-polar and highly polar media as model systems for DNA-assembled exciplex detectors.

    Science.gov (United States)

    Bichenkova, Elena V; Sardarian, Ali R; Wilton, Amanda N; Bonnet, Pascal; Bryce, Richard A; Douglas, Kenneth T

    2006-01-21

    Organic intramolecular exciplexes, N-(4-dimethylaminobenzyl)-N-(1-pyrenemethyl)amine (1) and N'-4-dimethylaminonaphthyl-N-(1-pyrenemethyl)amine (2), were used as model systems to reveal major factors affecting their exciplex fluorescence, and thus lay the basis for developing emissive target-assembled exciplexes for DNA-mounted systems in solution. These models with an aromatic pyrenyl hydrocarbon moiety as an electron acceptor appropriately connected to an aromatic dimethylamino electron donor component (N,N-dimethylaminophenyl or N,N-dimethylaminonaphthyl) showed strong intramolecular exciplex emission in both non-polar and highly polar solvents. The effect of dielectric constant on the maximum wavelength for exciplex emission was studied, and emission was observed for 1 and 2 over the full range of solvent from non-polar hydrocarbons up to N-methylformamide with a dielectric constant of 182. Quantum yields were determined for these intramolecular exciplexes in a range of solvents relative to that for Hoechst 33,258. Conformational analysis of 1 was performed both computationally and via qualitative 2D NMR using (1)H-NOESY experiments. The results obtained indicated the contribution of pre-folded conformation(s) to the ground state of 1 conducive to exciplex emission. This research provides the initial background for design of self-assembled, DNA-mounted exciplexes and underpins further development of exciplex-based hybridisation bioassays.

  19. Microwave-Assisted Multicomponent Synthesis of Heterocycles

    NARCIS (Netherlands)

    Kruithof, A.; Ruijter, E.; Orru, R.V.A.

    2011-01-01

    Multicomponent reactions are valuable tools for the generation of diverse heterocycles. As in many fields or organic chemistry, microwave irradiation is rapidly replacing conventional heating methods in multicomponent chemistry. In this review, we present an overview of recent applications of the

  20. On the synthesis of 11C-labelled aromatic amino acids

    International Nuclear Information System (INIS)

    Halldin, C.

    1984-01-01

    The use of 11 C-labelled aromatic amino acids in positron emission tomography (PET) and their importance in physiological studies, especially cerebral protein synthesis or their role as precursors of neurotransmitters, is discussed. The synthesis of 11 -C-labelled aromatic amino acids by various routes is presented and new 11 C-labelled precursors, aromatic and aliphatic 11 C-aldehydes, are reported. The 11 C-aldehydes were obtained in 60-95% radiochemical yield and reaction times were of the order of 5 min. The 11 C-aldehydes have been used in condensation reactions with 2-aryl-5-oxazolones in the presence of a tertiary amine, diazabicyclooctane (DABCO), to produce the corresponding [α- 11 C]-4-arylene-2-aryl-5-oxazolones. Ring opening, hydrogenation and removal of protecting groups were carried out in one step to produce the racemic [3- 11 C]-labelled aromatic amino acids in 8-30% radiochemical yield. The total reaction time was 52-60 min. L-[3- 11 C]Phenylalanine was obtained by a seven-step synthesis in 80% e.e. (enantiomeric excess) and 60% e.e., respectively, in 10-15% radiochemical yield within 60 min, by use of the chiral rhodium complex of (R)-1,2-bis(diphenylphosphino)propane ((R)-PROPHOS) or (+)-2,3-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane ((+)-DIOP) in the hydrogenation reaction. Racemic [2- 11 C]-labelled aromatic amino acids were produced by a high-pressure, high-temperature modification of the Buechere-Strecker synthesis. [2- 11 C]Phenylglycine was obtained in 20% radiochemical yield within 50 min. [3- 11 C]Phenylpyruvic acid was prepared via the aldehyde-oxyzolone condensation reaction in 40% radiochemical yield within 40 min (not including LC separation). Its use in the synthesis of [3- 11 C]-phenylalanine by enzymatic transamination is also discussed. With 32 refs.(Author)

  1. Evaluation of Biogenic Amines in Organic and Non-Organic Wines by HPLC OPA Derivatization

    Directory of Open Access Journals (Sweden)

    Ali Üren

    2007-01-01

    Full Text Available Organic and non-organic wines, selected on the basis of consumers’ preference towards healthy products, were produced from the grapes of Vitis vinifera varieties Semillon, Colombard, Cabernet Sauvignon, Merlot and Carignan and possible effects of different wine making techniques were considered. Concentrations of histamine, tyramine, putrescine, cadaverine, ethylamine, methylamine, tryptamine, agmatine and β-phenylethylamine were quantified by HPLC fluorescence detection of o-phthaldialdehyde (OPA derivatives. The order of analyzed parameters in all wines from the highest to the lowest quantities was determined as follows: putrescine > histamine > ethylamine > methylamine > agmatine > tyramine > cadaverine > tryptamine. One of the analyzed compounds (β-phenylethylamine was not detected. The highest average values for organic and non-organic wines were found as follows (in mg/L: putrescine 5.55, ethylamine 0.825 and histamine 0.628 in organic wines, and putrescine 3.68, histamine 1.14 and agmatine 0.662 in non-organic wines. Considering the wine type (organic/non-organic, an important difference was determined for putrescine. Putrescine content in organic wines was significantly greater than in non-organic ones (p=0.008. Evaluating colour of wines (white/red, a statistically significant difference was obtained for methylamine (p=0.028. Taking into account only grape varieties, statistically significant differences were found for histamine, methylamine, tyramine and cadaverine (p<0.05. The results of principal component analysis demonstrated close relations between the following biogenic amines and wines: agmatine and non-organic Colombard; tryptamine or cadaverine and both organic and non-organic Cabernet Sauvignon wines.

  2. The economics of amine usage

    International Nuclear Information System (INIS)

    Fountain, M.J.

    1994-01-01

    The EPRI computer programm, 'Aminemod', a PWR chemistry model, has been used to compare the technical advantages of the 'advanced' amines, ethanolamine, 1,2 diaminoethane and 5 aminopentanol over morpholine in generating an elevated pH in the moisture separator and the economics of using these amines has been assessed by using an MS Excel spreadsheet in conjunction with Aminemod. The advanced amines are capable of achieving 1 pH unit above neutrality, the EPRI target for prevention of erosion-corrison, at acceptable cost and, compared with 'conventional' amines, at considerably reduced ionic load on the condensate polisher. The exercise demonstrates that it is essential to evaluate the effect of an amine dosing regime on the total operating cost and that it is not possible to prejudge the economic outcome on the basis of an amine's purchase price. (orig.)

  3. Transition-Metal-Controlled Inorganic Ligand-Supported Non-Precious Metal Catalysts for the Aerobic Oxidation of Amines to Imines.

    Science.gov (United States)

    Yu, Han; Zhai, Yongyan; Dai, Guoyong; Ru, Shi; Han, Sheng; Wei, Yongge

    2017-10-09

    Most state-of-art transition-metal catalysts usually require organic ligands, which are essential for controlling the reactivity and selectivity of reactions catalyzed by transition metals. However, organic ligands often suffer from severe problems including cost, toxicity, air/moisture sensitivity, and being commercially unavailable. Herein, we show a simple, mild, and efficient aerobic oxidation procedure of amines using inorganic ligand-supported non-precious metal catalysts 1, (NH 4 ) n [MMo 6 O 18 (OH) 6 ] (M=Cu 2+ ; Fe 3+ ; Co 3+ ; Ni 2+ ; Zn 2+ , n=3 or 4), synthesized by a simple one-step method in water at 100 °C, demonstrating that the catalytic activity and selectivity can be significantly improved by changing the central metal atom. In the presence of these catalysts, the catalytic oxidation of primary and secondary amines, as well as the coupling of alcohols and amines, can smoothly proceed to afford various imines with O 2 (1 atm) as the sole oxidant. In particular, the catalysts 1 have transition-metal ion core, and the planar arrangement of the six Mo VI centers at their highest oxidation states around the central heterometal can greatly enhance the Lewis acidity of catalytically active sites, and also enable the electrons in the center to delocalize onto the six edge-sharing MO 6 units, in the same way as ligands in traditional organometallic complexes. The versatility of this methodology maybe opens a path to catalytic oxidation through inorganic ligand-coordinated metal catalysis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Synthesis of heterocycles through transition-metal-catalyzed isomerization reactions

    DEFF Research Database (Denmark)

    Ishøy, Mette; Nielsen, Thomas Eiland

    2014-01-01

    of structurally complex and diverse heterocycles. In this Concept article, we attempt to cover this area of research through a selection of recent versatile examples. A sea of opportunities! Transition-metal-catalyzed isomerization of N- and O-allylic compounds provides a mild, selective and synthetically...... versatile method to form iminium and oxocarbenium ions. Given the number of reactions involving these highly electrophilic intermediates, this concept provides a sea of opportunities for heterocycle synthesis, (see scheme; Nu=nucleophile). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim....

  5. Structural Influence on Excited State Dynamics in Simple Amines

    DEFF Research Database (Denmark)

    Klein, Liv Bærenholdt

    experiments with calculations, provides new insight into the nature of the internal conversion processes that mediate the dynamical evolution between Rydberg states, and how structural variations in simple amine system have a large impact on the non-adiabatic processes. The experimental method of choice...... is femtosecond time-resolved photoelectron velocity map imaging (VMI), which is a newtechnique in the Copenhagen lab. The design, building and implementation of the VMI spectrometer has been a very substantial part of the thesis work. This techniques oers enhanced information content in the form of ecient...... and sensitive collection of photoelectron spectra. In particular, the angleresolved data available from the VMI approach provides highly detailed mechanistic insight about the relaxation pathways. One striking novel nding is that for tertiary amines, the critical factor driving the non-adiabatic dynamics...

  6. Conformation-Induced Remote meta-C–H Activation of Amines

    Science.gov (United States)

    Tang, Ri-Yuan; Li, Gang; Yu, Jin-Quan

    2014-01-01

    Achieving site selectivity in C–H functionalization is a long-standing challenge in organic synthesis. The small differences in intrinsic reactivity of C–H bonds in a given organic molecule often lead to poor discrimination by a catalyst. One solution to this problem is to distinguish C–H bonds based on their location with respect to a particular functional group. In this context, the activation of C–H bonds 5 or 6 bonds away from a functional group via cyclometalation has been extensively studied.1-13 However, directed activation of C–H bonds that are distal (>6 bonds away) from functional groups has remained difficult, especially when the target C–H bonds are geometrically inaccessible through directed metalation due to the ring strain encountered in cyclometalation.14,15 Herein we report a recyclable template that directs the olefination and acetoxyation of distal meta-C–H bonds (as far as 11 bonds away) of anilines and benzylic amines. Remarkably, this template is able to direct the meta-selective C–H functionalization of bicyclic heterocycles via highly strained tricyclic cyclophane-like palladated intermediates. X-ray and NMR studies reveal that the conformational biases induced by a single fluorine substitution in the template can be enhanced by a ligand to switch from ortho- to meta-selectivity. PMID:24622200

  7. Amine Measurements in Boreal Forest Air

    Science.gov (United States)

    Hemmilä, Marja; Hellén, Heidi; Makkonen, Ulla; Hakola, Hannele

    2015-04-01

    Amines are reactive, volatile bases in the air with a general formula of RNH2, R2NH or R3N. Especially small amines can stabilize sulphuric acid clusters and hence affect nucleation. Amines react rapidly with hydroxyl radical (OH˙) thus affecting oxidative capacity of the atmosphere. The amine concentrations are higher in forest air than in urban air (Hellén et al., 2014), but the sources are not known. In order to get more information concerning amine sources, we conducted a measurement campaign in a boreal forest. At SMEAR II station at Hyytiälä, Southern Finland (61°510'N, 24°170'E, 180 m a.s.l.) The measurements cover seven months, from June to December 2014. For sampling and measuring we used MARGA (The instrument for Measuring AeRosols and Gases in Ambient air) which is an on-line ion chromatograph (IC) connected to a sampling system. The IC component of the MARGA system was coupled to an electrospray ionization quadrupole mass spectrometer (MS) to improve sensitivity of amine measurements. This new set-up enabled amine concentration measurements in ambient air both in aerosol and gas phases with a time resolution of only 1 hour. With MARGA-MS we analysed 7 different amines: monomethylamine (MMA), dimethylamine (DMA), trimethylamine (TMA), ethylamine (EA), diethylamine (DEA), propylamine (PA) and butylamine (BA). In preliminary data-analysis we found out, that in June and July most of the measured amines were in gas phase, and particle phase amine concentrations were mostly under detection limits (<1.7 pptv). In June the gaseous amine concentrations were higher than in July. The measured concentrations of gaseous amines followed temperature variation, which could indicate that amines are produced and emitted from the environment or re-emitted from the surfaces as temperature rises after deposition during night-time. All measured amines had similar diurnal variation with maxima during afternoon and minima during night. Results from other months will also

  8. Multicomponent reactions: A simple and efficient route to heterocyclic phosphonates

    Science.gov (United States)

    2016-01-01

    Summary Multicomponent reactions (MCRs) are one of the most important processes for the preparation of highly functionalized organic compounds in modern synthetic chemistry. As shown in this review, they play an important role in organophosphorus chemistry where phosphorus reagents are used as substrates for the synthesis of a wide range of phosphorylated heterocycles. In this article, an overview about multicomponent reactions used for the synthesis of heterocyclic compounds bearing a phosphonate group on the ring is given. PMID:27559377

  9. Some regularities in formation and solvent extraction of complexes in metal-salicylic acid or its derivative- organic base systems

    International Nuclear Information System (INIS)

    Alimarin, I.P.; Fadeeva, V.I.; Tikhomirova, T.I.

    1982-01-01

    The influence of concentrations of the reagents, pH and solvent on the conditions for the formation and extraction of Sc, Ti, Zr, Hf, Th complexes has been examined in salicylic acid (H 2 Sal)-heterocyclic amine systems. The extraction chemism and factors, which affect the reactions between the metal ions and the ligands, are discussed. It has been shown that Zr, Hf, Ti form species of ion associate type, Sc and Th form different-ligand complexes under conditions for interphase equilibrium in a Me-H 2 Sal-heterocyclic amine system

  10. Di-n-butyl 4,4′-dihydroxy-3,3′-{[(3aRS,7aRS-2,3,3a,4,5,6,7,7a-octahydro-1H-1,3-benzimidazole-1,3-diyl]bis(methylene}dibenzoate

    Directory of Open Access Journals (Sweden)

    Augusto Rivera

    2011-09-01

    Full Text Available The complete molecule of the title compound, C31H42N2O6, is generated by crystallographic twofold symmetry, with one C atom lying on the axis. The dihedral angle between the aromatic rings is 57.03 (6°. The central heterocyclic ring adopts a half-chair conformation. The molecular conformation is stabilized by two intramolecular O—H...N hydrogen bonds with the N atoms of the heterocyclic ring as the acceptors. In the crystal, molecules are linked into chains along the c axis by non-classical C—H...O hydrogen bonds.

  11. The Azomethine Ylide Route to Amine C–H Functionalization: Redox-Versions of Classic Reactions and a Pathway to New Transformations

    Science.gov (United States)

    2016-01-01

    processes, have been identified as common intermediates. Extension of this chemistry to amine α,β-difunctionalization has been shown to be possible by way of converting the intermediate azomethine ylides into transient enamines. This Account details the evolution of this general strategy and the progress made to date. Further included is a discussion of related decarboxylative reactions and transformations that result in the redox-neutral aromatization of (partially) saturated cyclic amines. These processes also involve azomethine ylides, reactive intermediates that appear to be far more prevalent in condensation chemistry of amines and carbonyl compounds than previously considered. In contrast, as exemplified by some redox transformations that have been studied in greater detail, iminium ions are not necessarily involved in all amine/aldehyde condensation reactions. PMID:25560649

  12. The azomethine ylide route to amine C-H functionalization: redox-versions of classic reactions and a pathway to new transformations.

    Science.gov (United States)

    Seidel, Daniel

    2015-02-17

    identified as common intermediates. Extension of this chemistry to amine α,β-difunctionalization has been shown to be possible by way of converting the intermediate azomethine ylides into transient enamines. This Account details the evolution of this general strategy and the progress made to date. Further included is a discussion of related decarboxylative reactions and transformations that result in the redox-neutral aromatization of (partially) saturated cyclic amines. These processes also involve azomethine ylides, reactive intermediates that appear to be far more prevalent in condensation chemistry of amines and carbonyl compounds than previously considered. In contrast, as exemplified by some redox transformations that have been studied in greater detail, iminium ions are not necessarily involved in all amine/aldehyde condensation reactions.

  13. New Palladium-Catalyzed Approaches to Heterocycles and Carbocycles

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Qinhua [Iowa State Univ., Ames, IA (United States)

    2004-12-19

    The tert-butylimines of o-(1-alkynyl)benzaldehydes and analogous pyridinecarbaldehydes have been cyclized under very mild reaction conditions in the presence of I2, ICl, PhSeCl, PhSCl and p-O2NC6H4SCl to give the corresponding halogen-, selenium- and sulfur-containing disubstituted isoquinolines and naphthyridines, respectively. Monosubstituted isoquinolines and naphthyridines have been synthesized by the metal-catalyzed ring closure of these same iminoalkynes. This methodology accommodates a variety of iminoalkynes and affords the anticipated heterocycles in moderate to excellent yields. The Pd(II)-catalyzed cyclization of 2-(1-alkynyl)arylaldimines in the presence of various alkenes provides an efficient way to synthesize a variety of 4-(1-alkenyl)-3-arylisoquinolines in moderate to excellent yields. The introduction of an ortho-methoxy group on the arylaldimine promotes the Pd-catalyzed cyclization and stabilizes the resulting Pd(II) intermediate, improving the yields of the isoquinoline products. Highly substituted naphthalenes have been synthesized by the palladium-catalyzed annulation of a variety of internal alkynes, in which two new carbon-carbon bonds are formed in a single step under relatively mild reaction conditions. This method has also been used to synthesize carbazoles, although a higher reaction temperature is necessary. The process involves arylpalladation of the alkyne, followed by intramolecular Heck olefination and double bond isomerization. This method accommodates a variety of functional groups and affords the anticipated highly substituted naphthalenes and carbazoles in good to excellent yields. Novel palladium migratiodarylation methodology for the synthesis of complex fused polycycles has been developed, in which one or more sequential Pd-catalyzed intramolecular migration processes involving C-H activation are employed. The chemistry works best with electron-rich aromatics, which is in agreement

  14. An exploration on the synthesis and bio-applications of derivatives ...

    African Journals Online (AJOL)

    Keeping in view of the importance of this organic moiety in the field of medicine and biology here an attempt has been made to review the synthesis and biological importance of heterocyclic Mannich base derivatives. Keywords: Amines, β-amino carbonyl compounds, Biological activity, Heterocyclic Mannich base derivative ...

  15. Absolute fragmentation cross sections in atom-molecule collisions : Scaling laws for non-statistical fragmentation of polycyclic aromatic hydrocarbon molecules

    NARCIS (Netherlands)

    Chen, T.; Gatchell, M.; Stockett, M. H.; Alexander, J. D.; Zhang, Y.; Rousseau, P.; Domaracka, A.; Maclot, S.; Delaunay, R.; Adoui, L.; Huber, B. A.; Schlathölter, T.; Schmidt, H. T.; Cederquist, H.; Zettergren, H.

    2014-01-01

    We present scaling laws for absolute cross sections for non-statistical fragmentation in collisions between Polycyclic Aromatic Hydrocarbons (PAH/PAH+) and hydrogen or helium atoms with kinetic energies ranging from 50 eV to 10 keV. Further, we calculate the total fragmentation cross sections

  16. Tuning the acid/base properties of nanocarbons by functionalization via amination.

    Science.gov (United States)

    Arrigo, Rosa; Hävecker, Michael; Wrabetz, Sabine; Blume, Raoul; Lerch, Martin; McGregor, James; Parrott, Edward P J; Zeitler, J Axel; Gladden, Lynn F; Knop-Gericke, Axel; Schlögl, Robert; Su, Dang Sheng

    2010-07-21

    The surface chemical properties and the electronic properties of vapor grown carbon nanofibers (VGCNFs) have been modified by treatment of the oxidized CNFs with NH(3). The effect of treatment temperature on the types of nitrogen functionalities introduced was evaluated by synchrotron based X-ray photoelectron spectroscopy (XPS), while the impact of the preparation methods on the surface acid-base properties was investigated by potentiometric titration, microcalorimetry, and zeta potential measurements. The impact of the N-functionalization on the electronic properties was measured by THz-Time Domain spectroscopy. The samples functionalized via amination are characterized by the coexistence of acidic and basic O and N sites. The population of O and N species is temperature dependent. In particular, at 873 K nitrogen is stabilized in substitutional positions within the graphitic structure, as heterocyclic-like moieties. The surface presents heterogeneously distributed and energetically different basic sites. A small amount of strong basic sites gives rise to a differential heat of CO(2) adsorption of 150 kJ mol(-1). However, when functionalization is carried out at 473 K, nitrogen moieties with basic character are introduced and the maximum heat of adsorption is significantly lower, at approximately 90 kJ mol(-1). In the latter sample, energetically different basic sites coexist with acidic oxygen groups introduced during the oxidative step. Under these conditions, a bifunctional acidic and basic surface is obtained with high hydrophilic character. N-functionalization carried out at higher temperature changes the electronic properties of the CNFs as evaluated by THz-TDS. The functionalization procedure presented in this work allows high versatility and flexibility in tailoring the surface chemistry of nanocarbon material to specific needs. This work shows the potential of the N-containing nanocarbon materials obtained via amination in catalysis as well as electronic

  17. Synthesis and Cyclopolymerzation of N-Aryl Di ‎AllylAmins As Antioxidants for Lubricant's Oil

    Directory of Open Access Journals (Sweden)

    Firyal M. Ali ‎

    2017-12-01

    Full Text Available In this research many new N-aryl substituted di allylAmins were  synthesized [ A1-A2 ] which were Polymerized by free radically mechanism by using Ammonium per sulfate  as an initiator at 700C .The new hindered   amines   as  cyclo  polymers  were  characterized  by FTIR  and  H-NMR Spectroscopies ,Physical   and   chemical properties were measured  using TGA and DSC to   study   the thermal stability  of   prepared  cyclopolymers  . These   prepared  N-aromatic  substituted di allylamins cyclopolymers [ A3 - A4 ]  were  used  as  antioxidants  for  lubricant  oil  .   which   give    high stability   when  comparing  with standard  antioxidant . The oxidation stability of base  oil with (1% additive  were  examined according to Institute of Petroleum testing method IP280 

  18. Synthesis and Cyclopolymerzation of N-Aryl Di ‎AllylAmins As Antioxidants for Lubricant's Oil

    Directory of Open Access Journals (Sweden)

    Firyal M. Ali ‎

    2017-12-01

    Full Text Available In this research many new N-aryl substituted di allylAmins were  synthesized [ A1-A2 ] which were Polymerized by free radically mechanism by using Ammonium per sulfate  as an initiator at 700C .The new hindered   amines   as  cyclo  polymers  were  characterized  by FTIR  and  H-NMR Spectroscopies ,Physical   and   chemical properties were measured  using TGA and DSC to   study   the thermal stability  of   prepared  cyclopolymers  . These   prepared  N-aromatic  substituted di allylamins cyclopolymers [ A3 - A4 ]  were  used  as  antioxidants  for  lubricant  oil  .   which   give    high stability   when  comparing  with standard  antioxidant . The oxidation stability of base  oil with (1% additive  were  examined according to Institute of Petroleum testing method IP280

  19. Antiradiation compounds XV: condensations of carbon disulfide with amino, chloro, cyanomethyl, and sulfonamido heterocycles

    International Nuclear Information System (INIS)

    Foye, W.O.; Kauffman, J.M.; Lanzillo, J.J.; LaSala, E.F.

    1975-01-01

    Condensations of carbon disulfide were carried out with amino, chloro, and diamino heterocycles to give condensed ring thiazoline-2-thiones and imidazoline-2-thiones, with cyanomethyl heterocycles to give dithio acid derivatives, and with heterocyclic sulfonamides to give sulfonyldithiocarbamates. Of several examples tested, pyrido[3,2-d]thiazoline-2-thione, disodium 2-(5-chloro-2-thienyl)-3,3-dimercaptoacrylonitrile, triethylammonium 4-sulfamoylphenyldithiocarbamate, ammonium β-phenethyldithiocarbamate, and methyl N-(thiophene-2-sulfonyl)dithiocarbamate, only the last-named compound showed any radiation protection for mice. Several compounds gave negative tests for antimalarial activity

  20. New heterocyclic compounds from Ranunculus ternatus Thunb.

    Science.gov (United States)

    Feng, Zi-Ming; Zhan, Zhi-Lai; Yang, Ya-Nan; Jiang, Jian-Shuang; Zhang, Pei-Cheng

    2017-10-01

    Five new heterocyclic compounds, 5-α-d-fructofuranosylmethyl-furfural (1), 5-β-d-fructofuranosylmethyl-furfural (2), 5-β-d-fructopyranosylmethyl-furfural (3), 4-(2-((2S-2,3-dihydroxypropoxy)methyl)-5-formyl-1H-pyrrol-1-yl)butanoic acid (4), and 3S,4S-4,5,8-trihydroxy-3-(prop-1-en-2-yl)isochroman-1-one (5), were obtained from the root of Ranunculus ternatus Thunb., which is a traditional Chinese anti-tuberculosis medicine. Their structures were elucidated by UV, IR, HRESIMS, NMR data, and the comparison of experimental and calculated electronic circular dichroism (ECD) spectra. Notably, compounds 1-3 are rarely occurring furfural fructosides in natural sources. These heterocyclic compounds could be further studied for the synthetic chemists and pharmacologists due to the source and structural properties. Copyright © 2017 Elsevier Inc. All rights reserved.